Hu F19 Me431 All

ME 431– Introduction to Engineering Materials
IDEE – Interdisciplinary Engineering Elective

Fall 2019
Lecture 1
Introduction to the Course
Ali Zahid
Tuesday 27th August 2019 @ 10 00
Rationale | Aims | Objectives | Format
The current electronics industry is focused on miniaturization of electronic devices. This is possible through understanding the correlation between properties desired in
electronics and their acquisition through relevant concepts in Materials Science, focusing on crystal structures, semiconductor physics, charge carrier generation &
Rationale
transport, appropriate material selection and fabrication methodologies for electronic devices. A large emphasis in this course would be placed on acquiring concepts and
skills for selecting the optimal material, through relevant acceptable compromises and considering the underlying physical principles, for miniaturized electronics.
This course will cover the fundamental aspects of Materials Science with a focus on understanding the physics related to the functioning and development of electronics.
The course content is divided into three parts:
Aims i. Fundamentals of Materials Sciences relevant to electronics
ii. Materials Processing
iii. Materials Selection and Application
• Understanding different classes of materials and their properties relevant for electronic applications.
• Understanding the band structure of solids.
Objectives • Understand the principles behind selecting the appropriate materials for a specific electronic device.
• Gaining an appreciation and principles of charge transportation in electronic materials.
• Recognizing the tools in Materials Science that are required to characterize electronic materials.
• Lectures
• Quizzes
Format • Assignments
• Midterms
• Final
Offering Offered for the 2nd time [1st offered in Fall 2018]
Required Text
William D. Callister Jr – Fundamentals of Materials Science and Engineering - John Wiley & Sons Inc - 5th Edition
Recommended Texts
S.M.Sze - Physics of Semiconductor Devices – John Wiley & Sons, Inc
Reading Material provided each week

References:
Course Content | CLOs | Assessments
Course Content Course Learning Outcomes

Week
Topics CLO Description Domain
Introduction to the course Identify the nature of bonding in materials (primary and
1 secondary bonding) and classify materials based on their atomic Cog – 1
CLO 1
Bonding in Solids I structure, bonding and functionalities.
2
Describe the relevant quantum mechanical properties of solids
Bonding in Solids II CLO 2 and electron – solid interactions. Have an understanding on the Cog – 2
3
origin of energy bands in solids.
4 Structure of Crystalline Materials I Apply the concepts of electron excitation events that produce free
electrons / holes in metals, semiconductors (intrinsic and C og – 3
CLO 3
5 Structure of Crystalline Materials II extrinsic) and insulators.
Outline the basic thermodynamics of materials to understand
6 Solid State Principles and Thermostatistics I material stability through comprehending the energies of solid Cog – 4
CLO 4
formation, interface formation and the principle of energy
7 Solid State Principles and Thermostatistics II minimization
Explain the relevant concepts behind material selection of
8 Band Theory relevant electronic devices (p-n diodes, light emitting diodes,
CLO 5 Cog – 4
solar cells, MOFSETs, printed circuit boards and thermal
9 Semiconductivity I management materials) based on their operating characteristics.
10 Semiconductivity II Items Weights (%) How many?
11 Device Fabrication Technology I | Materials Processing Assignments 18 3
12 Device Fabrication Technology II | Materials Processing Quiz / Tests 18 3

Assessments
Device Fabrication Technology III | Materials Processing Mid Term 28 1
13
14 Device Fabrication Technology IV | Materials Processing End Term 36 1
References:
The Journey of an Atom
* Atoms smallest building block

* Atoms of an element are similar
* Compounds have a combination of atoms
X Atoms are not indivisible

* Discovered electrons – Noble Prize
* Electrons scattered through spherical cloud of positive charges
X No Nucleus – experimentally debunked
* Experimental verification of nucleus

* Realization – positive charge in the center of the atom
X Why electrons orbit the nucleus?

X Moving electrons should fall in the nucleus * Electrons orbit the nucleus
* Electron orbits are quantized
* Start of Quantum Physics
X Heisenberg’s Uncertainty Principle
* Wave – Particle Duality

* Introduction of probability
* Electrons move around in clouds
* Orbitals – Clouds of Probability
Still the widely accepted model • Age of Particle Accelerator

• 1980 - Present
References:
What Shall We Do ?
Assemblies We can touch

[many clusters]
[microstructures]
Clusters
[lattice formation]
Molecules | Bond Formation

[few atoms]
Atomic
[individual atoms]
Emergent Collective Properties

Sub – atomic
[electrons | protons | neutrons] Magnetic | Electronic | Optical | Physical
Femto [10-15] | Pico [10-12] Nano [10-9] Micro [10-6] | Milli [10-3] Macro [100]
Modification of Material Properties

*References:
Length scale in meters * The Kochmann Research Group – Mechanics and Materials – ETH Zϋrich - Switzerland
What happens in Materials Science?
The Scientific Principle:

Model – Experiment - Accept
References:
Material Structure Determination – An example from XRD
Generation Filtration Collimation Directed
Detection
X-rays Monochromatic Concentrate Sample – X-ray
Scintillators
CRT X-rays X-rays interaction
‘ Scattering - waves or particles are forced to deviate from a straight trajectory because of scattering centers in the propagation medium’
References:
Habib University
Fall 2019 | ME 431 | Introduction to Engineering Materials
Introduction to Fall 2019 | ME 431 | Introduction to Engineering Materials
Lecture 2 | White-board Lecture
Thursday 29th August 2019
• Atomic Properties
Properties of a single atom | 2 atoms | a cluster of atoms | lattices. Existence and balancing of attractive and repulsive
forces between atoms
• Solid State Physics

Rudimentary concepts on electronic energy levels of a single atom | 2 atoms | group of atoms
• Quantum mechanical model of an electron

probability of an electron spending most of its time at the discrete shells | orbitals
• Material Classification
metals | polymers (organic) | ceramics | glass
• Material Properties
Electrical conductivity in materials | localized & de-localized electrons
Grains | grain boundaries | orientational differences between lattice arrangements.
Existence of a long-range order in crystalline materials and a short-range order in amorphous materials.
Observation of the microstructure of crystalline materials (metals | ceramics) under a light microscope.
The concept of fracture | rupture in polycrystalline materials and single crystals | stress concentration areas | initiation
of crack formation and propagation at the grain boundaries.
• Material Thermodynamics
Gibbs Free Energy as an indication of material stability.
Higher energy of a surface of a material than the bulk of the material
• Material Characterization
Applications of Scanning Electron Microscopy | Transmission Electron Microscopy to characterize material structure.
CLO 1 | CLO 2 | CLO 3 | CLO 4 | CLO 5

Summarization of the course content | concepts to be covered in later lectures
Fall 2019
Lecture 3
Introduction to Quantum Mechanics | I
Ali Zahid
Tuesday 3rd September 2019 @ 10 00

Agenda
- The Band Theory of Solids | brief introduction | white board lecture
- The ‘apparent’ continuity of Bands | plethora of electron energy states | white board lecture
- Formation of a Band | orbital overlap | white board lecture
- Localized & delocalized electrons | Silicon atoms | conduction | white board lecture
- The ‘Deterministic’ and ‘Probabilistic’ nature of Newtonian & Quantum Physics | white board lecture
- Excitation and Relaxation Processes in atoms | emission of photons | white board lecture
- The Particle Zoo | Standard Model of Particles
- What is Quantum Mechanics? | historical rant
- The Photoelectric Effect | Wave Particle Duality | introduction
Topics for next lecture

- Wave Particle Duality | The Double Slit Experiment
- The Copenhagen Interpretation of Quantum Mechanics
- Rudimentary Concept of a Photon | particles of light
Things I will ask with a 100% probability !
References:
The Particle Zoo – Standard Model of Particles
Matter Forces
Particles
- Standard Model
Fermions Bosons
Photons W/Z Bosons Gluons
Leptons
Quarks
Electrons Weak Nuclear
EM Force
Tau Force
Protons Strong Nuclear
Muon Material interaction with light
Optical Microscope Force
Neutrons Neutrinos Semiconductors
LED
Fermions – electrons, neutrons, protons

Fermi Dirac Statistics
Understanding of material properties Gravity Gravitons
CERN still smashing particles at high energy to discover
References:
‘ Bring forth what is true; Write it so it’s clear. Defend it to your last breath.’
What is Quantum Mechanics ? – a brief historical rant | birth of discretization - Faust | Goethe
Like everything in modern physics, it all started with Ludwig Boltzmann

- used statistical mechanics to explain the ‘collective behavior of atoms’ | atomistic explanation for this universe
- is acclaimed to lay down the foundations of a Quantum Mechanics | the Kinetic Theory of Gas model (taken for granted these days)
- proposed | in 1877 | ‘energy levels of a physical system could be discrete | not continuous’ | discrete energy levels
validated 20 years later | 1900 | Max Planck | Planck’s Law

Einstein | 1905 | the photoelectric effect | energy quanta concept
‘According to the assumption to be contemplated here, when a light ray is spreading from a point, the energy is not distributed continuously over ever-
increasing spaces, but consists of a finite number of 'energy quanta' that are localized in points in space, move without dividing, and can be absorbed or
generated only as a whole.’
- Einstein | On a heuristic viewpoint concerning the emission and transformation of light
- emission of electrons or other free carriers when light hits a material
- electron removed | photoelectron
electron goes to CB | free to move around
Any energy of photon would induce an electron to eject?

- NO!
- energies equal to or higher than the required energy
Basic postulate of QP | Discretization of energy

- electrons orbit the nucleus in orbitals that have fixed energies – not high not low – fixed discrete energies
- 1913 | ‘On the Constitution of Atom and Molecules’ | Niels Bohr | spectral lines in Hydrogen
Wave Particle Duality
- 1923 | Louis de Broglie | particles can behave as waves
- Heisenberg, Born, Schrodinger | wave mechanics | matrix mechanics
- Heisenberg | 1927 | Uncertainty Principle
- Feynman | Quantum Electrodynamics
* QP – Quantum Physics | ** Wikipeda | *** Boltzmann’s Atom: The Great Debate that Launched a Revolution in Physics
References:
Band Theory of Solids | Brief Introduction – white board lecture
References:
Fall 2019
Lecture 4
Introduction to Quantum Mechanics | II
Ali Zahid
Thursday 5th September 2019 @ 10 00

Agenda
- Wave Particle Duality | The Double Slit Experiment
- electron excitation | electron relaxation
- The 5th Solvay Conference | 1927
- What happened to the electron? | Bohr’s Determinism | Schrödinger's Probability

- when to consider the electron as a particle | wave
- when to use Bohr’s | Schrodinger’s model || bonding | ‘nature’
- Concepts explained on the white board

- the ‘non-intuitive’ nature of quantum mechanics
- electron gun | producing electrons using the photelectric effect | filaments
- quantization principle
- ‘act of observation’ | collapse of the wavefunction | effects on experiments at the quantum scale | ‘observe oriented’
- electron perturbation | balancing of repulsive + attractive forces | atoms coming together in a solid
- energy level splitting
- the wave | particle nature of light
- Schrödinger’s Cat | thought experiment | cat alive or dead depends on the act of observation
References:
Wave Particle Duality – The Double Slit Experiment
Demonstration of the wave nature of matter | probabilistic nature of quantum mechanics
‘…all of quantum mechanics can be gleaned from carefully thinking through the implications of this single experiment..’
- Feynman
- every information about the particle is encoded in a function that describes its ‘wave-like character’ | wavefunction ψ
- the particle (electron) has BOTH a wave + particle nature | important to deduce
constructive | destructive interference

- classical | Newtonian Mechanics prediction - but experiments disagree!!
- group particles allowed through 2 slits
- our own intuition - expectation | particles will only register at only 2 places on the screen
- particles = electrons | protons | molecules
- particles will go through the slit in a straight line - reality | interference pattern emerges!
- just like what you would get for waves!
‘It seems as though we must use sometimes the one theory and sometimes the other, while at times we may use either. We are faced with a new kind of difficulty. We have two
contradictory pictures of reality; separately neither of them fully explains the phenomena of light, but together they do’ -Einstein
What properties do wave exhibit?

- reflection | refraction | diffraction
-‘quantum particles’
- exhibit these properties too!
References:
The 5th Solvay Conference | 1927 – the best Science had to offer | at that time!
“…each sleepless night, Bohr would worry and fume and ruminate about Einstein's attack, and then he would respond the next day with a keen rebuttal, showing where Einstein has
missed something, and salvage Heisenberg's principle. This debate went on for days at that Solvay conference and continued on 3 years later at the next conference…“
- Jonathan P. Dowling | Schrödinger's Killer App
- lead to the Copenhagen Interpretation of Quantum Mechanics | set of mathematical formalisms to follow
- determinism | continuity (replaced) | uncertainty | probability | discontinuity (now we have this, for better or for worse!)
References:
What happened to the electron? – Bohr’s Determinism | Schrödinger's Probability
Since we are concerned with how electrons move in solids | electron-phonon interaction
- Bohr’s Deterministic Model of the Atom
- Schrodinger’s Probabilistic Model of the Atom
Bohr’s deterministic model of the atom

- nucleus in the center Collective atoms Isolated atom
- energy level splitting - allowed distinct energy levels
- electrons orbits the nucleus in discrete energy levels
- allowed electron energies associated with energy levels or states.
- Electron considered as a Particle
Schrodinger’s probabilistic model of the atom
- probability of finding an electron at the nucleus = Zero [0]
- probability of finding an electron at the furthest shell = maximum
- ‘electron density clouds’
- Electron considered as a Waves | associated with a wavefunction
For bonding in solids For understanding the ‘nature’ of electrons
- Bohr’s Atomic Model is sufficient - Quantum Mechanical Model
- electrons as particles | quantized energies | quantized shells + orbitals - electrons as ‘density clouds’
* William D. Callister Jr & David G. Rethwisch | Fundamentals of Materials Science and Engineering | An Integrated Approach
References:
Concepts - whiteboard
References:
I do draw waves quite nicely!

I must practice how to draw a cat apparently!!
References:
Fall 2019
Lecture 5
Materials Science for Electrical & Computer Engineers | a reminder
Ali Zahid

Agenda
- Reminder | structure of matter at different length scales | examples from electronics
- transistors
- metal oxide semiconductor field effect transistors
- control of spatial charge carriers’ movement | control of number of charge carriers
- Concepts covered on the whiteboard

- sputtering | bombardment through ions
- MOSFETS | how to make them
- layer by layer deposition | control
- ion implantation for doping
- Physical Vapor Deposition | PVD
'To see the world in a grain of sand,

And heaven in a wildflower.
To hold infinity in the palm of your hands
And eternity in an hour’
- William Blake
References:
Reminder – electronic devices | computing power
How to fabricate | increase performance | miniaturize electronic devices
- consider a very simplistic transistor
- work as a switch | amplifier takes in small input current and produced a large output current | apply ‘base voltage’ current flows and vice-versa
- how does it do that?
each transistor can have 2 states | ON or OFF | can store binary (0|1)
the structure of the materials composing the ‘transistor’ dictates properties
- should have an appreciable charge carrier density
- should be able to move charge carriers in response to an external stimuli | apply small voltage
Transistor
Diode
The MOSFET [metal oxide semiconductor field effect transistor]

- considered to be the most important transistor
- possibly the most important invention in electronics and the birth of modern electronics Sputtering | bombardment of ions on the target
References:
References:
Fall 2019
Lecture 6
Introduction to Quantum Mechanics | III
Ali Zahid
Tuesday 17th September 2019 @ 10 00

Agenda
- Quantum Numbers | characterizing electrons
- quantum states | electron configuration
- 4 quantum numbers | probability density of finding an electron
- orbital energies | comparison in a single sub-shell
- attractive pull of the nuclear force | degrees of freedom
- Wavefunction ψ(x) | description of the wave-like behavior
- The Copenhagen Interpretation of Quantum Mechanics | relevant for this course

- the wavefunction | ψ(x)
- Born’s statistical interpretation of the wavefunction ψ(x) | probability density of finding a particle
- the act of observation | wavefunction collapse
- Schrödinger’s Cat
- Whiteboard Concepts
Electrons | Atom(s) | Lattices | Assemblies | Solid Things I will ask with a 100% probability !
References:
Quantum Numbers | fixing the ‘quantum state’ of an electron | characterizing electrons
Quantum State | electron configurations
- electrons exhibit wave | particle duality
- Bohr’s model fixed the energies that an electron can take in a shell | but does it give us the whole picture?
- how do we characterize the electron? | how can we ascertain where it is? | what is the behavior of the electrons?
- nature of bonding || sharing | donation | delocalization
- movement || free | hindered | interactive
We need to fix the ‘Quantum State’ of the electron!

- defined by 4 Quantum Numbers | fixes the probability of electron motion [x] wrt its energy [E] Bohr Model | refined | Wave Mechanics Model
- what we get is ‘size, shape, and spatial orientation of an electron’s probability density’
Principal Quantum Number | ‘n’
shells | distance of the electron from nucleus | Bohr’s Atomic Model
Azimuthal Quantum Number | ‘l’
subshells | electron orbital shapes | s,p,d,f | Wave Mechanics Model
Magnetic Quantum Number | ‘m’
number of electron orbitals | Wave Mechanics Model
Spin Quantum Number | ‘s’
orientation of electron | ‘up’ or ‘down’ | Wave Mechanics Model
Principle Quantum Number | n

Electrons having the same l | m | s | n how many shells are present What? | How? | Why?
Same quantum state | shown on similar energy levels Wave Nature of Matter
Some important considerations Ψ(x)
- smaller ‘n’ | lower energy state | E2s > E1s | WHY? Azimuthal Quantum Number | l
- E3d > E3p > E3s | WHY? how many subshells are present
Orbitals with higher energies | more degrees of freedom
- more possibilities of electron spatial arrangements Magnetic Quantum Number | m
- effect of nuclear force decreases how many orbitals in each subshell
Electrons | Atom(s) | Lattices | Assemblies | Solid References:
Wavefunction Ψ(x) | mathematically telling particles how to behave as waves
Classical Mechanics | Newtonian Mechanics
- configuration | state of a system of particles
Momentum (p)
- given by a point (x, p) in the momenta | position coordinate space
- fully deterministic information about the system | any observable Y expressed as Y (x, p)
Quantum Mechanics
- impossible to know BOTH the position and momentum of a particle at every point of its trajectory
- position-momentum uncertainty principle | Heisenberg’s Uncertainty Heisenberg’s Uncertainty Principle Position (x)
- particles have a ‘wave-like’ character | can it be mathematically expressed?
Yes! Introducing the Wavefunction Ψ(x)

- gives a mathematical description of the ‘wave-like’ character | notice that it depends on (x)
- the configuration or state of a quantum object is completely specified by Ψ(x)
- Ψ ∈ C | the wavefunction is a complex function | it has an imaginary and a real part
Interpretation of the Wavefunction Ψ(x) | Probability Density |Ψ(x)|2 = probability of finding a particle @ a certain position
- p(x) = |Ψ(x)|2 | square of the absolute value of Ψ(x)
- determines the probability (density) that an object in the state Ψ(x) will be found at position x
- Ψ(x) is sharply peaked at a particular value of x

Real and imaginary parts of Ψ(x)
Ψ(x) - |Ψ(x)|2 | the probability density | being the square of Ψ(x) | likewise peaked there as well
|Ψ |(x) 2
- the width of the peak is small | the uncertainty in the position is very small
- localization | probability density increases
- Ψ(x) here looks like sinusoid of a different spatial periods | not localized The cumulative probability over all possible positions is unity
- Ψ(x) | complex functions | Ψ(x) = N eikx | only the real part plotted here
- consider |Ψ(x)|2 | |eikx |2 = 1 | hence |Ψ(x)|2 = 1
Ψ(x) |Ψ(x)|2
- sinusoidal Ψ(x) not well localized | large uncertainty in their position
Electrons | Atom(s) | Lattices | Assemblies | Solid ikx = cos (kx) + i sin (kx) | Euler
eReferences:
Schrödinger Equations | how to find the wavefunction Ψ(x) | different particle system(s)
We, now, know what the Wavefunction Ψ(x) is | but how do we get it?
- Ψ(x) = N eikx | was a very special case of Ψ(x)
- every system of particle(s) | every energetic state(s) would have its own Ψ(x)
- there must be a way to get Ψ(x) for any system of particle(s) | energy state(s) | for every ‘characteristic behavior’ of electron(s)
Turns out, there is! But you are not going to like it!
Solve it to get Ψ(r) | r is the position
Time independent Schrödinger Equation
the total energy is the summation of the KE and PE | Hamiltonian Simulations | analytical solutions
In simpler terms
multiply both sides by Ψ(x, t) | both position and time - you need Ψ(x) | to know where the electrons are (for example)
- solve the relevant Schrodinger’s equation | time dependent | time independent
consider Planck’s equation | Broglie’s equation
- Ψ(x) | are solutions to the Schrodinger Equations
reduced Planck constant ‘h’ NOT the only way to study quantum mechanical systems | make predictions.
- matrix mechanics | introduced by Werner Heisenberg
let’s assume Ψ(x, t) is a plane wave in x-direction - the path integral formulation, developed chiefly by Richard Feynman
combine all the equations that you have before The basis for Schrödinger's equation
- the energy of the system | started with the Hamiltonian description
plug it in the Hamiltonian - the wave function Ψ(x) is a description of the system
Instead of having Newton’s 3 equations | deterministic | Classical Physics

after some more calculations | toldya you are not going to like it We have 2 Schrödinger’s Equations | probabilistic | Quantum Mechanics
A linear partial differential equation | solve it to get Ψ(x, t) ‘Where did we get that (equation) from? Nowhere.
Time Dependent Schrödinger Equation It is not possible to derive it from anything you know.
Hard to solve for large system of particles | simulations It came out of the mind of Schrödinger’
-- Richard Feynman
The Copenhagen Interpretation | relevant for ME 431
Schrodinger’s Cat | the curse of observation

- the cat is alive OR dead (2 possible states) before you observe it
- your act of observation either kills the cat or keeps it alive
- the wavefunction collapses and you only get one wavefunction for 1 state
AFTER the act of observation
- don’t observe | don’t kill the cat!
(please play the presentation in slideshow to see the accompanying gif)
Act of observation Act of observation | Ψ(x)

- observe something | you perturb the system during observation - before observation | Ψ(x) exists for every possible state (configuration)
- information you acquire is have large uncertainty - after observation | the act of observation has caused ‘wave function collapse’
- the ‘quantum state’ of the observed entity changes due to the act of observation - you see only 1 possible state of the system due to wave function collapse

Whiteboard | concepts

Whiteboard | concepts

Habib University
ME 431 Introduction to Engineering Materials
Fall 2019
Worksheet | Class Discussion Lecture | Concepts Covered
Bonding and Structure | Lecture 7 | Thursday 19th September 2019
The following concepts were covered in the class:
• Bonding in Solids | Primary Bondings | Ionic | Covalent | Metallic | Mixed

• Bonding in Solids | Secondary Bondings | Van Der Waals | Hydrogen Bonding | Polarity in Bonds
• Concept of Solubility | Formation of polar bonds | Hydrogen bonding | Dissolving
• Ionic Radii | Anions | Cations
• Structure of Ionic Lattices | Lattices | Repeating Units | Identification of a regular atomic
configurational pattern | Coordination number
• Properties of Covalent Bonds | Carbon Allotropes | Diamond | Strong 3-dimensional macromolecular
covalent bonds | Weak interlayer Van Der Waal forces
• Dot – Cross Model | Bonding in Covalent Bonds
Habib University | Fall 2019 | ME 431 | Introduction to Engineering Materials
Lecture 7 | Thursday 19 September 2019 | Bonding and Structure | Class Discussion
Fall 2019
Lecture 8
Bonding and Structure | I
Ali Zahid
Tuesday 24th September 2019 @ 10 00

Agenda
- Revisiting the Length Scales | where are we?
- revising the Quantum Scale | Newtonian Scale
- applicability of wave particle duality @ nano scale
- characterization of electrons | orbitals | probability density maps
- Atoms Coming Together | the power of a collection

- what happens when 2 atoms come together | balancing of electrostatic forces & energies | bond formation(s)
- effect | reasons for the attractive force & repulsive force | relationship between force & energy
- electron cloud interaction | nucleus – electron cloud interaction
- balancing of repulsive | attractive forces | equilibrium distance | ro
- principle of energy minimization | consequences for stability | effect of energy vs r curve on ‘type’ of bonding
- example | hydrogen molecule | characteristic bond length | intermolecular distance
- Bondings | primary
- reason for bonding | energies @ infinite distance of atoms vs @ intermolecular distance
- consideration of Pauli Exclusion Principle | Lone Electron Pair | Ψ for bonding | Lewis Dot Cross Model
- Valence Bond Theory | VB | localized orbital overlap | Ψ overlap | increased electron probability @ internuclear distance
- Molecular Orbital Theory | MO | LCAO | add all the Ψ of all participating electrons of all atoms in the molecule
- when to use VB | MO || localized bonds | whole molecule contribution
- Bondings | secondary
References:
Revisiting the Length Scales | where are we now
Law applicable | Quantum Mechanics
Behavior | Wave Particle Duality | Wavefunction Ψ(x) Solids
[3-dimensional structures]
Clusters
[lattice formation]
Law applicable | Newtonian Mechanics
Atomic
[individual atoms]
Nanoflake
What happens when a few atoms come together? Electrons | Atom(s) | Lattices | Assemblies | Solid
Sub – atomic
[electrons | protons | neutrons]

Atoms! Assemble! | 2 atoms coming together
Individually | atoms aren’t ‘interesting’ | we cannot do much with them | unless of-course in particle physics
- interesting things happen when atoms ‘assemble’ | they start coming closer | they start forming conglomerates
- the easiest way to understand what happens ‘fundamentally’ is to consider atomic energies | variation of E from the nucleus
Nanosheets
Consider 2 isolated atoms | brought to a ‘closed proximity’ infinite distance
- forces exerted by the atoms on each other become ‘non-negligible’ | significant ‘no interactions’
- balancing of attractive force | repulsive force | variation of FA | FR is dependent on the distance
- net force between the atoms | combination of the repulsive + attractive force | FN = FA + FR
- equilibrium exists when both the forces balance each other out | FA = FR FA
FA = FR
Consideration of Energies | atoms brought to a ‘closed proximity’ FR
- much more intuitive | how to connect force and energy
- EN | net energy ro
- EA | attractive energy
- ER | repulsive energy
- observe an ‘energy minimum’ | stability | ‘Principle of Energy Minimization’

- Bonding Energy | Eo | @ ro | @ minimum energy
- magnitude | shape | energy vs r curve | varies
- depends on type of bonding | Covalent | Ionic | Metallic
minima | stability
minimization of energy
Hydrogen Molecule | an example
- notice | the ro || energy required to break the bond | BDE
- BDE | bond dissociation energy * Hydrogen | E vs r

Bond! Chemical Bond! | consequence of energy minimization | primary bonds ‘A bond does not really exist at all - it is a most convenient fiction’ | Charles Coulson
What exactly is ‘bonding’? | Why do atoms need to ‘bond’? |

- physically | bonding is nothing! | cannot see a bond even with powerful microscopes
- conceptually | sharing || donation of electrons | has everything to with electrons!
- then how do we know | characterize bonds? | theories | the Scientific Method | the one that works the best || explains most things || have experimental justification
Valence Bond Theory [VB] | Molecular Orbital Theory [MO] | 2 theories Time Independent
- both applicable at different scenarios | decide which one to invoke Schrödinger Equation
- any theory to explain bonding | Electron Pair || Schrodinger’s Equation || Pauli Exclusion Principle
Ψ(x) | E
Problems | yes, they are many | approximations are required
- nuclei || electrons | both ‘move’ | nuclei are heavier | electrons ‘lighter’ || responds instantaneously The Pauli Exclusion Principle | quantum mechanical principle
- Born Oppenheimer Approximation | separate the motion of the nucleus from that of the electron two identical fermions | cannot occupy same quantum state | simultaneously
- consider the nucleus as stationary | solve the Schrödinger’s Equations | deduce how electrons interact
Similar spins in same orbital | NO
Valence Band Theory [VB] | localized bonding model
- bond is formed between 2 atomic orbitals from each atom | considering 2 atoms
- Ψ overlaps | atomic orbitals overlap | electrons pair up | ↓↑
- constructive interference of Ψ | increased probability of finding electrons in the ‘internuclear region’
- orbital merging || pairing of spins | Pauli Exclusion Principle | lowering of energies
Molecular Orbital Theory [MO] | dominant in computational modelling
- molecular orbital | MO wave function | electron distribution all over ALL the nuclei of a molecule
- Linear Combination of Atomic Orbitals | LCAO
- LCAO | each MO is constructed from a superposition of atomic orbitals in the atoms in the molecule
- ‘size’ of the contribution of an orbital | probability that the electron will be found on that atom in the molecule
Valence bond theory | used when the molecular property identifiable | properties of individual bonds
- organic chemistry | molecules | properties of their functional groups
Molecular orbital theory | describe properties discussed in terms of delocalization
- spectroscopic properties of molecules
- electromagnetic radiation is used to excite an electron from one molecular orbital to another
Fall 2019
Lecture 9
Super Elements | Progress in Materials Science
Ali Zahid

Agenda
- Concepts Covered in the Documentary
- Extractive Metallurgy
- Tungsten Carbide | hard material | very large toughness
- Indium | properties | uses | extractive metallurgy
- Rhenium | properties | uses | extractive metallurgy | how is it used in aerospace technologies
- Turbine blades | how they are formed | what do you need to form them
- Rare Earth Magnets | lanthanide chemistry | exemplify using neodymium | superior magnetism
- Battery Materials | lithium | how does is it extracted | why is it used as a battery material |
- Helium in MRI scans | medical perspective | Super-fluids
References:
Super Elements | BBC documentary
References:
Fall 2019
Lecture 10
Quiz 1
Bonding and Structure | II
Structure of Crystalline Materials | Crystallography | I
Ali Zahid
Tuesday 1st October 2019 @ 10 00

Agenda
- Quiz 1 | graded | 45 minutes | write concise | write precise
- Bondings | secondary
- Dipoles | the concept
- Van Der Waals Bonds | physical
- Fluctuating Induced Dipole Bonds
- Permanent Dipole Bonds | Hydrogen Bonding
- Lattices | basic Crystallography | 3-d periodic atomic arrangements

- 3 dimensional repeating geometric patterns
- Crystalline Materials | atomically periodic
References:
Quiz 1 | 45 Minutes | 35 Marks

Secondary Bonds | Van Der Waals Bonds | yes, these are the weak ones!
Weak forces of attraction | repulsion | weaker than primary bonds Dipoles | electron(s) fluctuations
- occurs due to dipole formation | temporary | permanent - asymmetrical distribution of electron cloud | over the molecule
- dipole formed in one atom | induces a dipole in another atom | chain reaction continues - random fluctuations of electron cloud | polar & non-polar entities involved
- Hydrogen Bonding | Fluctuating Induced Dipole Bonds - are only significant when the species involved | close together
- Polar Molecule - Induced Dipole Bonds | Permanent Dipole Bonds
Fluctuating Induced Dipole Bonds | temporary | weakest

- neutral atom | electrically symmetrical | uniform electron spatial distribution
- instantaneous vibrational motion of atom | temporary alterations of electrical symmetry Fluorine | F | highly electronegative
- dipoles created | electron spatial distribution non-symmetrical Hydrogen | H | highly electropositive
- distribution of electrons displaced | dipole formed | spreads through the collection Electron Cloud | attracted towards H
- liquefaction | solidification | gases | H2 | Cl2 Electrons spend more time around H
Dipole | un-symmetrical electron cloud distribution | electronegativity
Neutral Atom Dipole Formed | Induces Van der Waals Forces

electrically symmetrical electrically un - symmetrical temporary | short lived | weak
Permanent Dipole Bonds | Hydrogen Bonding | permanent

- hydrogen | covalently bonded | HF | H2O | NH3
- single Hydrogen electron | shared due to bonding
- Hydrogen nucleus | unscreened by any electrons | positive + charge
- strong positive charge | attract any negatively charged dipole
- high boiling points of | HF | H2O | NH3
- strongest of the Van Der Waals Forces
Electrons | Atom(s) | Lattices | Assemblies | Solid * Callister | Chapter 2 | Section 2.7

References:
Lattice | Crystallography | a conceptual look
Let’s take a bunch of atoms | arranged || with balanced repulsive | attractive forces | stable
- let’s try and find if there is any smallest unit | geometric shape | repeating itself
- Repeating Geometric Pattern | simplest | reproducible in all 3 dimensions
Square | 2 dimensional || Cube | 3 dimensional | Hard Sphere Model

- smallest arrangement of atoms possible | extends throughout the solid
- Lattice | replicating the arrangement of the smallest repetitive pattern of atoms in a solid
- simplest array of lattice points from which a crystal can be constructed | represents the overall symmetry
A Crystal | Crystalline Material

- pattern of objects | repeats itself periodically
- the property of translational symmetry | repeats in 3 - D
- three-dimensional array of lattice points | periodicity
- atoms | ions | molecules || held together in the solid state
- balance of attractive | repulsive force
Metallic Bonding | Metallic Structures | FCC

- electron cloud spread over the whole structure
- non directional bonding
- lattice | minimal restrictions
- large numbers and position of nearest neighbors
- dense atomic packings | face centered cubic | FCC
FCC HCP
BCC Simple Cubic

Fall 2019
Lecture 11
Structure of Crystalline Materials | Crystallography | II
Ali Zahid
Thursday 3rd October 2019 @ 10 00

Agenda
- Lattices | basic Crystallography | 3-d periodic atomic arrangements

- 3 dimensional repeating geometric patterns
- Worksheet | Basic Crystallography
- Get Your Quiz Checked!
References:



FCC HCP
BCC Simple Cubic

Worksheet | Crystallography

Habib University | Fall 2019 | ME 431 | Introduction to Engineering Materials
Lecture 11 | Thursday 03rd October 2019 | Crystallography | Work Sheet
Fall 2019
Lecture 12
Structure of Crystalline Materials | Crystallography | III
Ali Zahid
Tuesday 8th October 2019 @ 10 00

Agenda

- Crystalline Materials II | Single Crystals | Polycrystalline
- Anisotropy
- Polymorphism
- Unit Cells | an in-depth look |
- Atomic Packing Factor | APF
- Linear Densities | Planar Densities
- Linear Densities | Planar Densities | Calculations
- Critically Resolved Shear Stress | Deformation of Crystalline Materials
- Mid Term Examination | Thursday 17th October 2019 | 10 00 - 11 15

Chapters from Callister | 1 - 2 - 3
Chapter 3 | Principles of Inorganic Chemistry | Pfennig | QM
Readings 4 | In Search of “Forever,” Continued Transistor Scaling One New Material at a Time
Lectures | 1 to 14 (@ Tuesday | 15th October 2019) | inclusive
1 A4 paper | both sides | Only Formulas! | No Concepts | No copying from the slides!
References:
Crystalline Materials | I | atomically periodic
Crystalline Materials | Solid | highly ordered atomic structure Unit Cell
- a specific packing order | organization of a constituent unit cell | periodicity of a basic geometric atomic arrangement - smallest arrangement of atoms possible
- consist of atoms, ions, or molecules | arrayed into a long-range | regularly ordered structure | Lattice - extends throughout the solid
- replicating | arrangement | smallest repetitive pattern
Symmetry of the Crystal | translational | orientational | rotational - having translational symmetry | repeats in 3-D
- constrained by the requirement | unit cells stack perfectly with no gaps | closely packed
- 219 possible crystal symmetries | Crystallographic Space Groups | yes there are many
- grouped into 7 crystal systems | all crystals can be grouped according to them
Crystal Systems | Parameters
- how to group these crystal systems? | framework required for
- Unit Cell Configurations | Atomic Configurations
- 6 parameters required 3 edge lengths | cartesian coordinates | a, b, c

3 interaxial angles | α, β, γ
7 different possible combinations | a, b, c | α, β, γ

accordance with symmetry considerations

Worksheet | Crystallography

Habib University
Fall 2019 | ME 431 Introduction to Engineering Materials
Mid Term Discussion Lecture | Concepts Covered
Lecture 13 | Thursday 10th October 2019
The following concepts were revised | discussed during the Fall 2019 | ME 431 | Introduction to
Engineering Materials | Lecture 13.
Most of these discussed concepts would be part of the Mid Term Examination.
• Properties of a single atom | 2 atoms | a cluster of atoms | lattices | balancing of attractive and
repulsive forces between atoms.
• Rudimentary concepts on electronic energy levels of a single atom | 2 atoms | group of atoms.
• Quantum mechanical model of an electron | probability of an electron spending most of its time at
the discrete shells | orbitals.
• Length Scale of Things | sub-atomic particles | atoms | lattices | cluster of atoms
• Quantum Laws | Pico - Angstrom - Nano Scale
• Quantum Laws | Orbitals
• Atoms | balancing of forces | balancing of energies
• Bondings | primary | secondary
• Band Theory of Solids | electron excitation | electron relaxation
• Crystallography | unit cells | packing factors | influence of bonding
Fall 2019
Lecture 14
Mid Term Examination Review
Ali Zahid
Tuesday 15th October 2019 @ 10 00

Agenda
The length scales | where do we modify materials Wavefunction | Ψ(x) | mathematical expression | wave-like nature
- long range order | short range order - Heisenberg's Un-certainty | position and momentum disparity
- emergent collective properties - real | imaginary | particle position | square of the absolute value of Ψ(x)
The P's of Materials Science | abridged - dependence of Ψ(x) on x
- Structure | Properties | Performance | Processing - formulation of the Schrodinger's Equation | Hamiltonian | wave particle duality
- properties determined by material atomic structure | lattices - act of observation in QM | Ψ(x) collapse during the act of observation
- performance determined by material atomic structure | lattice Bond Formation | atoms coming together | primary bondings
- processing route | decided by atomic structure | properties desired - balancing of attractive - repulsive forces | balancing of energies
Quantum Mechanical Laws | laws governing small length scales - energy minimization | attain stability
- electrons behaving as waves | double slit experiment - mathematical connection between energy | force
- exhibition of all wave like properties | sub-atomic particles - equilibrium atomic spacing | atoms conglomerating peacefully
- deterministic | probabilistic nature of matter at different length scales - molecular orbital theory | valence orbital theory
- wave-particle duality | discretization of energy | quanta - generalized over the whole molecule | localized to the bonded region
- photo-electric effect | electron excitation | electron de-excitation Secondary Bondings | weaker than primary bonds
- band theory | electron-photon interactions | energy shell excitation - fluctuating dipoles | temporary | permanent
- bonding electrons | conduction electrons - Van der Waals forces | hydrogen bonding | strongest
Bohr's Model | Schrodinger's Model - cause high melting | boiling
- determinism of Bohr's Model | probabilism in Schrodinger's Model - asymmetrical distribution of the electron cloud
- electron probability spread | Bohr's Model vs Schrodinger's Model - electronegativity | electropositivity of the chemical entities
- orbital's formation | probability density maps for electrons in an atom Lattices | Crystallography | atoms forming repetitive arrangements
Fabricating Devices | Thin Films - atoms grouping | formation of simplest geometric repetitive units
- sputtering process | plasma formation | bombardment of ions - translation symmetry | symmetry conditions for unit cells
- material properties of a transistor | spatial charge control - 6 parameters required to characterize unit cells | edge lengths | interaxial angles
- crystal systems | 7 possible combinations
Unit cells | detailed look
- mathematical framework | position of atoms
- identifying coordinates to fix atomic positions
References:
Length Scales | where is engineering of materials carried out?
Assemblies We can touch
[many clusters]
[microstructures]
Clusters
[lattice formation]
Molecules | Bond Formation

[few atoms]
Atomic
[individual atoms]
Emergent Collective Properties

Sub – atomic
[electrons | protons | neutrons] Magnetic | Electronic | Optical | Physical
Modification of Material Properties

*References:
Length scale in meters * The Kochmann Research Group – Mechanics and Materials – ETH Zϋrich - Switzerland
‘ Bring forth what is true; Write it so it’s clear. Defend it to your last breath.’
What is Quantum Mechanics ? – a brief historical rant | birth of discretization - Faust | Goethe
Like everything in modern physics, it all started with Ludwig Boltzmann

- used statistical mechanics to explain the ‘collective behavior of atoms’ | atomistic explanation for this universe
- is acclaimed to lay down the foundations of a Quantum Mechanics | the Kinetic Theory of Gas model (taken for granted these days)
- proposed | in 1877 | ‘energy levels of a physical system could be discrete | not continuous’ | discrete energy levels
validated 20 years later | 1900 | Max Planck | Planck’s Law

Einstein | 1905 | the photoelectric effect | energy quanta concept
‘According to the assumption to be contemplated here, when a light ray is spreading from a point, the energy is not distributed continuously over ever-
increasing spaces, but consists of a finite number of 'energy quanta' that are localized in points in space, move without dividing, and can be absorbed or
generated only as a whole.’
- Einstein | On a heuristic viewpoint concerning the emission and transformation of light
- emission of electrons or other free carriers when light hits a material

- electron removed | photoelectron
electron goes to CB | free to move around
Any energy of photon would induce an electron to eject?

- NO!
- energies equal to or higher than the required energy
Basic postulate of QP | Discretization of energy

- electrons orbit the nucleus in orbitals that have fixed energies – not high not low – fixed discrete energies
- 1913 | ‘On the Constitution of Atom and Molecules’ | Niels Bohr | spectral lines in Hydrogen
Wave Particle Duality
- 1923 | Louis de Broglie | particles can behave as waves
- Heisenberg, Born, Schrodinger | wave mechanics | matrix mechanics
- Heisenberg | 1927 | Uncertainty Principle
- Feynman | Quantum Electrodynamics
* QP – Quantum Physics | ** Wikipeda | *** Boltzmann’s Atom: The Great Debate that Launched a Revolution in Physics
References:
Band Theory of Solids | Brief Introduction – white board lecture
References:
Wave Particle Duality – The Double Slit Experiment
Demonstration of the wave nature of matter | probabilistic nature of quantum mechanics
‘…all of quantum mechanics can be gleaned from carefully thinking through the implications of this single experiment..’
- Feynman
- every information about the particle is encoded in a function that describes its ‘wave-like character’ | wavefunction ψ
- the particle (electron) has BOTH a wave + particle nature | important to deduce
constructive | destructive interference

- classical | Newtonian Mechanics prediction - but experiments disagree!!
- group particles allowed through 2 slits
- our own intuition - expectation | particles will only register at only 2 places on the screen
- particles = electrons | protons | molecules
- particles will go through the slit in a straight line - reality | interference pattern emerges!
- just like what you would get for waves!
‘It seems as though we must use sometimes the one theory and sometimes the other, while at times we may use either. We are faced with a new kind of difficulty. We have two
contradictory pictures of reality; separately neither of them fully explains the phenomena of light, but together they do’ -Einstein
What properties do wave exhibit?

- reflection | refraction | diffraction
-‘quantum particles’
- exhibit these properties too!
What happened to the electron? – Bohr’s Determinism | Schrödinger's Probability
Since we are concerned with how electrons move in solids | electron-phonon interaction
- Bohr’s Deterministic Model of the Atom
- Schrodinger’s Probabilistic Model of the Atom
Bohr’s deterministic model of the atom

- nucleus in the center Collective atoms Isolated atom
- energy level splitting - allowed distinct energy levels
- electrons orbits the nucleus in discrete energy levels
- allowed electron energies associated with energy levels or states.
- Electron considered as a Particle
Schrodinger’s probabilistic model of the atom
- probability of finding an electron at the nucleus = Zero [0]
- probability of finding an electron at the furthest shell = maximum
- ‘electron density clouds’
- Electron considered as a Waves | associated with a wavefunction
For bonding in solids For understanding the ‘nature’ of electrons
- Bohr’s Atomic Model is sufficient - Quantum Mechanical Model
- electrons as particles | quantized energies | quantized shells + orbitals - electrons as ‘density clouds’
* William D. Callister Jr & David G. Rethwisch | Fundamentals of Materials Science and Engineering | An Integrated Approach
References:
Reminder – electronic devices | computing power
How to fabricate | increase performance | miniaturize electronic devices
- consider a very simplistic transistor
- work as a switch | amplifier takes in small input current and produced a large output current | apply ‘base voltage’ current flows and vice-versa
- how does it do that?
each transistor can have 2 states | ON or OFF | can store binary (0|1)
the structure of the materials composing the ‘transistor’ dictates properties
- should have an appreciable charge carrier density
- should be able to move charge carriers in response to an external stimuli | apply small voltage
Transistor
Diode
The MOSFET [metal oxide semiconductor field effect transistor]

- considered to be the most important transistor
- possibly the most important invention in electronics and the birth of modern electronics Sputtering | bombardment of ions on the target
References:
Wavefunction Ψ(x) | mathematically telling particles how to behave as waves
Classical Mechanics | Newtonian Mechanics
- configuration | state of a system of particles
Momentum (p)
- given by a point (x, p) in the momenta | position coordinate space
- fully deterministic information about the system | any observable Y expressed as Y (x, p)
Quantum Mechanics
- impossible to know BOTH the position and momentum of a particle at every point of its trajectory
- position-momentum uncertainty principle | Heisenberg’s Uncertainty Heisenberg’s Uncertainty Principle Position (x)
- particles have a ‘wave-like’ character | can it be mathematically expressed?
Yes! Introducing the Wavefunction Ψ(x)

- gives a mathematical description of the ‘wave-like’ character | notice that it depends on (x)
- the configuration or state of a quantum object is completely specified by Ψ(x)
- Ψ ∈ C | the wavefunction is a complex function | it has an imaginary and a real part
Interpretation of the Wavefunction Ψ(x) | Probability Density |Ψ(x)|2 = probability of finding a particle @ a certain position
- p(x) = |Ψ(x)|2 | square of the absolute value of Ψ(x)
- determines the probability (density) that an object in the state Ψ(x) will be found at position x
- Ψ(x) is sharply peaked at a particular value of x

Real and imaginary parts of Ψ(x)
Ψ(x) - |Ψ(x)|2 | the probability density | being the square of Ψ(x) | likewise peaked there as well
|Ψ |(x) 2
- the width of the peak is small | the uncertainty in the position is very small
- localization | probability density increases
- Ψ(x) here looks like sinusoid of a different spatial periods | not localized The cumulative probability over all possible positions is unity
- Ψ(x) | complex functions | Ψ(x) = N eikx | only the real part plotted here
- consider |Ψ(x)|2 | |eikx |2 = 1 | hence |Ψ(x)|2 = 1
Ψ(x) |Ψ(x)|2
- sinusoidal Ψ(x) not well localized | large uncertainty in their position
Electrons | Atom(s) | Lattices | Assemblies | Solid ikx = cos (kx) + i sin (kx) | Euler
eReferences:
Schrödinger Equations | how to find the wavefunction Ψ(x) | different particle system(s)
We, now, know what the Wavefunction Ψ(x) is | but how do we get it?
- Ψ(x) = N eikx | was a very special case of Ψ(x)
- every system of particle(s) | every energetic state(s) would have its own Ψ(x)
- there must be a way to get Ψ(x) for any system of particle(s) | energy state(s) | for every ‘characteristic behavior’ of electron(s)
Turns out, there is! But you are not going to like it!
Solve it to get Ψ(r) | r is the position
Time independent Schrödinger Equation
the total energy is the summation of the KE and PE | Hamiltonian Simulations | analytical solutions
In simpler terms
multiply both sides by Ψ(x, t) | both position and time - you need Ψ(x) | to know where the electrons are (for example)
- solve the relevant Schrodinger’s equation | time dependent | time independent
consider Planck’s equation | Broglie’s equation
- Ψ(x) | are solutions to the Schrodinger Equations
reduced Planck constant ‘h’ NOT the only way to study quantum mechanical systems | make predictions.
- matrix mechanics | introduced by Werner Heisenberg
let’s assume Ψ(x, t) is a plane wave in x-direction - the path integral formulation, developed chiefly by Richard Feynman
combine all the equations that you have before The basis for Schrödinger's equation
- the energy of the system | started with the Hamiltonian description
plug it in the Hamiltonian - the wave function Ψ(x) is a description of the system
Instead of having Newton’s 3 equations | deterministic | Classical Physics

after some more calculations | toldya you are not going to like it We have 2 Schrödinger’s Equations | probabilistic | Quantum Mechanics
A linear partial differential equation | solve it to get Ψ(x, t) ‘Where did we get that (equation) from? Nowhere.
Time Dependent Schrödinger Equation It is not possible to derive it from anything you know.
Hard to solve for large system of particles | simulations It came out of the mind of Schrödinger’
-- Richard Feynman
The Copenhagen Interpretation | relevant for ME 431
Schrodinger’s Cat | the curse of observation

- the cat is alive OR dead (2 possible states) before you observe it
- your act of observation either kills the cat or keeps it alive
- the wavefunction collapses and you only get one wavefunction for 1 state
AFTER the act of observation
- don’t observe | don’t kill the cat!
(please play the presentation in slideshow to see the accompanying gif)
Act of observation Act of observation | Ψ(x)

- observe something | you perturb the system during observation - before observation | Ψ(x) exists for every possible state (configuration)
- information you acquire is have large uncertainty - after observation | the act of observation has caused ‘wave function collapse’
- the ‘quantum state’ of the observed entity changes due to the act of observation - you see only 1 possible state of the system due to wave function collapse

Atoms! Assemble! | 2 atoms coming together
Individually | atoms aren’t ‘interesting’ | we cannot do much with them | unless of-course in particle physics
- interesting things happen when atoms ‘assemble’ | they start coming closer | they start forming conglomerates
- the easiest way to understand what happens ‘fundamentally’ is to consider atomic energies | variation of E from the nucleus
Nanosheets
Consider 2 isolated atoms | brought to a ‘closed proximity’ infinite distance
- forces exerted by the atoms on each other become ‘non-negligible’ | significant ‘no interactions’
- balancing of attractive force | repulsive force | variation of FA | FR is dependent on the distance
- net force between the atoms | combination of the repulsive + attractive force | FN = FA + FR
- equilibrium exists when both the forces balance each other out | FA = FR FA
FA = FR
Consideration of Energies | atoms brought to a ‘closed proximity’ FR
- much more intuitive | how to connect force and energy
- EN | net energy ro
- EA | attractive energy
- ER | repulsive energy
- observe an ‘energy minimum’ | stability | ‘Principle of Energy Minimization’

- Bonding Energy | Eo | @ ro | @ minimum energy
- magnitude | shape | energy vs r curve | varies
- depends on type of bonding | Covalent | Ionic | Metallic
minima | stability
minimization of energy
Hydrogen Molecule | an example
- notice | the ro || energy required to break the bond | BDE
- BDE | bond dissociation energy * Hydrogen | E vs r

Bond! Chemical Bond! | consequence of energy minimization | primary bonds ‘A bond does not really exist at all - it is a most convenient fiction’ | Charles Coulson
What exactly is ‘bonding’? | Why do atoms need to ‘bond’? |

- physically | bonding is nothing! | cannot see a bond even with powerful microscopes
- conceptually | sharing || donation of electrons | has everything to with electrons!
- then how do we know | characterize bonds? | theories | the Scientific Method | the one that works the best || explains most things || have experimental justification
Valence Bond Theory [VB] | Molecular Orbital Theory [MO] | 2 theories Time Independent
- both applicable at different scenarios | decide which one to invoke Schrödinger Equation
- any theory to explain bonding | Electron Pair || Schrodinger’s Equation || Pauli Exclusion Principle
Ψ(x) | E
Problems | yes, they are many | approximations are required
- nuclei || electrons | both ‘move’ | nuclei are heavier | electrons ‘lighter’ || responds instantaneously The Pauli Exclusion Principle | quantum mechanical principle
- Born Oppenheimer Approximation | separate the motion of the nucleus from that of the electron two identical fermions | cannot occupy same quantum state | simultaneously
- consider the nucleus as stationary | solve the Schrödinger’s Equations | deduce how electrons interact
Similar spins in same orbital | NO
Valence Band Theory [VB] | localized bonding model
- bond is formed between 2 atomic orbitals from each atom | considering 2 atoms
- Ψ overlaps | atomic orbitals overlap | electrons pair up | ↓↑
- constructive interference of Ψ | increased probability of finding electrons in the ‘internuclear region’
- orbital merging || pairing of spins | Pauli Exclusion Principle | lowering of energies
Molecular Orbital Theory [MO] | dominant in computational modelling
- molecular orbital | MO wave function | electron distribution all over ALL the nuclei of a molecule
- Linear Combination of Atomic Orbitals | LCAO
- LCAO | each MO is constructed from a superposition of atomic orbitals in the atoms in the molecule
- ‘size’ of the contribution of an orbital | probability that the electron will be found on that atom in the molecule
Valence bond theory | used when the molecular property identifiable | properties of individual bonds
- organic chemistry | molecules | properties of their functional groups
Molecular orbital theory | describe properties discussed in terms of delocalization
- spectroscopic properties of molecules
- electromagnetic radiation is used to excite an electron from one molecular orbital to another
Secondary Bonds | Van Der Waals Bonds | yes, these are the weak ones!
Weak forces of attraction | repulsion | weaker than primary bonds Dipoles | electron(s) fluctuations
- occurs due to dipole formation | temporary | permanent - asymmetrical distribution of electron cloud | over the molecule
- dipole formed in one atom | induces a dipole in another atom | chain reaction continues - random fluctuations of electron cloud | polar & non-polar entities involved
- Hydrogen Bonding | Fluctuating Induced Dipole Bonds - are only significant when the species involved | close together
- Polar Molecule - Induced Dipole Bonds | Permanent Dipole Bonds
Fluctuating Induced Dipole Bonds | temporary | weakest

- neutral atom | electrically symmetrical | uniform electron spatial distribution
- instantaneous vibrational motion of atom | temporary alterations of electrical symmetry Fluorine | F | highly electronegative
- dipoles created | electron spatial distribution non-symmetrical Hydrogen | H | highly electropositive
- distribution of electrons displaced | dipole formed | spreads through the collection Electron Cloud | attracted towards H
- liquefaction | solidification | gases | H2 | Cl2 Electrons spend more time around H
Dipole | un-symmetrical electron cloud distribution | electronegativity
Neutral Atom Dipole Formed | Induces Van der Waals Forces

electrically symmetrical electrically un - symmetrical temporary | short lived | weak
Permanent Dipole Bonds | Hydrogen Bonding | permanent

- hydrogen | covalently bonded | HF | H2O | NH3
- single Hydrogen electron | shared due to bonding
- Hydrogen nucleus | unscreened by any electrons | positive + charge
- strong positive charge | attract any negatively charged dipole
- high boiling points of | HF | H2O | NH3
- strongest of the Van Der Waals Forces
Electrons | Atom(s) | Lattices | Assemblies | Solid * Callister | Chapter 2 | Section 2.7

References:



FCC HCP
BCC Simple Cubic




FCC HCP
BCC Simple Cubic




Unit Cells | in-depth look | ‘fixing’ atomic positions
Geometric | mathematical framework | characterize the Unit Cell Body Centered Cubic | BCC
- how to characterize the unit cell | where are at the atoms - smallest arrangement of atoms possible
- translational symmetry elements | mathematical | time to play! geometric ways | atoms present | unit cell - extends throughout the solid
Position of an atom | vectoral representation - having translational symmetry | repeats in 3-D
- linear characterization
- how many atoms are present on a single vector?
Position of many atoms | planar representation
- planar characterization
- how many atoms are present on a single plane?
Planes | where the atom are in 2-d Atomic Position
Develop the mathematical framework | how to do that
- take a cartesian coordinate axes | fix it to the unit cell Unit Cell
- mathematical framework | 3 edge lengths (cartesian coordinates) | 3 interaxial angles (consider them to be similar) 1,1,1
x,y,z
- position of any atom in the unit cell | coordinates as fractional multiples of the unit cell edge
Body Centered Cubic | BCC Face Centered Cubic | BCC

- coordinates of the atom in the middle | position of the atom - position of the atom on the front face
- follow the black lines | start from the origin (0,0,0) 1
- is @ (1,1, )
1 1 1 2
- is @ ( , , )
2 2 2

* Callister | Chapter 3
Fall 2019
Lecture 17
Structure of Crystalline Materials | Crystallography | III
Ali Zahid
Tuesday 07th November 2019 @ 10 00

Agenda

- Crystalline Materials II | Single Crystals | Polycrystalline
- Anisotropy
- Polymorphism
- Unit Cells | an in-depth look |
- Atomic Packing Factor | APF
- Linear Densities | Planar Densities
- Linear Densities | Planar Densities | Calculations
- Critically Resolved Shear Stress | Deformation of Crystalline Materials
References:



Unit Cells | in-depth look | ‘fixing’ atomic positions
Geometric | mathematical framework | characterize the Unit Cell Body Centered Cubic | BCC
- how to characterize the unit cell | where are at the atoms - smallest arrangement of atoms possible
- translational symmetry elements | mathematical | time to play! geometric ways | atoms present | unit cell - extends throughout the solid
Position of an atom | vectoral representation - having translational symmetry | repeats in 3-D
- linear characterization
- how many atoms are present on a single vector?
Position of many atoms | planar representation
- planar characterization
- how many atoms are present on a single plane?
Planes | where the atom are in 2-d Atomic Position
Develop the mathematical framework | how to do that
- take a cartesian coordinate axes | fix it to the unit cell Unit Cell
- mathematical framework | 3 edge lengths (cartesian coordinates) | 3 interaxial angles (consider them to be similar) 1,1,1
x,y,z
- position of any atom in the unit cell | coordinates as fractional multiples of the unit cell edge
Body Centered Cubic | BCC Face Centered Cubic | BCC

- coordinates of the atom in the middle | position of the atom - position of the atom on the front face
1
- follow the black lines | start from the origin (0,0,0) - is @ (1,1, )
1 1 1 2
- is @ ( , , )
2 2 2

Crystalline Materials | II | single crystals | polycrystalline
Polycrystalline Materials
- majority of crystalline solids are composed of a collection of ‘small crystals’ | Grains
atoms assemble form repetitive 3-dimensional structures | Unit cells collective behavior of Unit cells
Similar orientation
Single Crystal
Dissimilar orientation
Grains and Grain Boundaries

Anisotropy | directional dependence of properties
Directional Dependence | physical properties Direction-dependent properties of materials
- properties that manifest themselves in any 1 cartesian axes | Anisotropic Property - Magnetic Anisotropy | magnetic properties in a specific direction
- no directional dependency in properties | property same wherever we take the measurement | Isotropic Property - Polycrystalline materials | directionality depends on processing
Crystallographic Directions
Directional dependence of Modulus of Elasticity
- preferential increase in GPa | in a certain direction
- densely populated planes | more atoms on a certain plane
Mechanical Properties of Materials | directional dependence

- grain structure | dictates the mechanical properties
- grain alignment | dictates the mechanical properties
Composite Materials | structures made of more than 1 material
- reinforcements + matrix | 2 components
- direction of reinforcement alignment | strength in that direction
- carbon fibers | glass fibers | particulate reinforcement
- specialized applications | fast cars | airplanes
Transformer Cores | high magnetic permeability | confine magnetic fields

- iron alloys | magnetic | ferrous magnetism.
- magnetic properties are anisotropic | directional dependence | how can it be controlled ?
Magnetism | is an individualistic quantum phenomenon | Magnetic Moment on an atom
- atoms collectively | unit cells | align the unit cells | magnetic moment of all atoms one particular direction
- rolling operations | Texturing
Rolling Operations | align grains
- grains | preferentially aligned in the <100>
- magnetic texturing | <100> direction grains | aligned parallel to the direction of the applied magnetic field

Polymorphism | same material | different conditions | different atomic structure
Polymorphism | multiple crystal structures
- presence of more than 1 crystal structure | solid | any crystalline material
- interrelated | allotropy | different structural modifications of an element
- more than 1 repetitive representation of the crystal structure | more than 1-unit cell
- polymorphic transformation | accompanied by | change in density + other physical properties
Crystallographic Structure 1 Crystallographic Structure 2
Materials’ processing induced Polymorphism | how the solid is made
- changes in structure + properties | due to the processing route | fabrication
- diamond | natural | synthetic | high pressures + high temperatures | single element
- graphite | graphene | room temperature + room pressure | single element Allotropes of Carbon | single element polymorphism | room temperature Carbon
Bi-elemental | Steel | iron + carbon - 3-dimensional macrostructure | covalent macromolecular | Diamond
- at high temperatures | 950oC | Austenite phase | Face Centered Cubic Unit Cell - 2-dimensional | weak inter layer bonding | Van der Waals | Graphite | Graphene
- at room temperature | Ferrite phase | Body Centered Cubic Unit Cell
References:
Atomic Packing Factor | in-depth look | Unit Cells How many atoms can I pack in an Unit cell ?
How many atoms in a Unit Cell | atomic density | characterize the Unit Cell
The APF is the sum of the sphere volumes of all atoms within a unit cell divided by the unit cell volume
Volume of spheres
Volume of cube Hard-sphere model
FCC structure | the atomic packing factor is 0.74 | maximum packing possible for spheres all having the same diameter
Volume of spheres
Volume of cube
* William D. Callister Jr & David G. Rethwisch – Fundamentals of Materials Science and Engineering - An Integrated Approach - Chapter 3 References:
Fall 2019
Lecture 18
Phases | Phase Diagrams | Iron Carbon System | I
Ali Zahid

Agenda
- Phases | formal introduction

- Phase Equilibria
- One Component Systems | Unary phases diagrams
References:
Phases | a formal introduction | Solid Solutions | Solubility Limit
Consider | sugar dissolving in water | C12H22O11 in H2O
- weak interactions between C12H22O11 + H2O molecules | solvent in a solution
- maximum amount of C12H22O11 can be dissolved | @ specific temperature
- add more sugar | it will not dissolve | additional sugar settled at the bottom
- solubility limit reached | liquid solution + solid sugar
Solid Solutions | they too exist and exhibit the solubility limit
- Solid Solutions | contains 2 parts | solvent + solute
- Solvent | element of compound present in a large concentration | Fe in Steel (Fe + C) | host atoms
- Solute | element or compound present in minor concentration | C in Steel (Fe + C)
- solid cannot accommodate the addition of another solid | becomes saturated | Fe cannot accommodate more C
Solute atoms | modification of material properties
- distorting the crystal lattice
- disrupting the physical | electrical homogeneity of the solvent material
Phase | the concept Solid Solutions | 2 types | Hume Rothery Rules
I | Substitutional | solute atoms replace the solvent atoms
- defined as a homogeneous portion of a system | has uniform physical and chemical characteristics
II | Interstitial | solute atoms fills void between solvent atoms
- sugar-water solution 1 phase | solid sugar 1 phase
Factors deciding solubility:
- each phase have different composition | chemically different
i. Atomic Size
ii. Crystal Structure
Water | 3 phases present
iii. Electronegativity
- solid phase | low temperatures
iv. Valences
- liquid phase | above 0oc | below 100oC I II
v. Solubility
- gaseous phase | above 100oC
- differences in thermodynamic quantities | new phases form
- structural changes | indicates a phase change
- chemical changes | indicates a phase change Iron | Fe
- phases are separated by phase boundaries | a-b-c

- across PB | abrupt and discontinuous change in properties Carbon | C
- 2 or more polymorphic forms | different phases
References:
Binary Phase Diagrams | 2 phases present | solid solution formation | Isomorphous
Copper – Nickel System | solid solution | isomorphous
- solid solution | with complete solubility in each other | isomorphous solid solution
- 3 phases are apparent | α-phase (solid solution) | L-phase (liquid) | (α + L)-phase
- notice | 3 phases separated by phase boundaries
Cu-Ni Phase diagram | detailed look | 3 phases present
- L-phase | homogenous solution of both Cu + Ni
- α-phase | substitutional solid solution | FCC L-phase | Cu + Ni
- complete | mutual solubility of Cu and Ni | both are FCC - completely soluble
- similarity in lattice | similarity in valence | similarity in electronegativities
Liquidus Line | above this line only the liquid phase exists | pb
Solidus Line | below this line only the solid phase exists | pb
Region between Liquidus & Solidus line | between these lines both phases co-exist | pb
α -phase | Cu + Ni
- substitutional solid solution
- FCC | complete solubility
- alloy contains Cu(x) + Ni(y)
- Hume Rothery Rules
Copper - Zinc Alloys | not complete solubility

- substitutional solid solution
- above 30% Zn | second phase form | compound of Cu + Zn
- 3 phases in Cu | Ni phase diagram
- limited solubility of Zn in Cu | not isomorphous
- complete solubility | enclosed curved space | always
- move on the liquidus line | melting point | CuxZny
- formation of a new compound phase | induces stress
- leads to Solid Solution Strengthening | we will look this in detail
References:
* Callister | Chapter 10 || ** Phase Boundary | pb
Fall 2019
Lecture 19
Phases | Phase Diagrams | Iron Carbon System | II
Ali Zahid
Thursday 14th November 2019 @ 10 00

Agenda
▪ Phases | microstructural development | Binary Phase Diagram | equilibrium cooling
▪ Phases | microstructural development | Binary Phase Diagram | non-equilibrium cooling
References:
Phases | microstructural development | Binary Phase Diagram | equilibrium cooling
Copper (Cu) - Nickel (Ni) Binary System | microstructural evolution | equilibrium cooling
- 3 phases are apparent | α-phase (solid solution) | L-phase (liquid) | (α + L)-phase | Isomorphous System
- consider | the microstructure evolves during the equilibrium cooling of the Cu-Ni binary alloy system
- primarily considerations | how to cool down the melt | Cu (65%) + Ni (35%) | considering all the 3 phases
- slow cooling | equilibrium cooling | inhibit compositional gradients | don’t allow for ‘coring’
- have a relevant cooling cycle | temperature vs time
- diffusion process | dependent on temperature and time | allow readjustment of phase(s) composition
• Point ‘a’ | liquid phase L | contains 35% Ni + 65% Cu
• Point ‘b’ | solidification starts as soon as the phase boundary is reached | α-phase starts to ‘nucleate’
- α-phase (solid solution) | contains 46% Ni | draw a tie line towards the solidus lie
• Point ‘c’ | solidification continuing | α-phase growing | Ni% getting closer to 35%
• Point ‘d’ | solidus line | L-phase present in small quantity | α-phase growing larger
• Point ‘e’ | α-phase region | only α-phase present | 35% Ni + 65% Cu
Important considerations | phase changes | solidification
- with cooling | the relative amount of both phases will change | till equilibrium reached
- when the phase crosses a solidus line | solidification of the alloy solid solution initiates
- solidification will complete when solidus line is breached | L-phase no longer exists
- compositions of the liquid and α phases | follow the liquidus and solidus lines
- with continued cooling | the fraction of the α phase will increase
- overall alloy composition | 35% Ni - 65% Cu remains unchanged | during cooling
- redistribution of copper and nickel between the phases | during cooling
Similar solidification processes occur for binary | ternary | quaternary compounds
Lattice Electronegativity Atomic Radius (nm)
Ni FCC 1.9 0.1246
II | group of atoms | thermo. stable | nucleus III | nucleus grows Cu FCC 1.8 0.1278
I | isolated atoms
References:
Callister | Chapter 10
Phases | microstructural development | Binary Phase Diagram | non-equilibrium cooling
Copper (Cu) - Nickel (Ni) Binary System | microstructural evolution | non-equilibrium cooling
- 3 phases are apparent | α-phase (solid solution) | L-phase (liquid) | (α + L)-phase | Isomorphous System
- consider | the microstructure evolves during the non-equilibrium cooling of the Cu-Ni binary alloy system
- primarily considerations | how to cool down the melt | Cu (65%) + Ni (35%) | non-equilibrium
- inhibit diffusional processes | not allow equilibrium readjustments in compositions of liquid and solid phases
- increase the cooling rate | decrease the diffusion rate
- practically | the cooling rate is always inconsistent | too rapid to allow for compositional readjustments
• Point ‘a’ | liquid phase L | contains 35% Ni + 65% Cu

• Point ‘b’ | solidification starts as soon as the phase boundary is reached | α-phase starts to ‘nucleate’
- α-phase (solid solution) | contains 46% Ni | draw a tie line towards the solidus lie
• Point ‘c’ | solidification continuing | α-phase solidifying with a variable composition | 46% & 40%
- the (α + L)-phase region on phase diagram | expanded | multiple solidus lines | non-equilibrium conditions
• Point ‘d’ | solidus line | L-phase present in small quantity | α-phase growing larger | 3 different compositions
• Point ‘e’ | α-phase region | only α-phase present | 31% Ni + 35% Ni + 40% Ni + 46% Ni + 65% Cu
- average composition | Point ‘e’ | 35% Ni + 65% Cu
Important considerations | solidification | non-equilibrium cooling

- degree of displacement | nonequilibrium solidus curve from the equilibrium | depends on the rate of cooling
- the slower the cooling rate | the smaller displacement
- non-uniform distribution of the 2 elements in the grains | segregation
- concentration gradients established in the grains | coring
- eliminate coring | homogenization heat treatment | atomic diffusion | compositionally homogenous grains
Lattice Electronegativity Atomic Radius (nm)
Ni FCC 1.9 0.1246

Cu FCC 1.8 0.1278
References:
White Board
References:
White Board
References:
IDEE - Interdisciplinary Engineering Elective
Fall 2019
Lecture 20
Phases | Phase Diagrams | Iron Carbon System | III
Ali Zahid

“[I do not] carry such information in my mind since it is readily available in books.
Agenda ...The value of a college education is not the learning of many facts but the training of the mind to think.” - Einstein
▪ Phase | Gibbs Phase Rule

- important considerations in the phase diagram
▪ Phase Diagrams | Thermodynamics
- phase equilibria
▪ Phase Diagrams | Lead - Tin Phase Diagram | binary eutectic
▪ Phases Diagrams | Iron - Carbide Phase Diagram
▪ Nucleation & Growth | birth of crystallization
▪ Phase Transitions | Classical Theory
References:
Phase Diagrams | important considerations | Gibbs Phase Rule
Equilibrium Phase Diagrams | equilibrium cooling | all phase diagrams | unless mentioned
Cu-Ni System
- enables prediction | sequence of events during solidification | equilibrium cooling conditions
- Isomorphous
- compositions of solid + liquid phase | evolves continuously during cooling | readjustment of phase(s) compositions
- 3 phases
- slow cooling | atomic diffusion | inhibit compositional gradients | equilibrium is maintained
-α|α+L|L
- rapid cooling | inhibits diffusion | compositional gradients | in-homogenous compositional solidification
- complete solubility
- rapid cooling | coring | dendritic micro-structures | ingrowth of micro-structures
- FCC | parent | resultant
Hume-Rothery Rules
- crystal structure
- electronegativity
- valence
Gibbs Phase Rule | phase diagrams - atomic radii
- thermodynamic criterion | number of phases co-existing within a system | equilibrium Isomorphism
P + F = C + N where P: number of phases present | F: degrees of freedom (externally controlled variables) - similarity in all HR rules
C: number of components | N: number of non-compositional variables (temp or pressure)
- consider the Cu-Ni phase diagram | single phases | α or α+L or L
N = 1 (constant pressure (1 atm | eqm)) | C = 2 (Cu & Ni) | P = 1 (single phase)
1+F=2+1|F=2
i.e. to completely specify the characteristics of the phase within one of the boundaries | 2 parameters
~ composition and temperature I | isolated atoms II | group of atoms | thermo. stable | nucleus
- consider the Cu-Ni phase diagram | binary phase | (α+L)
N = 1 (constant pressure (1 atm | eqm)) | C = 2 (Cu & Ni) | P = 2 (single phase)
2+F=2+1|F=1 2 types of nucleation
i.e. only 1 parameter is required to know the characteristic of the phase within the boundary - Homogenous
fix temperature | automatically a tie line is formed to know the composition - Heterogenous
- if 3 phases are present | F = 0 | compositions of all 3 phases are fixed | the temperature is fixed III | nucleus grows
you can only have those 3 phases | under those specific conditions | only
* eqm | equilibrium * pb | phase boundary * L | Liquid * S | Solid * HR | Hume Rothery Rules * Callister
References: | Chapter 10
Phase Diagrams | thermodynamics | phase equilibria
Phase Diagrams | equilibrium conditions
- phase diagrams | graphical | represents phases present in equilibrium stable conditions
- simplistic | 2 variables | phases present due to variations of those variables | degrees of freedom | F
How are phase diagrams constructed? | thermodynamic basis
- select external variables | Temperature | Pressure | Concentration | Volume | State Variables (SVs)
- determine the Gibbs Free Energy (G) | possible phases | existing for possible combinations of SVs
I
- one specific combination of SV | one state point | many many many state points are possible
- phase diagrams | record the state points | representing the lowest value of G at each state point
Isomorphous Solid Solution

- complete solubility
Equilibrium states | 3 types :

- stable | (A)
- metastable | (B)
II - unstable
Gibbs Free Energy | G | conditions for stability
Phase Stability | which phases exist - G = H - TS
- dependent on | extent of solid solubility of phases | the temperature dependence of stability - system having no tendency to change | dG = 0
- stability of a certain phase | dependent on competing factors - all reactions | if kinetically favorable | decrease G
- respective values of G | of each competing phase | variation of G with chosen state variables (T,C..) - condition for stability | ∆G = G2 - G1 < 0
- when considering stability | G matters | G = H - TS - phases pass through different metastable phases
- contributions to ‘S’| statistical mixing of atoms (∆Smix) | vibrational effects (∆Svib) | config. effects - settle on the stablest phases | ∆G = G2 - G1 < 0
- contributions to ‘H’ | atomic mixing (∆Hmix) | related to the interaction energies between atoms - stable equilibrium is not necessarily direct
Which phases make to the phase diagram? | stable phases

- phases that make to the phase diagram | derived from the G vs SV (of concern, here C) variations
- the minimum G point is plotted on the phase diagram | consider this approach for all values of T
- thousands of values of T | find minimum | plot its variations | II
Only those phases that are in stable equilibrium with the lowest G makes it on the phase diagram
*SV | State Variable *G | Gibbs Free Energy *H | enthalpy *S | entropy *T | temperature References:
*config | configurational | long range interaction between atoms * Callister | Chapter 10
IDEE - Interdisciplinary Engineering Elective
Fall 2019
Lecture 21
Quiz 2 | Class Discussion | Assessment Discussion
Ali Zahid
Thursday 21at November 2019 @ 10 00

Habib University
Phase Diagrams | Microstructures in Steel | Interpretation of Phase Diagrams
Lecture 22 | Lecture 23 | Tuesday 26th November 2019
You have been provided a reading:

Alloys and Phases: Microstructures | Iron Carbide (Fe-Fe3C) Phase Diagram
Please form a group of 3 members, read the relevant sections of the provided reading. You should use an hour
going through the article in silence, discuss and then attempt the questions, given below. Please write in bullet
points. You are allowed to Google anything you like. You can ask the instructor any question you like.
1. What are the different microstructures formed in Steel (Fe + C)?

2. Why are these different microstructures formed? Please consider the thermodynamic aspects of phase
transformations.
3. What is the Eutectic Reaction?
4. How can you identify a Eutectic Reaction on the phase diagram?
5. What is the influence of the rate of cooling on microstructure evolution?
6. What is the influence of the addition of Carbon on Iron?
7. What are the crystal structures of (i) Austenite (ii) Martensite (iii) Ferrite?
8. How does the Pearlite phase form?
9. What are the components of the Pearlitic phase?
10. How does Carbon diffusion influence the thickness of the Cementite plates in the Pearlitic phase?
11. What is the TTT diagram?
12. What microstructures can be represented on the TTT diagram?
Chapter 2
Alloys and Phases: Microstructures
Previously, we saw how a metal can be composed of grains,which are single crystals, possibly of
different phases. Therefore in a single phase material, there are three lengthscales we consider;
that of the component, of the microstructure and of the crystal lattice, Figure 2.1. In general,
the smaller the grains in a material, the stronger it is, so one of the key questions is how we
can make fine-grained materials.
Alloys are mixtures of two or more elements, usu-

ally made by mixing the elements together in a liq- Pure Metal
uid. This is because most elements are soluble in Crystal / Grain
each other in the liquid state, allowing a randomly

mixed solution to form. However, solid metals of- Atomic lattice
ten have a restricted capacity to take other elements
into solution - they have limited solubility, and so
alloys are often composed of two or more different
phases. For the rest of this section, we will consider
alloys composed of two elements generically termed
‘A’ and ‘B’. Figure 2.1: Hierarchy of length scales in a
pure metal; the atomic lattice, grain struc-
ture and component scales.
2.1 Single and Multi-Phase Alloys
In the simplest case, if we take an alloy composed mostly of A with limited amounts of B where
the two elements are soluble in each other, then we can form a single phase material, called a
solid solution, Figure 2.2. This occurs most commonly where the elements have similar atomic
sizes and crystal structures. Only a few pairs of atom form a solid solution over the entire
range of compositions from 100% A to 100% B but when this occurs each grain or crystal is a
random mixture, at the atomic scale, of the two elements. For example, an alloy with 70% A
and 30% B would appear the same as an alloy of pure A - the only difference would be that
30% of the sites in the crystal structure would have B atoms rather than A atoms. This is
called a substitutional solid solution.
Whilst complete solid solubility is rare, most combinations of elements have some solubility in
each other - for example A might be able to take only 5% B into its crystal structure with phase
α, and conversely B might be able to take only 7% of A into its structure β. This situation is
termed partial solubility.
14
2. Alloys and Phases: Microstructures 15
Substitutional Interstitial
Pure A
Solid Solution Solid Solution
Atoms ~ same size Solute atoms much smaller
Figure 2.3: Substitutional and Interstitial solid solutions.
Pure Metal Another possibility is where the A and B atoms

Crystal / Grain
have very different sizes - for example iron Fe and
carbon C. In a steel, that is, an iron-based alloy,
Atomic lattice
the majority element is iron. The majority element
is called the solvent and the minority element the
B atom solute. If the solute atoms are very much smaller
A atom than the solvent, e.g. C in a solvent of Fe, then it
is possible to form a solid solution where the solute
Figure 2.2: Arrangement in a single phase atoms fit into some of the gaps in the crystal struc-
impure metal alloy: a substitutional solid so- ture. These gaps are termed the interstitial sites
lution. and so this type of solution is called an interstitial
solid solution.
In general, we find that solid solutions are very

Pure Metal much (3-4×) stronger than pure metals.
Crystal / Grain Phase β
In our alloy above with partial solubility, what hap-

pens when we make an alloy of A and B that lies
Phase α outside the solubility range for either the α or β
phases? If there were no intermediate compounds,
an alloy with a B content between 5 and 95% would
then be composed of an appropriate mixture of the
Figure 2.4: Arrangement of atoms in a two- α and β phases, with both phases taking the com-
phase alloy. position of their solubility limit. So, for example, if
we made an alloy with 10% B, then we would form
16 MSE 104: Phase Metallurgy: David Dye (2012-13)
a mixture of α phase out of A with 5% B and β phase composed of B with 7% A.
Sometimes, intermediate compounds can form

in the phase diagram; technologically important Pure Metal
Phase β
examples include Ni3 Al, Fe3 C, NiTi and Nb3 Ti. Crystal / Grain
Ni3 Al is used in nickel superalloys, which have
the best high temperature mechanical perfor-
mance of all known alloys and are consequently
Phase α
used in aero-engines and rockets. Fe3 C is the
basis of plain carbon steels and therefore one of
the foundations of modern society. NiTi takes
on different crystal structures under varying con-
ditions of temperature and stress; the result- Figure 2.5: Arrangement of atoms in a two-
ing shape change allows actuators to be made phase alloy, where the second phase β in an
that respond to temperature and stress. Finally, intermetallic with composition AB. Notice how
Nb3 Ti is superconducting at low temperatures the arrangement of the atoms in the β phase is
and is used in the majority of superconducting ordered.
magnets used in the world today, for instance in
the hundreds of multi-billion $ particle physics facilities in the world.
Take the example of a phase α with solubility for 7% B and a phase δ with composition
A3 B, then an alloy with 15% B would be composed of a mixture of α (A with 7% B) and δ.
Conversely, an alloy with only 3% B would be pure α.
2.2 Counting up the atoms: Weight and Atom Fractions
Alloys are defined according to the fractions of each element they

contain. Often, the fractions are defined by weight - the number
of grammes of each element they contain, since weight is the
quantity that the person making the alloy can most conveniently
measure. However, scientifically the atomic bonds are defined by
the number of atoms - the number or atom fraction.
For example, consider a molten alloy in a bucket, Figure 2.6.

Ignoring the weight of the container, how much will it weigh?
Defining each atom type x with atomic mass per mole mx and
atomic fraction Cxa , then N atoms of alloy will weigh
N X
mx Cxa (2.1)
NA x
where NA is Avagadro’s number. The weight of only the atomic Figure 2.6: A bucket con-
species x is just NNA mx Cxa . So the weight fraction Cxw of species x taining a mixture of two
is; species of elements (white and
N
mx Cxa m Ca black).
w
Cx = N P
NA
= P x x a (2.2)
x mx Cx
a
N
A x mx Cx
As an example, consider the compound Fe3 C. Obviously, the atomic fractions Cxa must sum to
1, so these are 0.75 for Fe and 0.25 for C. So the weight fraction of carbon in Fe3 C is
12.01 × 0.25
CCw = = 0.0668 (2.3)
12.01 × 0.25 + 55.85 × 0.75
so the atom fraction of carbon in Fe3 C is 6.68%. The inverse operation is to convert from weight
fraction to atomic fraction. If we consider 1 kg of alloy in our bucket, that has a weight fraction
of atom x of Cxw , the x atoms will weigh Cxw kg. A mole of them would weigh mx and therefore
there must be Cxw /mx mol of them in our bucket, or Cxw NA /mx atoms in total. Therefore the
total number of atoms in the bucket is just the sum of this quantity over all the elements, and
so atomic fraction of x, Cxa , is
C w /mx
Cxa = P x w (2.4)
x Cx /mx
For example, the alloy Ti-10V-2Fe-3Al has weight fractions of 85% Ti, 15% V, 2% Fe and 3%
Al. However, the at.%’s are quite different for Fe and Al - in at.% the alloy would be quoted
as Ti-9.3V-1.7Fe-5.2Al.
Exercise: check for yourself that, if you repeat these two examples working the other way
around, you recover the original data.
Question: Conventionally, alloy compositions are given in wt.% - is this appropriate or would
at.% be better?
2.3 Formation of a microstructure
As stated earlier, most engineering alloys are made by mixing together the alloying elements in
the liquid state and then solidifying the alloy into a suitable shape, a process known as casting.
It is possible to cast the alloy directly into a shape at or close to the dimensions of the finished
component, but commonly cast materials have large grain sizes, vary in composition within
the alloy (segregation) and contain pores (holes) and inclusions (e.g. oxide particles). All of
these give rise to poor mechanical properties, especially in cyclic loading conditions, called
fatigue. Therefore very commonly the cast ingot is first hot worked and heat treated, that is,
deformed at high temperatures, to break up the inclusions, close the pores, homogenise the
composition and reduce the grain size. These optimization of the material processing sequence
is a major topic in materials development, since it concerns the control and optimisation of the
microstructure that gives rise to the properties of the material.
Molten Metal
Slab Caster
Hot R
Ho Rolling
lli
Cooled to room
temperature or
Heat Treated
Re-Heat
Re
Solid
S lid IIngott
Finished Product
Figure 2.7: Alloys are usually made my mixing metals in the liquid state and then casting them into
a solid shape. Often, the material is then deformed at high temperatures (hot working) to make the
final microstructure.
In metallurgy we use the physical processes that operate in materials to produce the microstruc-
ture we desire, using processing techniques that we can, by and large, control for large quantities
(tonnes) of material at a time. This enables us to produce large amounts of material quickly
and cheaply with good properties. This is contrast with nanotechnology, where very typically
the microstructure is produced step-by-step, layer-by-layer, very laboriously and expensively.
2.4 Solidification
Therefore the first process we should aim to

understand in the solidification process. In a
pure metal, or any pure material, the liquid-solid 100% Liquid
Temperature (T)
transition occurs at a single temperature, the
melting point, at which latent heat is evolved. Solid Crystals
This latent heat is the energy difference between Grow
the high energy, disordered, liquid state and the Liquid
lower energy, ordered, solid state - in the liq- Solid
uid the atoms are arranged randomly whereas in
the solid they are arranged on a regular crystal
lattice. Therefore the solidification reaction is Solidification
exothermic, i.e. it produces heat. Complete
Time (t)
If heat is continuously extracted from the liquid, Figure 2.8: Cooling curve of a pure metal,
therefore, the temperature drops. When the so- showing a temperature arrest at the melting
lidification process starts, the latent heat evolved point.
prevents the metal from continuing to cool. The
rate of solidification is therefore determined by the rate at which the latent heat can be ex-
tracted from the metal. After the solidification process completes, the solid metal then resumes
cooling as heat is extracted. If we then wanted to re-melt the material, we would have to supply
heat (thermal energy) to overcome the latent heat required for melting.
2.5 Continuous Solid Solutions; The Lever Rule
The simplest type of alloy phase diagram is the continuous solid solution, Figure 2.9. Here we
have two metals, probably with very similar atomic sizes and crystal structures, that form a
single continuous phase in both the liquid and solid states but have different melting points.
Therefore there are only two phases - the liquid L and the solid S. A pure solution of either
A or B would have a single melting point, Tm (A) or Tm (B). For compositions in between, say
at the point identified with composition C(x), on cooling the liquid phase will first cool with a
single composition C(x), until it reaches the liquidus line.
An alloy of A and B would therefore cooling in the following way: first, it would cool to
a temperature below the melting point of pure A, until it reached the liquidus line of the
diagram. At this point it would become thermodynamically favourable for the alloy to split
into two phases, solid S which was relatively pure in A, and liquid with composition C(x).
Initially only very little solid would form, as the overall mixture of the two phases would have
to have the same overall composition as the alloy. As the alloy cooled down in the two-phase
field L+S, the alloy would solidify, with both the solid and liquid phases increasing in their
overall content of B, but the fractions of phases would change with more solid being formed
keeping the overall composition of the system the same. The solid phase would follow the limit
of solubility of S with temperature - the solidus, while the liquid phase L would follow the
liquidus.
On the cooling curve the latent heat of solidifi-

cation would therefore be evolved over the range
Temperature (K)
Liquid of temperatures between the solidus and liquidus

temperatures for an alloy of that composition,
So
lidu and so the cooling curve would appear as shown
s
Liquid in Figure 2.11. In this Figure, we can see that
+
Solid L iqu we can identify the liquidus and solidus temper-
idu atures for any alloy with composition from pure
s
Solid A to pure B, enabling us to determine the phase
diagram in Figure 2.9 experimentally. This di-
agram shows the phases that will form at equi-
librium, that is, at the lowest energy state the
Pure A Pure B
Composition (%B) system can be in. If the atoms are sufficiently
mobile, given enough time equilibrium will al-
Figure 2.9: Phase Diagram for a continuous
solid solution between alloying elements A and ways be obtained. Therefore phase diagrams are
B in both the liquid and solid phases. the most important tool we have for understand-
ing how microstructures form in materials. How-
ever, care should be taken when using equilibrium phase diagrams as they tell us only what
is favourable to occur; we require an understanding of kinetics (diffusion) to understand what
happens and how fast.
In order to calculate the fractions of the phases that form, we need to perform a calculation
that embodies our understanding of the physical processes that occur - in this case that the
mass of atoms is conserved. At a point in the middle of the two phase field, let us denote the
composition of the alloy C, of the solid CS (T ) and of the liquid CL (T ). The volume fraction of
the phases we will denote VS and VL . The volume fractions must add to 1, so
VS + VL = 1 (2.5)
Temperature (K)
Liquid L
Last liquid
disappears
First solid here
forms here
Solid S
A C(x) B
Composition (%B)
Figure 2.10: Formation of solid and liquid on cooling of an alloy of composition C(x).
Pure A A-B Alloy Pure B

Temperature (K)
Liquid
Liquid
Melting
point of A
Liquidus
Liquid + Temperature Liquid
Solid Solid Solidus
Temperature Melting
point of B
Solid Solid
Time (s)
Figure 2.11: Cooling Curve of A-B alloys showing complete solubility.
The composition of the system will then be given
Temperature (K)
by Liquid L
C = CS VS + CL VL (2.6)
because the mass of element B in the alloy is CL
given by the total of the mass in each phase.
CS
Therefore we have two equations and two un-
knowns V . Since VS = 1 − VL we can substitute
for VS into the second equation to obtain
C = CS (1 − VL ) + CL VL (2.7) Solid S
A C B
expanding and collecting terms we obtain
Composition (%B)
C = CS + VL (CL − CS ) (2.8)
Figure 2.12: Construction of the equilibrium
and therefore phases that form in a two phase region.
C − CS
VL = (2.9)
CL − CS
Therefore the volume fraction of liquid is given by
distance between the alloy composition and solidus
VL = (2.10)
distance between the solidus and liquidus
If we had substituted for VL instead of VS we would instead have obtained
CL − C
VS = (2.11)
CL − CS
The ratio between the fractions is therefore given by
VS CL − C
= (2.12)
VL C − CS
This is called the lever rule, as it is analogous to a lever. Imagine the volume fractions as
weights hanging on a lever, where the fulcrum of the lever is placed at the composition of
the alloy C and the lever is the horizontal line joining the compositions. Taking moments we
therefore find
VS (C − CS ) = VL (CL − C) (2.13)
Temperature (K) which is the same as Equation 2.12. This en-

Liquid L ables us to determine the phase fractions and
compositions that form at any point in a phase
CL diagram, which is amazingly useful - it enables
us to use phase diagrams to understand how a
CS microstructure will evolve in a material.
Returning to our alloy cooling curve, we can now

VS VL depict how the microstructure will evolve during
solidification. As the liquid cools, when we first
Solid S reach the liquidus we can draw a tie line between
A C B the liquid and solid and use the lever rule to de-
Composition (%B) termine the fraction of solid that forms. Since
C = CL at this point, VS = 0. At a tempera-
Figure 2.13: Construction of the lever rule: ture just below this point, V becomes greater
S
it is geometrically similar to taking moments
than zero and some solid starts to form. As so-
about the fulcrum of the alloy composition.
lidification proceeds, VS and CS increase. Also,
CL increases, but VL decreases. Eventually, as
the alloy cools the alloy composition enters the
single phase field again where it intercepts the
solidus line, and VS becomes 1; solidification is
complete.
Composition
All liquid, composition C. C

T1
Liquid
Distance
Solid crystals of composition C

T2 CS start to form, liquid Liquid
composition C. Solid
Solid crystals grow and CL

become richer in B. C
T3 Liquid Composition CL also CS
Solid Liquid
becomes richer in B.
Solidification complete.
Last liquid to solidify has Liquid
T4 composition CL. Solid has C
composition C. Solid
Figure 2.14: Microstructure development during cooling of a solid solution alloy.

Chapter 3
Eutectic Phase Diagrams
In the last lecture, we saw how a metal solidifies

for the case of a continuous solid solution. In this
Temperature
lecture, we will examine the situation where the
alloying elements do not have complete solubility Liqu
idus
L
for each other, but have only a limited capacity
So
lid
us
to take each other into solution. So again, we re- idus
L + α Eutectic Liqu
turn to a material composed of two atoms A and
s
Point
idu
B, but this time the A atoms prefer to form an
Sol
α phase and the B atoms a β phase. As is usu-
L+β
α β
Eutectic Temperature
ally the case, complete solubility in the liquid is
observed. Therefore we obtain a phase diagram
Solid solubility lim

it m
ility li
like Figure 3.1. The limit of stability of the liq- α+β

uid phase is the liquidus line, and this decreases
solub
in temperature as we move away from the pure

Solid
metals - the liquid becomes more stable relative

it
to the solid phases. There are two-phase regions
where we must form mixtures of both phases, A B
and then there are the solid phase fields them- Composition
selves. Their limits of stability with respect to Figure 3.1: Schematic eutectic phase diagram.
the liquid are the solidus lines, and with each
other simply the ‘solid solubility limits’.
Geometrically there has to be a point therefore where the liquid transforms to the two solid
phases at a single temperature, called the eutectic point. This occurs at the eutectic tempera-
ture. We will spend most of this lecture examining how alloys in different regions of the eutectic
phase diagram behave.
There are three or four regions we can identify, coloured in Figure 3.2. The blue region at the
edges denotes regions that will end up as a single phase at equilibrium at room temperature;
the red region denotes those compositions that enter the single phase field at temperature,
but exit it again in the solid state. The green region represents the eutectic and near-eutectic
compositions. Let us examine each one in turn.
An alloy in the single phase region, Figure 3.3, will solidify just as for the continuous solid
solution. Starting from the liquid, when it first reaches the liquidus line on cooling solid crystal
of α start to form. Solidification then proceeds and, for slow cooling under equilibrium condi-
22
3. Eutectic Phase Diagrams 23
tions, the α phase composition increases in B as the volume fraction increases and temperature
decreases. Eventually, when the solidus line is reached, solidification finishes and only solid α
phase remains. This phase then has the composition of the alloy. The cooling curve shows no
arrest because the latent heat of solidification is evolved over a range of temperatures and so
three distinct gradients are observed in the cooling curve - one for the liquid, for the solid and
a third during the solidification process.
For an alloy in the two-phase region, Figure 3.4, the same

solidification process is observed, but in the solid state the
Temperature
L alloy reaches the solubility limit of the α phase. At this tem-

perature, β phase crystals start to form, a process termed
L+α precipitation. This precipitation will often occur at the high-
energy features in the structure where there are nucleation
L+β sites for the new phase, such as at grain boundaries.
α β
α+β
At a temperature in the two-phase field T5 we can then use
the lever rule to determine the fraction of each phase;
C − Cα
Vβ = (3.1)
Cβ − Cα
A Composition B
As usual, this is the opposite ‘small distance’ divided by the
Figure 3.2: Different types of al-
‘big distance’ in the phase diagram. An alloy on the β side
loys that occur in different regions
of the phase diagram. of the diagram would behave similarly.
An alloy with the eutectic composition CE , Figure 3.5, behaves in another manner entirely. On
cooling, the liquid phase is stable to the lowest temperature possible, the eutectic temperature,
Temperature
T1 All liquid.
L
T2 Solid crystals
start to form.
L+α
Solid crystals grow
T3 and become richer
in B. Liquid also
becomes richer in B. L+β
α β
T4 Solidification complete.
Solid composition C.
Temperature (K)
α+β
Liquid
Liquidus
Liquid + Temperature
Solid Solidus
Temperature
Solid
A Composition B
Time (s)
Figure 3.3: Solidification sequence for a single-phase alloy.

Temperature
T1 All liquid.
L
T2 Solid crystals
start to form.
L+α
T3 Solidification complete.
Solid composition C.
L+β
T4
On cooling below
solubility limit of α,
α β
form some β phase.
α+β
T5
A Cα C Cβ B
Composition
Figure 3.4: Solidification and solid-state precipitation in a two-phase alloy.
Temperature
>TE All liquid.

L
At TE Solidifies into grains.

Each composed of L+α
α and β, usually in
fine lamellae.
L+β
TE α β
Temperature (K)
α+β
Liquid
Eutectic
Arrest at TE
Solid
Cα CE Cβ
Time (s) A Composition B
Figure 3.5: Solidification of the eutectic alloy.
Temperature
All liquid.
L
>TE LL α α L Solid grains of a start
α LL
to form in the liquid.
L+α
α α
LL α
At TE α Remaining liquid
L
α α
α
L
L
undergoes eutectic L+β

L α
α
solidification, again TE α β
usually in fine lamellae
of each phase.
α+β
Temperature (K)
Liquid
Liquidus
Liquid + Temperature
Solid Eutectic
Temperature Cα C CE Cβ
Solid
A Composition B
Time (s)
Figure 3.6: Solidification sequence in a near-eutectic alloy.
at which point it transforms into a mixture of α and β. The cooling curve therefore has a
eutectic arrest at TE where the latent heat of solidification is evolved, plus regions of cooling
of the liquid and solid phases. Often, this solidification results in a very fine-scale structure
composed of lamellae (plate-like structures) of α and β phase. The fraction of each phase in
the eutectic mixture we can again calculate using the lever rule;
CE − Cα
Vβ = (3.2)
Cβ − Cα
We are now prepared to look at the most complicated case, that of a near-eutectic alloy,
Figure 3.6. In this figure initially as the alloy cools from the liquid crystals of α form. As
the temperature decreases in the L + α region, the solute content in the α increases and the
volume fraction of α increases, whilst the liquid enriches in B. Eventually, the liquid becomes
so enriched in B that the eutectic point is reached at a composition CE . Over this first part of
solidification, the latent heat is evolved over a range of temperatures. The volume fraction of
the eutectic liquid is then
C − Cα
VL = VE = (3.3)
CE − Cα
The liquid then transforms to solid at the eutectic point, forming the eutectic lamellae where
the liquid was in between the grains of α that had already formed. The composition of both
the α lamellae and primary grains is then Cα and the β lamellae in the eutectic is then Cβ .
The volume fraction of β in the eutectic is then given by the lever rule;
CE − Cα
Vβ′ = (3.4)
Cβ − Cα
The overall volume fraction of beta is still given by

C − Cα
Vβ = (3.5)
Cβ − Cα
(a) (b) (c)
(d)
Figure 3.7: (a) A Hypoeutectic alloy (40wt.% Sn), showing dendrites of primary Pb in a Pb-Sn
eutectic, (b) a eutectic Pb-Sn alloy, (c) a hypereutectic alloy (80wt.% Sn) with dendrites of primary
Sn in a Pb-Sn eutectic, (d) the Pb-Sn binary eutectic phase diagram [micrographs from Richard
Dashwood; diagram from ASM handbook].
which is equal to the volume fraction of the eutectic liquid VE × Vβ′ . During this final part of
solidification the eutectic arrest is again observed in the cooling curve. Note that all eutectic
microstructures will be the same, since they all form from liquid of the same composition.
The lead-tin Pb-Sn phase diagram is shown in Figure 3.7. Primary lead (dark phase) composi-
tions are termed hypoeutectic (hypo=less than), whilst tin-rich compositions forming primary
tin (light phase) are termed hypereutectic. In your labs, you also examine the Al-Si eutectic
phase diagram, given in Figure 3.8. Notice that the primary phases that form during initial
solidification usually have a dendritic structure, whilst the eutectic lamellae are very much finer
in scale.
Often, intermetallic phases Ax B form in the phase diagram, and very often these intermetallic
compounds have no solubility range, Figure 3.9. This phase diagram can be divided in two,
700
660 oC
Liquid, L
L+ Si
α-Al + L
577 oC
α-Al
Temperature, oC
12.6
500
α-Al + Si
300
0 5 10 15 20
wt.% Si
Figure 3.8: The Al-rich end of the Al-Si binary eutectic phase diagram [redrawn from the ASM
handbook].
Temperature
Composition
Temperature
Temperature
Composition Composition
Figure 3.9: Schematic eutectic phase diagram with intermediate line compound Ax B; it can be
divided into two separate, non-interacting diagrams.
one eutectic diagram between α and Ax B and another eutectic diagram between Ax B and β.
These separated phase diagrams can then be treated in the same way as the normal eutectic
diagrams we have already seen.
The situation is slightly more complicated in the

case where the intermetallic has some solubility
Temperature
range, such as the phase γ shown in Figure 3.10.
L
However, despite the fact that there is no neat +
Liquid L
α L+ γ
division, we can still use this diagram using the α
simple approach of stepping through the solidi- γ
L+ γ
L+ β
β
fication sequence that we have already used.
An example of this type of more complicated

α +γ γ+ β
phase diagram is the Al-Cu system, which is
widely used as the basis for aerospace Al alloys,
e.g. in wing skins. Here we see a pure Al phase A B
Composition
and a θ phase that form a simple eutectic. At
richer copper compositions the situation is more Figure 3.10: Intermetallic compounds can
complicated because of the peritiectic transfor- themselves have some solubility range, such as
mations that occur, which you will meet later in the phase γ depicted here.
the degree programme.
Figure 3.11: The Al-Cu binary eutectic phase diagram [from the ASM handbook].
Chapter 4
Introduction to Thermodynamics
In the last lecture, we examined how to interpret and use eutectic phase diagrams to predict
and interpret microstructures. Over the next few lectures, we will examine how these phase
diagrams arise from thermodynamic considerations.
The Laws of Thermodynamics make some axiomatic statements that we shall use. Our con-
tention will be that systems tend towards equilibrium given the choice, based upon a blend of
arguments from the laws, i.e. they will attempt to minimise their energy.
First, let us consider a ball in a valley, Figure 4.1. It is stable

Potential
at point E at the bottom of the valley, i.e. for small pertur-
Energy bations a force will act that restores it to its original position.
Anywhere else on the hill it is in a state of unstable equilib-
rium where it is unstable to perturbations. It is also possible
for the ball to be in a metastable equilibrium, at point M.
M
Here the ball is stable to small perturbations, but for larger
E perturbations a lower equilibrium state can be found. Given
that, above absolute zero, there will always be thermal vibra-
Figure 4.1: Sketch of ball on
tions and excitations, a material will tend to be in a state of
hill, in a local minima.
stable equilibrium. It will be useful from herein to define some
thermodynamic quantities.
4.1 Internal Energy U
The first law says that the change in the internal energy is equal to the heat and work that it
does or are done by it;
∂U = ∂q − ∂w (4.1)
where we define the internal energy U as the sum of the kinetic, potential and electrical energy
of the atoms in the material, q is the heat energy and w is the work done. Generally we
consider thermodynamics as a system of atoms in a container under a regime of pressure and
temperature.
If the system expands the container, it performs work on the surroundings, equal to a force
29
times and distance or, equivalently, a pressure times the volume change of the system. Therefore
∂w = P ∂V (4.2)
Similarly, the change in temperature of the system is given by
∂q = C∂T (4.3)
where C is the heat capacity per mole of atoms and T the temperature. So we obtain
∂U = C∂T − P ∂V (4.4)
At constant volume therefore

CV
∂U = Cv ∂T (4.5)
where the subscript v reminds us that the heat capacity C is

the heat capacity at constant volume, also called the volumet-
ric heat capacity. We can therefore find the internal energy as
the integral of the heat capacity, together with the latent heats T
T
L due to the i phase changes and the energy at T = 0 K, U0 ;
Z T
Figure 4.2: Obtaining the heat
(4.6) content by integrating Cv from
X
U(T ) = U0 + Cv ∂T + Li
0 i
absolute zero.
Of course, this implies that measuring U is impossible because we can never measure U0 . In
practice what we do is we measure U0 relative to a standard reference material at a standard
reference state, and then measure changes from that reference.
4.2 Enthalpy H
Enthalpy is defined as
H = U + PV (4.7)
This is the constant pressure version of the internal energy, which more closely represents the
conditions under which experiments are performed. Therefore Enthalpy tends to be preferred
by experimentalists, whilst theorists find constant volume conditions easier to work with and
prefer internal energy. However, for condensed phases (liquids and solids), the differences will
be small. Taking the total differential of H we obtain
dH = dU + (P dV + V dP ) (4.8)
But, since dU = dq − dw = dq − P dV we find that
dH = dq + V dP (4.9)
and the change in heat dq = CdT . At constant pressure therefore we obtain
dH = Cp dT (4.10)
4. Introduction to Thermodynamics 31
where Cp defines the heat capacity at constant pressure. We can then measure the enthalpy is
a similar manner to before;
Z T X
H(T ) = H0 + Cp dT + Li (4.11)
0 i
Where H0 is the potential energy at 0 K. Enthalpy changes correspond to the heat required
when heating a material at constant pressure. Alternatively, we can measure the enthalpy
relative to a standard by measuring the heat evolved when dissolving the sample in a suitable
high-temperature liquid flux.
CP
T T
Figure 4.3: Obtaining the enthalpy content by integrating Cp from absolute zero.
The enthalpy change is therefore the amount of heat liberated or consumed when a reaction
takes place; if heat is required the reaction is termed endothermic and if heat is released it is
termed exothermic.
4.3 Entropy S
The direction of natural changes involves entropy, the degree of disorder in the system. The
third law of thermodynamics states that
As a system approaches absolute zero, all processes cease and the entropy of the system ap-
proaches a minimum value.
In an ideal thermodynamic system at equilibrium the entropy would be zero at absolute zero.
The second law of thermodynamics also states that
The entropy of an isolated system which is not in equilibrium will tend to increase over time,
approaching a maximum value at equilibrium.
So natural changes in the system tend to increase S, dS > 0. This does not preclude one part of
the system becoming more ordered whilst another becomes less ordered. In a reversible process,
the entropy change in the universe is zero, whereas an irreversible process is associated with
an increase in entropy; the third case, processes where the entropy of the universe decreases, is
impossible. The concept of entropy naturally gives rise to the idea of the arrow of time.
Entropy turns out to be a very important concept and has been worked on by very many
well-known scientists in history, including Boltzmann, Maxwell, Fermi, Claussius, Kelvin and
Planck, von Neumann, Kelvin and Carnot. Often, it is felt to be dismal in its outlook on life;
but science isn’t an outlook, just observation about the natural world.
The second law can also be restated to define the entropy, S, as

dq
dS ≥ (4.12)
T
where dq is the heat absorbed and T is the temperature. For a reversible process, which we
will most frequently consider, dq = T dS whereas for irreversible processes, dq < T dS. Since
we can measure dq from the heat capacity, then we can measure S;
Z T
Cp X Li
S = S0 + dT + (4.13)
0 T i
T
CP
T
T T
Figure 4.4: Obtaining the entropy content S by integrating Cp /T from absolute zero.
4.4 Gibbs Energy G
The Gibbs Energy (pre-1988: ‘Gibbs Free Energy’) is a quantity defined to be useful for defining
equilibria; the Gibbs energy is minimised when a system reaches equilibrium at a given pressure
and temperature. It is useful in that it allows us to do this by considering only the properties
of the system, not its surroundings. G is defined as
G = H − TS (4.14)
The total differential gives

dG = dH − SdT − T dS (4.15)
substituting for dH from Equation 4.9 gives
dG = V dP − SdT + dq − T dS (4.16)
For changes under isothermal, isobaric (pressure) conditions, dT = dP = 0, then
dG = dq − T dS (4.17)
Since T dS ≥ dq we immediately find that dG ≤ 0. For reversible changes dG = 0. Therefore

we see that G never increases, so that
G tends to a minimum at equilibrium.

4. Introduction to Thermodynamics 33
We also have the result that for two phases at equilibrium (at a particular T and P on a phase
boundary), the free energy of both phases is identical (e.g. L↔S in a pure metal). We can
obtain G from measurements of H and S.
In traditional use, the moniker ‘free’ was attached the Gibbs Energy, denoting the energy
available to do work; the Gibbs energy is the maximum amount of non-expansion work that
can be extracted from a closed system (which can only be obtained by a reversible process).
However, the concept is often felt to be misleading and therefore the term has been dropped
by IUPAC.
4.5 Relations for equilibrium
For equilibrium situations where dq = T dS we find from equation 4.16
dG = V dP − SdT (4.18)
Therefore we obtain the following relations

∂G
Entropy S = − (4.19)
∂T P

∂G
Volume V = (4.20)
∂P T
2
∂H ∂S ∂ G
Heat Capacity CP = =T = −T (4.21)
∂T P ∂T P ∂T 2 P
4.6 Helmholtz Energy F
The Helmholtz energy F is the equivalent of G for changes at constant volume, defined as
F = U − TS (4.22)
4.7 Intensive vs. extensive variables
We can distinguish two groups among the thermodynamics variables we have been defining
here. T , P and density are intensive variables that don’t change when two identical systems
are combined. V , U, H, S, G and F are all extensive variables that are (i) proportional to
the mass of the system, (ii) additive when two identical systems are combined and (iii) are
functions of state - i.e. can be used to define the state of the system. Typically, we quote these
extensive variables per mole in the system, i.e. for an energy, in kJmol−1 .
4.8 Energy of a single phase of constant composition
We take as our starting points Equations 4.16 and 4.17, that

G
dG = V dP − SdT + dq − T dS (4.23) H gra
die
nt =
-S
and the condition of reversible equilibrium, such that dq =
T dS. At constant pressure dP = 0 and so

dG
= −S (4.24)
dT P
T
0K
Therefore, since S increases with temperature, G must con-
tinuously decrease with temperature, always following the Figure 4.5: Form of variation of G
general form below. The intercept at 0 K is H0 , which is with T .
equal to G(0 K). The gradient is −S, and becomes increas-
ingly negative as T increases.
4.9 Two phases of identical composition
Each phase has its own G vs. T curve, as shown below. Where they intersect the two phases
may coexist at equilibrium, at TE . Below TE only one phase will exist in stable equilibrium,
but the other phase could exist in a metastable state; above TE the roles are reversed. When
one phase transforms into another, even though ∆G = 0 at TE , there are discontinuous changes
in entropy and enthalpy associated with the release of latent heat of transformation. Therefore
the transformation is termed first order.
If we define ∆ to be the change in an energy between two

different states, such as ice ↔ water, we define; G
∆G = GL − GS = 0 (4.25) ice
∆S = SL − SS ≥ 0 (4.26)
∆G = ∆H − T ∆S = 0 (4.27)
w
at
er
the last obtained if we impose the condition that ∂T = 0,

T
i.e. isothermal conditions. Therefore TE
∆H = T ∆S (4.28) Figure 4.6: Form of variation of

G with T for the phase change from
Since ∆S must be positive, we must supply latent heat to solid ice to liquid for water.
make the transformation ‘go’.
Chapter 5
Thermodynamics of Solutions
Having examined how pure materials transform in terms of their G-T curves, we are now in a
position to consider how dilute solutions behave.
If we had a complete theory of alloys it would be possible to deduce, e.g. U0 from first principles
quantum mechanical calculations. However, such calculations would need to be rather more
precise than is commonly attainable since, because of the nature of the metallic or free electron
bond, the free energies of formation tend to be rather similar. This makes it difficult to predict
reliably which alloy structure would be stable. Even the best theoreticians can often only
predict trends in metals. However, by making a small number of very simple assumptions we
can reproduce the form of the Gibbs energy curves and therefore the form of the phase diagrams
we observe.
Let us consider when we make of system that is a substitutional solid solution of N atoms,
with fraction xA of A atoms and fraction xB of B atoms (xA + xB = 1), by mixing together the
pure metals. We will define the G of the alloy as the sum of the G’s of the components plus
the energy of mixing, ∆Gmix , such that,
G = GA xA + GB xB + ∆Gmix (5.1)
This energy of mixing will be composed of (i) the enthalpy of mixing associated with the A–B
bonds, ∆Hmix and (ii) an entropy of mixing ∆Smix associated with the random mixing of A
and B atoms. Therefore we will write, following Equation 42,
∆Gmix = ∆Hmix − T ∆Smix (5.2)
5.1 Enthalpy of mixing ∆Hmix
Let us assume that only the potential energy part of H changes significantly on mixing, so that
∆Hmix = ∆Umix , i.e. there is no volume change on bringing together the system of A and B
atoms. Then, if we define wAA as the interaction energy of an A-A bond, wBB as the energy
of a B-B bond and wAB as the energy of an A-B bond, we will be able to find the total energy
by adding up the number of bonds. All of these energies w will be negative, as the zero in
potential energy if conventionally for infinite separation and bringing atoms together generally
is an exothermic process. We assume that each atom is co-ordinated with z neighbouring atoms,
so the total number of nearest neighbour pairs, or bonds, is 21 Nz.
35
Chapter 6
Faster Solidification: the Scheil

equation
So far, we have considered solidification to proceed in equilibrium conditions only, where slow
cooling conditions apply and the solid and liquid compositions are those given by the tie line
in the liquid + solid two-phase region. However, diffusion in solid phases is generally much
slower than diffusion in liquids. Therefore another approach to solidification is to consider
what happens when diffusion is limited in the solid but infinitely fast in the liquid, which
corresponds to the industrial situation where the cooling rate can be quite rapid. Expressing
the diffusion coefficient as D, this is equivalent to considering DS = 0 and DL = ∞. Then, the
first solid to form would enrich the liquid in solute by removing relatively pure material from
the system. The liquid would then move to a more enriched composition, and so the next solid
to form would form from a relatively enriched liquid. The situation will be like that depicted
in Figures 6.1–6.2.
We can equate the areas in Figure 6.1, which are amounts of solute, considering the change in
liquid composition that occurs due to the solidification of some fraction of liquid;
(CL − CS )dVS = VL dCL (6.1)
From the phase diagram, we can define the partition coefficient k to be
CS
k= (6.2)
CL
C
Solid Liquid
Temperature (°C)
Concentration C
CS Liquid dCL
CL
CL
α Liquid + α CS
C
α+ Al2Cu
Composition (wt.% Cu) dVS
Fraction Solid V
Figure 6.1: Incremental change in liquid composition with change in fraction solid.
42
6. Faster Solidification: the Scheil equation 43
Solidification so k < 1. In addition, mass must be conserved

C Begins
so
VS + VL = 1 (6.3)
Temperature (°C)
Liquid
Therefore we can obtain

Liquid + α
α Solid Liquid
Cu Concentration
α+ Al2Cu CL (1 − k)dVS = (1 − VS )dCL (6.4)
CS CL CL
Composition (wt.% Cu) C
CS which is a first order differential equation. It
will be subject to the boundary condition
(a) Fraction Solid
Solidification
C Progresses CL = C at VS = 0 (6.5)
Temperature (°C)
Liquid i.e. that the liquid composition is the alloy

composition at the beginning of solidification.
α
Liquid + α
Solid Liquid
We can rearrange the differential equation to
Cu Concentration
α+ Al2Cu
CL obtain
dCL dVS
CS CL CS
C = (1 − k) (6.6)
Composition (wt.% Cu)
CL 1 − VS
(b) Fraction Solid

integrating;
... final Eutectic
C solidification CL VS
dCL dVS
Z Z
= (1 − k) (6.7)
C CL 1 − VS
Temperature (°C)
0
Liquid
Liquid + α
[ln CL ]CL VS
C = (k − 1) [ln(1 − VS )]0 (6.8)
α Solid Liquid
Cu Concentration
α+ Al2Cu CS
CE so
CS CE
Composition (wt.% Cu) C CL
ln = (k − 1) [ln(1 − VS ) − ln(1)] (6.9)
C
(c) Fraction Solid
so
CL
= (k − 1) ln(1 − VS ) ln (6.10)
Figure 6.2: Evolution of solidification where C
there is no diffusion in the solid - (a) at the begin- and finally
ning of solidification, (b) mid-way and (c) at the
end.
CL = C(1 − VS )k−1 (6.11)
or, for the composition of the solid
CS = kC(1 − VS )k−1 (6.12)
This is called the Scheil Equation. It describes, for a continuous solid solution, the evolution
of the solid and liquid compositions for the case where diffusion in the solid is zero and liquid
mixing is fast. This is the situation that produces the most extreme compositional variation
in the final solid, compared to the slow cooling or equilibrium assumption that there is no
variation in the solid.
We can use the Scheil equation in several ways; to describe the maximum volume fraction of
eutectic that might form during solidification or to describe the evolution of composition of
the solid during casting. Note in addition that, compared to equilibrium cooling, the freezing
range may be greater for Scheil solidification.
This variation in the solid composition is 0.20

k=0.5
called segregation. In Al-Cu alloys, often this 0.18
is visible in an etched micrograph as the phe- 0.16
nomenon of coring, where the solidified grains 0.14
or dendrites appeared to be cored.
0.12
C (-)
The Scheil equation describes the situation 0.10
where there is no eutectic reaction in the 0.08

CL
phase diagram. Where a eutectic exists, when 0.06
CL reaches the eutectic point (as it always will 0.04
since CL → ∞ as VS → 1), then the eutectic C=0.04
0.02 CS
reaction will occur, with the two solid phases
0.00
being precipitated out of solution as the eu- 0 0.2 0.4 0.6 0.8 1
tectic mixture. The graph will therefore look
VS (-)
more like the one below, where once the eu-
tectic is reached the two phases of solid are at Figure 6.3: Scheil’s equation for the evolution of
each of their solubility limits. fraction solid and liquid during rapid solidification.
The fact that we don’t see eutectics in all so-

lidified alloys in eutectic systems therefore im-
plies that some diffusion indeed occurs in the
solid. Therefore the Scheil Equation describes
an extreme - an upper bound - to the amount
of segregation that occurs, whereas equilib-
rium slow cooling describes a lower bound (no
segregation).
(a)
(b)
Figure 6.5: Eutectic observed in an indus-
trial Al-4wt.%Cu casting. Under equilibrium Figure 6.4: (a) Coring in a cast AA7020 alu-
cooling conditions, no eutectic should be ob- minium alloy (courtesy D Garcia), and (b) close-up
served, which indicates that diffusion in the view of coring.
solid was restricted in this case.
Chapter 7
Diffusion, Nucleation and Growth
7.1 Homogenisation
The consequence of this alloy segregation is that the composition varies across the grains of the
material, which often take the shape of the dendrites (tree-like grains) shown in Figure 6.5. At
the end of the solidification sequence thermal expansion will mean that the first solid to solidify
will have shrunk, which in the absence of a good feed of liquid metal to the terminal eutectic
will mean that shrinkage pores may appear in the casting.
These two issues - the variation in composition and the appearance of casting pores - mean
that as-cast materials usually have poor mechanical properties. The pores act as small cracks
in the material, initiating fatigue cracks that grow to early failure. Therefore heat treatment
and further mechanical processing is often applied to even up to composition variations (ho-
mogenisation) and close the pores.
Homogenisation is typically performed at temperatures all the way up to the melting point,
for times varying from a few hours to a whole day. It proceeds by the diffusion of atoms in
the material. Atoms move down the gradient in internal energy, which is typically down the
gradient in composition. We relate the flux JB of B atoms - the number passing per unit area
per unit time - to the composition gradient ∂CB /∂x through Fick’s First Law
∂CB
J = −DB (7.1)
∂x
It is also interesting to consider the diffusion of an individual atom jumping from point to point
in the lattice, a process known as a random walk. √ It can be shown that after n jumps an atom
will, on average, have moved a net distance of αn, where α is the jump distance. In diffusion
problems, the characteristic distance is D, so we find that the distance r a diffusing species
moves is typically √
r ∝ Dt (7.2)
By considering the rate at which atoms enter and leave a control volume it is fairly easy to
derive from Fick’s First Law the following equation
∂C ∂2C
=D 2 (7.3)
∂t ∂x
which is Fick’s Second Law. It says that the rate of change of the composition is proportional
to the curvature of the composition curve.
45
These themes will be picked up and developed more fully in the rest of the course.
7.2 Processing of Al Alloys
Aluminium is an extremely abundant, light, and cor-

rosion resistant material. Unfortunately in its pure Control Valve Molten Metal
form it is extremely soft and therefore of no engineer- Transfer Trough
ing use. In general most high strength aluminium al- Baffle
loys are strengthened by alloying aluminium with other Quench Mold
elements. One particularly popular alloying addition is Water
Cu. When Cu is added to aluminium (normally no more Inlet Water Box
than 4wt.%) then strength can be increased by up to Water
10×. The process by which this occurs is known as pre- Spray Ingot
cipitation hardening. Liquidus Bottom
Surface Block
In general high strength aluminium alloys are processed
Hydraulic
in the following way. The aluminium is melted and any Ram
alloying elements added. The solidification of the melt is
normally conducted by semi-continuous DC (direct chill)
casting. The molten metal is cast onto a hydraulic ram
which is slowly lowered though a water cooled mould.
This process produces ingots that are several meters long
and can weigh up to 25, 000 kg. This process cools the
metal relatively rapidly, and results in a 100% equiaxed
dendritic microstructure. This is aided with the addition
of a grain refiner to the melt such as TiB2 to provide
heterogeneous nucleation sites for the solid aluminium
crystals. However the rapid cooling also gives rise to
microsegregation, which means that after solidification
the ingot has to be given a homogenisation treatment.
After the microstructure has been homogenised the in-
got will be worked into its near final shape by processes
such as hot rolling, extrusion or forging. This will nor-
mally take place at around 300–500◦C. After this pro-
Figure 7.1: The casting of Al ingots
cessing a very soft microstructure is obtained, that con- for rolling. In a semi-continuous pro-
tains α grains with coarse second phase particles at the cess, the Al ingot is solidified in a water-
grain boundary. Prior to being used the alloy will be cooled mould.
heat treated (solution treated and aged) to achieve full
strength. This occurs by precipitation of fine second
phase particles within the α grains.
7.3 Nucleation and Growth of a New Phase
Previously, we have considered the thermodynamics of phase transformations without any

consideration of the effects that the interfaces between phases have on the situation. Naturally,
one can imagine that there will be an energy associated with a surface or interface - for example,
7. Diffusion, Nucleation and Growth 47
the dangling bonds at the surface between a metal and vacuum, or more generally at any surface
or interface. Where a transformation is favourable (reduces the overall energy), then some of
the energy given up on transformation is available to be expended in creating the free surface.
The first step will therefore be to consider what energy is available to produce interfaces - the
driving force.
Driving Force for Transformation
For a first-order phase transformation between two phases of the same composition then we
can write
∆G = ∆H − T ∆S (7.4)
When considering the driving force, we take ∆G to be positive for a natural change. Then, at
the equilibrium temperature Te ,
∆G = 0 (7.5)
and so
∆H = Te ∆S (7.6)
We can therefore substitute for ∆H into the first equation to obtain
∆G(T ) = Te ∆S − T ∆S
(7.7)
= ∆S(Te − T )
Note that we have assumed here that ∆H and ∆S are independent of T , which will be true
when both phases have the same CP , which is a good approximation for condensed matter, as
long as T is close to Te .
We refer to (Te − T ) as the supercooling ∆T . The implication of this calculation is that the
driving force for transformation - the excess energy that is available to create new surfaces, for
example - is proportional to ∆T .
Nucleation of a New Phase
We can now consider what happens when we first start forming a new phase during a first
order phase transformation between two phases of identical composition. The simplest case is
where the new phase grows from an old phase with no heterogeneities. Such flaws in the crystal
structure - such as precipitates, voids, vacancies, grain boundaries or dislocations - are features
with raised internal energy that can acts as nucleation sites. Here we ignore these - the case of
homogeneous nucleation.
First we consider the driving force for transformation, the ∆G from Equation 7.7, which we
express per unit volume as ∆Gv (in kJm−3 - we do this by multiplying ∆G in kJmol−1 by the
molar mass mr in kgmol−1 and the density ρ in kgm−3 so ∆Gv = ∆Gmr ρ).
Defined as a the Gibb’s energy of the old phase minus that of the new, ∆Gv is a positive
quantity for a natural transformation.
We take the new interface created between the two phases to have an energy of σ per unit area,
which is again a positive quantity. The interface contributes an excess energy to the system and
is the energy associated with the defect in packing that must occur between the perfect crystal
lattices of the two phases. We assume that the interfacial energy σ is essentially independent
of T .
Now consider the case of a spherical nucleus of radius r. We assume that the formation of this
nucleus of new phase does not induce any stresses in the surrounding material, which is the
situation that occurs, for example, for the nucleation of solid in a liquid.
The work W of forming the nucleus is then the balance of the energy gained from the trans-
formation (a volume term) and the energy required to form the surface.
4
W = − πr 3 ∆Gv + 4πr 2σ (7.8)
3
The curve for W has a maxima, W ∗ at a crit-

ical radius r ∗ . Particles smaller than r ∗ in the W Surface
figure can therefore reduce the energy of the
system by shrinking, and particles larger than
r ∗ by growing. Hence
for r < r ∗ , a nucleus will shrink

W*
for r > r ∗ , a nucleus will grow r* r
We can evaluate r ∗ by finding the maxima in Volume

the curve;
dW
= −4πr 2 ∆Gv + 8πrσ (7.9)
dr
Figure 7.2: Variation of Work of formation W
dW
setting dr
= 0 at r = R∗ we obtain with nucleus size r.
0 = −4πr 2 ∆Gv + 8πrσ

(7.10)
0 = −∆Gv r ∗ + 2σ
so
2σ
r∗ = (7.11)
∆Gv
We can evaluate W by substituting for r in Equation 7.8 to obtain
∗ ∗
3 2
∗ 4 2σ 2σ
W =− π ∆Gv + 4π σ
3 ∆Gv ∆Gv
σ3

32
= π 16 − (7.12)
∆G2v 3
3
16π σ
=
3 ∆G2v
From Equation 7.7 we know that as T → Te , ∆Gv → 0, so r ∗ → ∞ and W ∗ → ∞, so nucleation
becomes impossible.
The maxima in the curve for W is termed the barrier to nucleation. In effect, a particle of
size r ∗ must spontaneously arise by atomic vibrations and diffusion in order for there to exist
7. Diffusion, Nucleation and Growth 49
a driving force for particle growth. If r ∗ is very large, then this will not occur and therefore
quite significant undercooling must occur for precipitation of the new phase to take place.
An example of this is purified and filtered water, where significant undercooling must be imposed
before homogeneous nucleation and hence freezing takes place.
Effect of Strain Energy
A volume change is likely to accompany the nucle-

W Surface ation of one solid in another, which we can consider
to be a strain. Of course, there will be some elas-
tic accomodation between the elastic matrix and
elastic precipitate phases, but the total strain en-
ergy will scale with the volume of the nucleus and
W* the difference in the lattice parameters in the un-
strained state. This acts to adsorb some of the
r* r Gibbs Energy driving force, so the work of nucle-
ation is modified;
Volume
4
W = − πr 3 (∆Gv − CKγ 2 ) + 4πr 2 σ (7.13)
3
Figure 7.3: Increase in W ∗ and r ∗ when where C is a constant, K is the bulk modulus and γ
strain energy is considered. is the strain or fractional difference in molar volume
of the two phases. As shown in the Figure below,
the effect is to increase r ∗ and W ∗ , possibly to the
point where nucleation becomes impossible.
Heterogeneous Nucleation
Nucleation may be made easier by the presence of particles in the original phase. This will be
discussed more in the Spring term, but here it will suffice to realise that the amount of new
surface that must be created can be reduced by precipitating the new phase on a favourable
surface. This reduces the size of the energy barrier W ∗ and therefore reduces r ∗ , making
nucleation easier and reducing the amount of undercooling that must take place for precipitation
of the new phase to occur.
We will consider the rate of nucleation in the next lecture.

Chapter 9
Microstructure and Properties of Plain

Carbon Steels
This Chapter covers the second half of lecture 8 and the whole of lecture 9. In years where the
course is over ten sessions, it also forms the first half of the 10th session, followed by a review.
Iron-based alloys are a foundation-stone of our civilization. Almost everything we do is depen-

dent on cheap, light weight, strong steels in a huge variety of forms, from forgings to sheet to
extrusions. The iron-carbon phase diagram is incredibly rich, with a number of phases and this
allows us to attain great variability in the microstructures we form in steels, which allows us
to attain strengths anywhere from 200 MPa to 2 GPa. Most often, other alloying elements are
added to further alter the situation, but most of the metallurgy can be understood using just
the Fe-C binary diagram.
At this stage in the course, we have examined most of the concepts required to understand
steels, so this is the point at which we put everything together and use our new understanding.
On solidification at 1534◦C pure iron initial forms as the bcc phase δ. Pure iron undergoes
two polymorphic changes, first at ∼ 1400◦C to the fcc austenite γ phase, and then at 910◦ C
to the bcc ferrite α phase, which is the stable form at room temperature. The carbon atom is
smaller than the iron atom and forms interstitial solid solutions with all three forms of iron.
The maximum solubility of C in δ, γ, and α is 0.1, 2.0 and 0.03 wt.%. respectively.
The Fe-C diagram shown is not a complete diagram, as it is only constructed for C contents
of less than 6.67wt.% (25 at.%), the composition of Fe3 C, an extremely hard and brittle inter-
metallic phase. Alloys with C contents greater than 6.67 are of little commercial interest, and
therefore this region of the phase diagram is rarely presented. Alloys with a carbon content
less than 2.06 (the maximum solid solubility of C in austenite), are referred to as steels (and it
composition in this range we will discuss in this course), whilst those greater than 2.06wt.% C
are referred to as cast irons. The majority of commercial steels have a carbon content of less
than 1wt.%, with the greatest production being in the range 0.2 to 0.3 wt.%C.
On cooling from the liquid, low C content Fe alloys undergo a peritectic transformation, and
enter the single phase austenite field, whilst steels with a higher C content solidify directly to
austenite. As it can be assumed that on cooling sufficient time is available to permit diffusion,
and bring about a homogeneous solid solution, the influence of the peritectic reaction on sub-
sequent lower temperature transformations can be ignored. Therefore by the time a steel of
54
9. Microstructure and Properties of Plain Carbon Steels 55
Figure 9.1: The iron-carbon phase diagram.
any composition has reached 1200C we can consider it as being a homogeneous solid solution
of C in γ-Fe (austenite).
The most important transformations that occur in steel are those that occur as we cool austenite
to room temperature. Looking at the phase diagram we can see that on cooling, austenite will
undergo a transformation that appears to be very similar to a eutectic transformation. In
fact the only difference between this reaction and a eutectic is that austenite is a solid not
a liquid. Such a solid state eutectic transformation is called a eutectoid transformation, and
is completely analogous to its liquid state counterpart. It is this eutectoid reaction which we
will now study in more detail. The term ‘Hypo-eutectoid’ is used to describe steel with a C
content less than 0.8wt.%, the eutectoid composition, whilst steels with a C content greater
than 0.8wt.% are referred to as ‘Hyper-eutectoid’.
9.1 Equilibrium Cooling of Steels
Eutectoid Composition
Eutectoid Steels
Hypo-eutectoid Steels Hyper-eutectoid Steels
Above TE
900 All Austenite
Temperature (°C) Austenite

800 Ferrite & Cementite &
Austenite Austenite
BelowTE
0.02% 0.8%
All Pearlite
700
Ferrite & Fe3C
Cementite (6.7wt.%C)
600
0.0 0.2 0.4 0.6 0.8 1.0 1.2 1.4 1.6
Wt. % Carbon
Figure 9.2: Formation of pearlite at the eutectoid temperature.
When a steel of composition of 0.8%C (eutectoid composition) is cooled to 723◦ C austenite will
decompose to form ferrite and cementite, which form as alternate plates of each phase, to yield
a structure called pearlite. The ferrite fraction in pearlite can be calculated using the lever rule
6.7 − 0.8
fraction of ferrite = = 88% (9.1)
6.7 − 0.02
As the density of ferrite and cementite are similar the plates (lamellae) of ferrite and cementite
have a ratio of widths approximately 8:1 (which gives a ferrite fraction of 88%). The decompo-
sition of austenite to form pearlite occurs by nucleation and growth, with nucleation occurring
heterogeneously at grain boundaries. The formation of pearlite is depicted in Figure 9.3.
a) Initial Fe3C nucleus forms b) α nucleates from C-depleted c) growth of α rejects C into γ,
at γ grain boundary γ around Fe3C plate nulceating more Fe3C plates
Figure 9.3: Co-operative growth of pearlite from a γ grain boundary.
Nucleation occurs by the formation of a lamella of

cementite that forms at an austenite grain bound-
ary and grows into an austenite grain. As this plate
grows, it removes carbon from the adjacent regions
of austenite. As a result the concentration of car-
bon in the austenite in contact with the cementite
falls, until it reaches a value where ferrite is nucle-
ated. As ferrite can only contain very low levels
of carbon, the growth of ferrite results in a build
up of carbon adjacent to the ferrite. This build-up
continues until a new layer of cementite nucleates,
50 μm
the process then repeats itself, and the alternating
lamellae of a pearlite colony are formed. Growth Figure 9.4: Microstructure of a eutectoid
of pearlite colonies occurs not only by the nucle- steel - 100% pearlite.
ation of additional lamella, but also by the advance
of ends of the lamellae. Nucleation of a pearlite
colony can also occur at the interface of an existing colony and the parent austenite. Pearlite
colonies grow unimpeded until they impinge on adjacent colonies.
Hypo-eutectoid Steels (< 0.8 wt.% C)
All austenite
Hypo-eutectoid Steels
900 a
Temperature (°C)
Pro-eutectoid ferrite forms b Austenite
at austenite grain boundaries 800 Cementite &
Ferrite &
Austenite Austenite
0.02% c 0.8%
700 d
Ferrite & Fe3C
Remaining austenite (6.7wt.%C)
Cementite
transforms to pearlite at eutectoid
600
0.0 0.2 0.4 0.6 0.8 1.0 1.2 1.4 1.6
Wt. % Carbon
Figure 9.5: Development of the microstructure of a hypo-eutectoid steel during equilibrium cooling.
Let us now look at the transformations that will oc-

cur when we slowly cool a hypo-eutectoid steel (for
example with a composition 0.3 wt. % C) from the
austenite phase field to room temperature (point a
to point d in the Figure). Initially we have grains of
pure austenite, and all the carbon is in solid solu-
tion. On cooling no transformation will take place
until the temperature reaches point b. At this point
the transformation begins, with ferrite being nucle-
50 μm ated at the austenite grain boundary. As the solu-
bility of C in ferrite is very low this transformation
Figure 9.6: Microstructure of a hypo- is associated with the rejection of C into the re-
eutectoid steel - grain boundary ferrite with maining austenite. As the temperature is further
pearlite in between. reduced the amount of ferrite present increases and
the concentration of C in the austenite increases.
When the temperature reaches point c, the concentration of C in austenite reaches 0.8% (the
eutectoid composition). The proportion of ferrite and austenite at this point can be calculated
using the lever rule, i.e.
0.8 − 0.3
fraction of ferrite = = 64% (9.2)
0.8 − 0.02
On cooling the alloy below the eutectoid temperature (to point d) all the remaining austenite
is transformed, via the eutectoid reaction, to produce pearlite. The fraction of ferrite in the
pearlite is the same as before, as the composition of the austenite forming the pearlite is always
the same. Continued cooling to room temperature (point e) causes no visible change in the
microstructure. Since the solubility of carbon in ferrite decreases with T a change should occur,
but it is extremely small.
Hyper-eutectoid steels (> 0.8 wt.% C)
All austenite
Hyper-eutectoid Steels
f
900
Temperature (°C)
Pro-eutectoid cementite forms Austenite
at austenite grain boundaries 800 Cementite &
Ferrite &
Austenite Austenite
0.02% 0.8% g
700 h
Ferrite & Fe3C
Remaining austenite (6.7wt.%C)
Cementite
transforms to pearlite at eutectoid
600
0.0 0.2 0.4 0.6 0.8 1.0 1.2 1.4 1.6
Wt. % Carbon
Figure 9.7: Development of the microstructure of a hyper-eutectoid steel during equilibrium cooling.
Let us now consider the cooling of a hyper-eutectoid

steel (for example with a composition of compo-
sition 1.2 wt.% C) from the austenite phase field
(point f). Transformation of the austenite begins
when the temperature falls to point g. At this
point cementite starts to form. As cementite is
rich in C the concentration of C in the austenite
decreases as the temperature falls, and more ce-
mentite is formed. By the time the temperature
reaches point h (just above the eutectoid tempera-
ture), the concentration of carbon in the austenite
falls to 0.8% (the eutectoid composition). At this 50 μm
point the fraction of cementite is
Figure 9.8: Microstructure of a hyper-
1.2 − 0.8 eutectoid steel - grain boundary cementite
fraction of Fe3 C = = 6.7% (9.3) Fe3 C with pearlite in between.
6.7 − 0.8
Below the eutectoid temperature all the remaining austenite transforms to pearlite. One of the
distinguishing features of hyper-eutectoid steels is the high percentage of pearlite present, in
this case ∼ 93.3%.
9.2 Non-Equilibrium Cooling of Steels
In the previous section we have looked at the microstructures of steels that are obtained when
they are cooled under equilibrium conditions from the austenite phase field to room temper-
ature. To achieve equilibrium conditions in reality entails placing the steel into a furnace,
heating the steel into the austenite phase field and then turning the furnace off and letting the
steel cool down in the furnace. This process takes many hours and is known as a ‘full process
anneal’. This is the softest state that a plain carbon steel will exist in. The strength of the
steel can be improved by a process called normalising. In this case the steel is again heated into
the austenite phase field, but in this case once the temperature of the steel has equilibrated
the steel is removed from the furnace and the allowed to cool down to the room temperature
in still air. The microstructures of normalised steels are similar to those shown above, however
the scale of the microstructure is refined (the ferrite grain size is reduced and the interlamellae
spacing in the pearlite is reduced), leading to a higher strength steels.
The two previous cooling paths are rela-

Slo tively slow and allow plenty of time for the
w eutectoid reaction to take place. That is
Co Pearlite
Fast Cooling
oli to say that as the temperature falls be-

ng
low the eutectoid temperature there is suf-
ficient time for the carbon atoms to dif-
Temperature
fuse out of the austenite to form Fe3 C, and

then the austenite to transforms to ferrite.
Martensite However if the steel is cooled very quickly
from the austenite phase field (i.e. by wa-
ter quenching) then a new structure known
as martensite can be formed. Martensite is
simply a supersaturated solid solution (i.e.
it contains more C than it should have)
of carbon in iron. The transformation of
austenite to martensite is a diffusionless
Time transformation, and can be thought of as
the fcc Fe structure trying to transform to
Figure 9.9: Effect of cooling rate; fast cooling rates bcc, but due to the presence of the C atoms
can lead to martensite formation. (which cannot diffuse away) this cannot oc-
cur, and a body centred tetragonal (bct)
structure is formed instead (see figure below). It is referred to as a displacive transformation,
as distinct from the reconstructive transformation that occurs when diffusion results in complete
reconstruction of the crystal lattice. The bct structure is highly stressed due to the entrapment
of the C atoms and as a result martensite is often hard and brittle.
As martensite is extremely brittle it is

Fe rarely used in engineering applications, ex-
cept where the steel has been alloyed to
produce a softer form of martensite. How-
C ever, in plain carbon steels by controlling
the cooling of a steel component it is pos-
Unit cell of fcc austenite Two unit cells of fcc austenite sible to create a surface layer of martensite
with a softer core of ferrite/pearlite. This
yields a tough component with a heard,
wear-resistant surface. Where the trans-
formation to martensite is useful is in a
process known as the quenching and tem-
Body centred tetragonal unit cell
pering of steels. In order to increase their
representation of austenite strength, steels can be quenched, from the
austenite phase field, to room temperature,
in order to form martensite. However steels
in the martensitic condition are too hard
and brittle for normal service. However
Body centred tetragonal unit cell Body centred cubic unit uell the properties are improved by re-heating
of martensite of ferrite
(tempering) the steel to a temperature be-
Figure 9.10: Construction of the martensite unit low the eutectoid temperature. During
cell: the bct unit cell can be constructed from two tempering carbon is removed from solution
unit cells of the austenite phase. by the precipitation of iron carbides, and
the matrix reverts to the bcc structure.
Martensite contains a lot more carbon in

solid solution than iron can normally ac- Ferrite with Precipitates of Fe3C
commodate. As a result the driving force
for the removal of carbon from solid solu-
tion and the formation of Fe3 C is extremely
high. The only factor that stops this hap-
Temperature
pening at room temperature is the fact
that diffusion of carbon cannot take place. Martensite
As a result martensite is in a metastable
state (i.e. it is thermodynamically unsta-
ble, but kinetically stable). If the struc-
ture is heated to a temperature where car-
bon can now diffuse the structure will try
and revert to the equilibrium condition of
ferrite and Fe3 C. As the driving force for
this transformation is very high this will Time
result in the formation of a large number Hardness (VHN) Ductility (%)
of small crystals of Fe3 C (known as pre-
cipitates). Once the carbon has been re- Pearlite
moved from solid solution the remaining
martensite transforms to ferrite. Whilst
the tempering process results in a reduc-
tion in the strength of the steel compared Martensite
to the martensitic condition, the ductility

and toughness are much improved.
Tempered
Martensite
If we cool a steel too quickly to form
pearlite but too slowly to form marten- 0 500 1000 0 10 20 30
site we can get yet another microstructure
known as bainite. Bainite is a very refined Figure 9.11: Formation of a fine microstructure by
microstructure containing ferrite and Fe3 C quenching to martensite and the tempering, and the
(as is the case with pearlite). The transfor- effect on properties.
mation starts with the nucleation of ferrite
plates at the austenite grain boundaries. The growth of these plates is similar to the formation
of martensite, i.e. it is displacive. However in this case as the temperature is high enough
for C to diffuse out of the lattice, the fcc structure can fully transform to bcc. As the ferrite
plates form the remaining austenite becomes richer in C. Eventually Fe3 C precipitates in the
remaining austenite layers in between the ferrite platelets. Bainite has a good combination of
strength and toughness, because it is very fine in scale but does not contain brittle martensite.
Pearlite Bainite
50 μm 1 μm
Figure 9.12: Microstructure of bainite compared to pearlite - the bainite microstructure is both
strong and tough, and is very much finer-scale than that of pearlite.
9.3 TTT diagrams
When steels are rapidly cooled from the austenite phase field a number of different microstruc-
tures are obtained depending on the rate at which the material is cooled.
The transformation of austenite to pearlite

Eutectoid Temperature occurs by nucleation and growth (i.e. be-
Temperature
fore pearlite can grow it has to be nucleated).

γ α+γ
That is to say that the overall rate of trans-
formation of austenite to pearlite is dependent
transformed
1% 99 % α + Fe C
3
on the combined rate of both nucleation and
with addition
(pearlite) of Mo growth. If either the nucleation rate or growth
untransformed
rate is slow then the overall transformation
(austenite) rate will be slow. The rate of nucleation de-
Ms
martensite pends on the driving force for the formation
of pearlite. Above the eutectoid temperature
austenite is stable and pearlite will not form
Time
and hence there is no driving force for pearlite
Figure 9.13: Schematic TTT diagram for a plain to form. As we lower the temperature below
carbon steel. The effect of Mo additions and the the eutectoid temperature austenite becomes
martensite start temperature are shown. unstable and wants to transform to pearlite.
As we keep on lowering the temperature the
austenite becomes more and more unstable and hence the driving force for pearlite formation
becomes greater and greater. What this means is that as we lower the temperature below the
eutectoid temperature that rate of nucleation of pearlite will increase, and the driving force
for its formation increases. At temperatures close to the eutectoid temperature the time re-
quired to effect complete transformation of the austenite will be large due to the fact that the
nucleation rate will be low. Decreasing the temperature will have the effect of increasing the
nucleation rate, and initially the overall transformation rate will increase. Further decrease in
the temperature leads to a decrease in diffusion rate (which controls the growth rate), hence
the growth rate will slow down leading to a decrease in the overall transformation rate. This is
summarised in the TTT diagram below which has two curves, representing the time required
for the onset and completion of the transformation.
As there is no long range movement of atoms involved in the transformation from austenite to
martensite this transformation is referred to as a diffusionless transformation. Therefore the
transformation from austenite to martensite must be independent of time and is dependent only
on temperature; it is purely thermodynamic in nature. The temperature at which the trans-
formation occurs depends on the carbon content, but is generally near to room temperature.
Therefore in order to form martensite we must prevent the eutectoid reaction from occurring
whilst cooling austenite to room temperature.
Effect of C on Martensite Formation
During the transformation of austenite to pearlite, decreasing the transformation temperature

has the effect of decreasing the inter-lamellae spacing in the pearlite. Therefore at high tem-
peratures coarse pearlite is formed, whilst at lower temperatures fine pearlite is formed. If the
transformation occurs at a temperature below ∼ 500◦C the product of the austenite transfor-
mation is bainite. If, on cooling, austenite remains present at even lower temperatures it will
transform to martensite. The extent of the transformation is independent of time, but depends
on the temperature to which it is cooled. There is a martensite transformation start tempera-
ture (Ms ) and decreasing the temperature below this temperature will result in an increasing
amount of martensite being formed.
The martensite transformation start and end temper-

atures are strongly influenced by the carbon content
Temperature (°C)
600
and decrease with increasing carbon content. For plain
400
carbon steels containing more than 0.7 wt.% C the Start
martensite finish temperature Mf is below room tem- 200
Stop
perature. This means that if we quench a eutectoid or
0
hyper-eutectoid steel to room temperature not all the
austenite will be transformed to martensite and some 800
Hardness (VHN)
austenite will be retained. The retention of austenite
600
affects the hardness of quenched steels. The hard-
ness of quenched steels containing up to 0.7 wt.%C 400 Martensite
increases markedly with carbon content due to the &
200 Martensite Austenite
strong solid solution strengthening effect of the in-
terstitial carbon atoms in the martensite. However 0
0.0 0.2 0.4 0.6 0.8 1.0 1.2
above 0.7 wt.% C the increasing proportion of retained
Wt.% Carbon
austenite, which is relatively soft, balances the increas-
ing hardness of martensite, and as a result the hard- Figure 9.14: Effect of C content on
ness of the steel remains essentially constant. the martensite start and finish tempera-
tures, and the hardness of a corresponding
rapidly quenched steel.
Example: Using a TTT diagram for a steel
Let us look now at the TTT diagram for a commercial eutectoid steel, Figure 9.15, and consider
some arbitrary time-temperature paths along which we will cool austenitic samples to room
temperature.
• Path 1: The specimen is rapidly cooled to 160◦ C and left there for 20 minutes.
The rate of cooling is too rapid for pearlite to form at the higher temperatures, there-
fore the steel remains in the austenite phase until the Ms temperature is passed, where
martensite begins to form athermally. Since 160◦ C is the temperature at which half the
austenite transforms to martensite, the direct quench converts 50% of the austenite to
martensite. Holding at 160◦ C forms only a very small quantity of additional martensite
because in simple carbon steels isothermal transformation to martensite occurs only to a
very limited extent.
• Path 2: The specimen is rapidly cooled to 250◦ C, held at this temperature for 100 s, then
quenched to room temperature.
Again the cooling is too rapid to form pearlite, and holding at 250◦ C for 100 s is not a
sufficiently long time to form Bainite, such that on quenching to room temperature a
martensitic structure is developed.
• Path 3: The specimen is rapidly cooled to 350◦ C, held at this temperature for 200 sec,
then quenched to room temperature.
The isothermal hold at 350◦C produces a structure composed of half bainite and half
austenite. Quenching this structure to room temperature results in the transformation of
Figure 9.15: TTT diagram for a commercial steel with 0.76% Mn and 0.79%C, with some arbitrary
time-temperature paths.
the remaining austenite to martensite. Therefore the final structure is half bainite, half
martensite.
• Path 4: The specimen is held at 600◦C for 104 s or 3 hours, then quenched to room
temperature.
At 600◦ C the transformation of austenite to pearlite is completed within ∼ 8 s. The
pearlite microstructure is reasonably stable, and therefore continued heating at this tem-
perature results in no change in the pearlite structure. As the sample now contains no
austenite, rapid cooling to room temperature does not yield any martensite. Therefore
the final structure is fine pearlite.
Quenching and Tempering of Steels
In order to increase their strength, steels can be quenched from the austenite phase field to room
temperature in order to form martensite. However steels in the martensitic condition are too
hard and brittle for normal service. The properties are improved by re-heating (tempering) the
steel to a temperature below the eutectoid temperature. During tempering carbon is removed
from solution by the precipitation of iron carbides, and the matrix reverts to the bcc structure.
At higher tempering temperatures some spheroidisation and coarsening of the carbides occurs.
Whilst the tempering process results in a reduction in the strength of the steel (as compared
to the martensitic condition) the ductility and toughness are much improved.
This hardening process is dependent on producing

a martensitic structure on quenching the material
from the austenite phase field. In the general TTT
curve for a eutectoid steel, cooling curve (a) rep-
resents a high enough cooling rate for this to oc-
cur. However cooling curve (b) on the same dia-
gram passes through the nose of the transforma-
tion curve, therefore some austenite will be trans-
formed, and only a partial martensitic structure will
result. With large components, this can be a prob-
lem, with the surface of the component being com-
pletely transformed to martensite, whilst the centre
(which cools at a slower rate), will only be partially
transformed. The ability of steel to form marten-
site on quenching is termed the hardenability. In
order to increase the hardenability, the rates of pro-
eutectoid, pearlitic and bainitic reactions must be
displaced to longer times, and this can be achieved
by the addition of alloying elements. With the ex-
ception of Co, all the common alloying elements in Figure 9.16: TTT diagram for a commer-
steel decrease the reaction rates, and increase the cial steel with 0.76% Mn and 0.79%C, sub-
hardenability. Alloying additions enable us to ob- jected to two cooling curves (a) and (b).
tain steels in the martensitic condition more easily, but they also affect the tempering charac-
teristics.
Firstly the precipitation and coarsening of the iron

carbides may be altered by the presence of an al-
loying addition. For example Si slows down the
precipitation and coarsening of the cementite, and
this can reduce the fall off in hardness during tem-
pering. More important is that some alloying ele-
ments, called carbide formers (Cr, Mo, Ti, V, & W),
form alloy carbides such as V4 C3 and Mo2 C which
are more stable than the iron carbides. Due to the
slow rate of diffusion of these substitutional alloying
additions, the alloy carbides do not form until tem-
pering temperatures in the range 450 − 600◦ C are
reached. The precipitation of the alloy carbides re-
sults in an increase in hardness, termed secondary
hardening, at high tempering temperatures. Sec-
ondary hardening enables us to produce steels with
a high hardness and strength, but with a better
ductility that that exhibited by a plain carbon steel
tempered to the same hardness by lower tempera-
ture tempering. Also, because of the slow diffu- Figure 9.17: Effect of tempering temper-
ature (amount of tempering) on the proper-
sion of the carbide forming elements, their carbides
ties of a quenched-and-tempered 0.55wt.%C
do not readily coarsen, consequently alloy steels so
steel.
hardened may be used for high temperature appli-
cations.
MSE 300 Materials Laboratory Procedures
The Iron–Iron Carbide (Fe–Fe3C) Phase Diagram
In their simplest form, steels are alloys of Iron (Fe) and

Carbon (C). The Fe-C phase diagram is a fairly complex
one, but we will only consider the steel part of the diagram,
up to around 7% Carbon.
University of Tennessee, Dept. of Materials Science and Engineering 2

Phases in Fe–Fe3C Phase Diagram
¾ α-ferrite - solid solution of C in BCC Fe

• Stable form of iron at room temperature.
• The maximum solubility of C is 0.022 wt%
• Transforms to FCC γ-austenite at 912 °C
¾ γ-austenite - solid solution of C in FCC Fe
• The maximum solubility of C is 2.14 wt %.
• Transforms to BCC δ-ferrite at 1395 °C
• Is not stable below the eutectic temperature
(727 ° C) unless cooled rapidly (Chapter 10)
¾ δ-ferrite solid solution of C in BCC Fe
• The same structure as α-ferrite
• Stable only at high T, above 1394 °C
• Melts at 1538 °C
¾ Fe3C (iron carbide or cementite)
• This intermetallic compound is metastable, it
remains as a compound indefinitely at room T, but
decomposes (very slowly, within several years)
into α-Fe and C (graphite) at 650 - 700 °C
¾ Fe-C liquid solution
A few comments on Fe–Fe3C system
C is an interstitial impurity in Fe. It forms a solid solution

with α, γ, δ phases of iron
Maximum solubility in BCC α-ferrite is limited (max.
0.022 wt% at 727 °C) - BCC has relatively small interstitial
positions
Maximum solubility in FCC austenite is 2.14 wt% at 1147
°C - FCC has larger interstitial positions
Mechanical properties: Cementite is very hard and brittle -
can strengthen steels. Mechanical properties also depend
on the microstructure, that is, how ferrite and cementite are
mixed.
Magnetic properties: α -ferrite is magnetic below 768 °C,
austenite is non-magnetic
Classification. Three types of ferrous alloys:

• Iron: less than 0.008 wt % C in α−ferrite at room T
• Steels: 0.008 - 2.14 wt % C (usually < 1 wt % )
α-ferrite + Fe3C at room T (Chapter 12)
• Cast iron: 2.14 - 6.7 wt % (usually < 4.5 wt %)

Eutectic and eutectoid reactions in Fe–Fe3C

Eutectic: 4.30 wt% C, 1147 °C
L ↔ γ + Fe3C
Eutectoid: 0.76 wt%C, 727 °C

γ(0.76 wt% C) ↔ α (0.022 wt% C) + Fe3C
Eutectic and eutectoid reactions are very important in

heat treatment of steels
Development of Microstructure in Iron - Carbon alloys

Microstructure depends on composition (carbon
content) and heat treatment. In the discussion below we
consider slow cooling in which equilibrium is maintained.
Microstructure of eutectoid steel (I)

Microstructure of eutectoid steel (II)

When alloy of eutectoid composition (0.76 wt % C) is
cooled slowly it forms perlite, a lamellar or layered
structure of two phases: α-ferrite and cementite (Fe3C)
The layers of alternating phases in pearlite are formed for
the same reason as layered structure of eutectic structures:
redistribution C atoms between ferrite (0.022 wt%) and
cementite (6.7 wt%) by atomic diffusion.
Mechanically, pearlite has properties intermediate to soft,
ductile ferrite and hard, brittle cementite.
In the micrograph, the dark areas are
Fe3C layers, the light phase is α-
ferrite

Microstructure of hypoeutectoid steel (I)
Compositions to the left of eutectoid (0.022 - 0.76 wt % C)

hypoeutectoid (less than eutectoid -Greek) alloys.
γ → α + γ → α + Fe3C

Microstructure of hypoeutectoid steel (II)

Hypoeutectoid alloys contain proeutectoid ferrite (formed
above the eutectoid temperature) plus the eutectoid perlite
that contain eutectoid ferrite and cementite.

Microstructure of hypereutectoid steel (I)
Compositions to the right of eutectoid (0.76 - 2.14 wt % C)

hypereutectoid (more than eutectoid -Greek) alloys.
γ → γ + Fe3C → α + Fe3C

Microstructure of hypereutectoid steel (II)

Hypereutectoid alloys contain proeutectoid cementite
(formed above the eutectoid temperature) plus perlite that
contain eutectoid ferrite and cementite.

How to calculate the relative amounts of proeutectoid

phase (α or Fe3C) and pearlite?
Application of the lever rule with tie line that extends from
the eutectoid composition (0.76 wt% C) to α – (α + Fe3C)
boundary (0.022 wt% C) for hypoeutectoid alloys and to (α
+ Fe3C) – Fe3C boundary (6.7 wt% C) for hypereutectoid
alloys.
Fraction of α phase is determined by application of the

lever rule across
University the entire
of Tennessee, Dept.(α + Fe3C)
of Materials phase
Science field:
and Engineering 12
Example for hypereutectoid alloy with composition C1
Fraction of pearlite:
WP = X / (V+X) = (6.7 – C1) / (6.7 – 0.76)
Fraction of proeutectoid cementite:
WFe3C = V / (V+X) = (C1 – 0.76) / (6.7 – 0.76)

Habib University
Phase Diagrams | Microstructures in Steel | Interpretation of Phase Diagrams
Lecture 24 | White Board Lecture | Thursday 28th November 2019
• Important considerations in a 2 solid solution eutectic phase diagram

• Important considerations in an Iron Carbon phase diagram
Habib University
Band Theory of Solids | Models of Electron Transport | Semiconductor Fabrication Methods
Lecture 25 | Lecture 26 | White Board Lecture | Class Exercise | Class Discussion
Tuesday 3rd December 2019
You have been provided 2 Readings for Fall 2019 | ME 431 | Lecture 25 and 1 Reading for Fall 2019 | ME 432 |
Lecture 26. Since today we are going to have 2 classes, please attempt to read all of the provided readings for both
Fall 2019 | ME 431 | Lecture 25 and Lecture 26.
Please form a group of 3 members and use an hour going through the provided Readings in silence. Discuss and
then attempt the questions, given below. Please write in bullet points. You are allowed to Google anything you
like. You can ask the instructor any question you like and are encouraged to do as such.
1. The Drude Model is still widely used to provide a classical picture of conduction in solids, particularly
metals. Considering the Drude Model and its application to conduction of electrons in solids, please
answer the following questions:
i. What were the basic assumptions of the Drude Model?

ii. What kind of particles was the Drude Model based on?
iii. What were the 2 reasons, with respect to conduction in solids, to replace the Drude Model?
iv. What is the relationship between the current density ‘j’ and the applied electric field ‘E’ in the
Drude Model? [just 1 word]
v. Explain, very briefly, what is meant by ‘independent electron approximation’?
2. The Drude Model was replaced by the Drude-Sommerfeld Model to consider certain inconsistencies in
electron conduction. Considering the Drude-Sommerfeld Model and its application to conduction of
electrons in solids, please answer the following questions:
i. What kind of particles was the Drude-Sommerfeld Model based on?

ii. What kind of statistics does the Drude-Sommerfeld Model follow?
iii. How does the probability of electron occupation changes from low temperatures to high
temperatures? Please explain your answer. [Why?]
iv. Explain what is meant by ‘Collective Emergent Properties’ in Statistical Physics by using energy
band formation as an example. [Just 3 lines]
3. The band theory of solids provides us with the acceptable electronic states that are either filled or empty.
It also provides the energy requirement for charge carriers to participate in the conduction process.
Considering the band theory of solids & conduction of charge carriers, please answer the following
questions:
i. Please sketch the energy band diagrams of metals, insulators and semiconductors
ii. What is the difference between electrons which participate in bonding and electrons that participate
in conduction?
iii. Considering the available states in the conduction band and valence band, what are the
requirements for good conduction of charge carriers in solids?
iv. Why is the application of an Electric Field necessary for conduction in metals?
v. Give a mathematical expression for the charge carrier conductivity in semiconductors (intrinsic)
4. A common conceptual model of electrons within atoms is the ‘planetary’ model, with electrons depicted
as orbiting satellites whirling around the ‘planet’ of the nucleus. The physicist Ernest Rutherford is known
as the inventor of this atomic model.
A major improvement over this conceptual model of the atom came from Niels Bohr, who introduced the
idea that electrons inhabited ”stationary states” around the nucleus of an atom, and could only assume a
new state by way of a quantum leap: a sudden ”jump” from one energy level to another.
i. What led Bohr to his radical proposal of ‘quantum leaps’ as an alternative to Rutherford’s model?
ii. What experimental evidence led scientists to abandon the old planetary model of the atom, and
how does this evidence relate to modern electronics?
5. In solitary atoms, electrons are free to inhabit only certain, discrete energy states. However, in solid
materials where there are many atoms in close proximity to each other, bands of energy states form.
Explain what it means for there to be an energy ‘band’ in a solid material, and why these ‘bands’ form.
6. Engineers and scientists often use energy band diagrams to graphically illustrate the energy levels of
electrons in different substances.
Based on these diagrams, answer the following questions:
i. Which type of material is the best conductor of electricity, and why?
ii. Which type of material is the worst conductor of electricity, and why?
• CLO 3 | Apply the concepts of electron excitation events that produce free electrons | holes in metals, semiconductors (intrinsic
and extrinsic) and insulators.
• CLO 5 | Explain the relevant concepts behind material selection of relevant electronic devices (p-n diodes, light emitting diodes,
solar cells, MOFSETs, printed circuit boards and thermal management materials) based on their operating characteristics.
• Band Theory of Solids | Fermi Dirac Statistics | Temperature dependency of the Fermi Level
• Semiconductor Fabrication
• Semiconductor Physics | holes | electrons
HU | Fall 2019 | ME 431 | Introduction to Engineering Materials
Lecture 25 | Theoretical Models of Electron Transport
Class Exercise | Reading 1
core electrons core electrons

ion
nucleus
nucleus
valence electrons
conduction electrons
(a) (b)
Lecture 25 | Band Theory of Solids
Face centered atoms
Atom bonded to 4 others
Other atoms bonded to

chain in cube
Atoms bonded outside of
cube
Significant leap required Overlap permits
for an electron to move Shorter leap electrons to freely
to the next higher level required drift between bands
3p 3p
3p
Overlap
3s
3s 3s
Single atom Five atoms Multitudes of atoms

in close proximity in close proximity
Conduction band
Significant leap required
for an electron to enter
the conduction band and "Energy gap"
travel through the material
Valence band
Multitudes of atoms
in close proximity
semiconducting substance
metalic substance for reference
Conduction band
Small leap required
Insignificant leap
for an electron to enter for electron to
"Energy gap"
the conduction band and enter conduction
travel through the material band
Valence band
(a) (b)
Specific resistance Electron Specific resistance Electron
Element ( ) at 20o Celsius configuration Element ( ) at 20o Celsius configuration
Silver (Ag) 9.546 cmil/ft 4d105s1 Molybdenum (Mo) 32.12 cmil/ft 4d55s1
Copper (Cu) 10.09 cmil/ft 3d104s1 Zinc (Zn) 35.49 cmil/ft 3d104s2
Gold (Au) 13.32 cmil/ft 5d106s1 Nickel (Ni) 41.69 cmil/ft 3d84s2
Aluminum (Al) 15.94 cmil/ft 3p1 Iron (Fe) 57.81 cmil/ft 3d64s2
Tungsten (W) 31.76 cmil/ft 5d46s2 Platinum (Pt) 63.16 cmil/ft 5d96s1
hole electron
(a) (b)
B Si Si Si Si Si Si Si Si
Si Si P Si Si Si B Si Si
P Si Si Si Si Si Si Si Si
(a) (b) (c)
electron hole
electron
hole movement movement
electron movement
hole movement
(a) (b) electron movement
electron enters electron exits
crystal lattice
(a) N-type
(b) P-type
Elemental semiconductors
C(diamond), Si, Ge
13 IIIA 14 IVA 15 VA
B B 5 C 6 N 7
P-type dopant for C Boron Carbon Nitrogen
10.81 12.011 14.0067
2p1 2p2 2p3 N, P
Al 13 Si 14 P 15 N-type dopant for C
B, Al, Ga, In Aluminum Silicon Phosphorus
P-type dopant for Si 26.9815 28.0855 30.9738
3p1 3p2 3p3
Al, Ga, In Ga 31 Ge 32 As 33
Gallium Germanium Arsenic P, As, Sb
P-type dopant for Ge 69.723 72.61 74.92159 N-type dopant for Si, Ge
4p1 4p2 4p3
In 49 Sb 51
Indium Antimony
114.82 121.75
5p1 5p3
no charge
separation
P N P
N
electron crystal lattice intrinsic

hole charge
separation
(a) (b)
depletion region
electrons holes electrons holes
N P N P
(a) Forward (b) Reverse

electrons holes
N P
mA
forward
reverse bias bias
(a)
N-type P-type
(not pointing) (pointing)
breakdown
A
(b) cathode anode (c)
Lecture 26 | Semiconductor Fabrication Techniques
lift rod
Si boule
fused silica crucible
graphite suceptor
RF induction coil
Si melt
Si boule
cut wafers
diamond blade
driven edge
(a) copper PCB (b) apply photoresist (c) place artwork (d) expose
(e) remove artwork (f) develop resist (g) etch copper (h) strip resist
(a) N-type wafer (b) grow SiO2 (c) apply photoresist (d) place mask
(e) expose (f) remove mask (g) develop resist (h) HF etch
BH3
(i) strip resist (j) P-type diffusion

(k) grow SiO2 (l) apply photoresist (m) place mask (n) expose
(o) remove mask (p) develop resist (q) HF etch (r) strip resist
POCl
C B E
(s) N-type diffusion (t) metalization

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ME 431– Introduction to Engineering Materials

IDEE – Interdisciplinary Engineering Elective

Reading Material provided each week

Course Content Course Learning Outcomes

10 Semiconductivity II Items Weights (%) How many?

11 Device Fabrication Technology I | Materials Processing Assignments 18 3

12 Device Fabrication Technology II | Materials Processing Quiz / Tests 18 3

14 Device Fabrication Technology IV | Materials Processing End Term 36 1

* Atoms smallest building block

X Atoms are not indivisible

X No Nucleus – experimentally debunked

* Experimental verification of nucleus

X Why electrons orbit the nucleus?

X Heisenberg’s Uncertainty Principle

* Wave – Particle Duality

Still the widely accepted model • Age of Particle Accelerator

Assemblies We can touch

Molecules | Bond Formation

Emergent Collective Properties

Modification of Material Properties

The Scientific Principle:

• Solid State Physics

• Quantum mechanical model of an electron

CLO 1 | CLO 2 | CLO 3 | CLO 4 | CLO 5

Tuesday 3rd September 2019 @ 10 00

- The Band Theory of Solids | brief introduction | white board lecture

- Formation of a Band | orbital overlap | white board lecture

- The Particle Zoo | Standard Model of Particles

- What is Quantum Mechanics? | historical rant

- The Photoelectric Effect | Wave Particle Duality | introduction

Topics for next lecture

Things I will ask with a 100% probability !

Photons W/Z Bosons Gluons

Fermions – electrons, neutrons, protons

CERN still smashing particles at high energy to discover

Like everything in modern physics, it all started with Ludwig Boltzmann

validated 20 years later | 1900 | Max Planck | Planck’s Law

electron goes to CB | free to move around

Any energy of photon would induce an electron to eject?

Basic postulate of QP | Discretization of energy

Thursday 5th September 2019 @ 10 00

- The 5th Solvay Conference | 1927

- What happened to the electron? | Bohr’s Determinism | Schrödinger's Probability

- Concepts explained on the white board

Things I will ask with a 100% probability !

constructive | destructive interference

What properties do wave exhibit?

Bohr’s deterministic model of the atom

I do draw waves quite nicely!

Thursday 12th September 2019 @ 10 00

- Concepts covered on the whiteboard

'To see the world in a grain of sand,

The MOSFET [metal oxide semiconductor field effect transistor]

Tuesday 17th September 2019 @ 10 00

- Wavefunction ψ(x) | description of the wave-like behavior

- The Copenhagen Interpretation of Quantum Mechanics | relevant for this course

We need to fix the ‘Quantum State’ of the electron!