Week 2 Lecture 1: Transformations 1

Phase Changes:
 Solidification
 Diffusion
 Shear
Solidification
 Solidification is a major phase change
 Start with liquid, then it cools and is solidified forming a solid and gases
forming liquids
 Lower temp, moving about less more packed together, so material has
opportunity to form stable bonds. If there is a pattern like FCC or BCC
then that pattern will form
 Pressure and temperature both affect solidification
Solidification brings about a number of important changes:
 Density increases
 Bonding increases
 Solubility of dissolved elements
 Diffusion occurs
 Phase separation may occur
Typical Solidification Curve for a Pure Metal

 When the metal is molten it will lose heat by the time we e.g. put it into
the mold to create something. That is just reality.
 So we superheat it and take it well above the melting point, so we have
enough time to get the metal out of the furnace where it is being melted
and into the mold where it is getting poured into, so the metal can flow
through the mold whilst retaining enough of its liquidity and fills the
mold completely without solidifying half way through.
 As the temp comes down the metal cools, the cooling rate depends on
what the metal is in contact with (e.g. air, sand or different metals and
what levels of convection and conduction of heat are in play at any
particular time)
 As it reaches the solidification point, it starts to plateau.
 This is because there are two energy changes. There is the heat in the
molten metal which is being given to the surroundings causing the temp
of the metal to go down
 But that actual process of solidification is releasing internal energy, so as
the metal loses heat to the surroundings, internally it is generating
energy from transforming from a liquid into an ordered solid, and these
two balance out causing the plateau called a thermal arrest
 Once the internal energy changes is finished and the structures are being
formed the material continues on its journey downwards in
temperature, so it has gone past its solidification point
  In a liquid state a pure metal has more internal energy than in solid
state
 At the freezing point the temperature plateaus as the energy
dissipated by the temperature drop is compensated by the release of
excess internal energy
Typical Phase Diagram for a Simple Alloy

 We have this
third area where liquid and solid can exist at the same time
 The dotted line is around 45% nickel and 55% copper
 As we go down the dotted line (temp going down) it is a liquid but as it
hits the blue line, solids start to form, but unlike a pure material with a
fixed melting point, there is a range of temperatures (in between where
the dotted line meets the blue line)
 Past the second intersection is when the material is fully solid
 A Phase Diagram indicated the phases present in an alloy system over
a range of temperatures
 If the elements in the alloy system have different freezing
temperatures then they will want to solidifying at different
temperatures
 In a mixture (an alloy) solidification can happen over a temperature
range between the freezing temperatures of the constituent elements
 The alloy system covers a range of element ratios (alloys), so the phase
diagram plots out these transformation temperature ranges
Simple Alloy Freezing

 Whereas with a pure metal we get a plateau forming where the thermal
arrest is. Stays flat until it loses all its internal energy
 With our alloy we get a slight gradient, occurring from out liquidous
point (everything above this is liquid) and the solidous point (everything
below is solid)
Complex Alloy Systems (like steels)
 There are 2 x-axis. Top one looks at the atomic proportion of carbon
(number of carbon atoms) and the bottom looks at mass.
 Liquidous line is where everything above it is liquid
 Everything below it is a solid-solid transformation
 The properties of steel changes as the composition of carbon goes up
 Steels stop around 1.4/1.5 % weight percent carbon
 Cast irons are about 2.5/4.5% weight person carbon
 The further you go on the more brittle the material gets
 In a complex alloy systems the phase diagram gets more complicated
but is giving the same information
 Elements like iron change crystal structure (FCC and BCC) with
temperature. So iron at high temps likes to be FCC and that is austenite
(gamma) and as we go down we get a transformation region, where we
are transforming from a higher temperature version of steel to a lower
temperature version of steel. In this case it is called ferrite (alpha) which
has a BCC structure. The carbon solubility in iron changes with these
different transformations, so the extra carbon needs to be controlled as
it can be harmful to the steel, so mapping is a way of working a way out
to minimise the harmful effects and maximise the useful effects
 We are only interested in the far left hand side of the phase diagram,
where the steels and cast irons are
 More accurately, this is an equilibrium phase diagram (EPD). It shows
diffusion-driven phase changes. This is because all these phases is
associated with diffusion bases (relatively slow changes in phase), if we
try increase the speed, we can lose these transformations and
something else occurs, so the material needs enough time to do these
changes. This is the difference between equilibrium phases (slow) and
shear phases (fast)
Diffusion
 Interdiffusion: In an alloy, atoms tend to migrate from regions of high
conc. To regions of low conc.
 We provide a bit of heat energy to allow diffusion to occur and we have
this mixture going on. The boundary between the two is blurred. If
there is enough heat for atoms to move then they are going to
randomly pop out.

Diffusion Mechanisms
 Self-Diffusion: In an elemental solid,
atoms also migrate (orange moving within
orange doesn’t change anything or have
any effect)
 Vacancy Diffusion: Atoms exchange with
vacancies (crystals have defects and some
of the are gaps/holes in a perfect lattice
structure, so the atom moves into these vacancies)
 Interstitial Diffusion: Smaller atoms can diffuse
between atoms. It is more rapid than vacancy
diffusion (things like carbon which is small can
move between iron atoms stuck on the lattice
and using lattice points as their basis for diffusion)
Diffusion and Temperature
 Diffusion is affected by temperature. Substitutional is normal. Carbon is
smaller than Al and Fe so it makes sense that it diffuses quicker as it can
dart around quickly than the atoms on the lattice which can only move
around due to the substitution of each other.

Equilibrium Transformations in Steel

 At high temps it forms austenite
which is FCC and at low temps it
forms ferrite which is BCC, and also
reduces in size.
 This means there is less room for
carbons to live in the little gaps
between the iron atoms (more in
the FCC than BCC)
 Diffusion driven – Carbon gets
diffused
 Solubility limit indicated the need
for new phases to manage the
carbon – Ferrite BCC is the
most energetically
favourable iron, meaning
the carbon needs to move
out from austenite as there
is no room for the carbon
to form
 More total carbon content
means more carbon-rich
phases
 Carbon-rich phases
progressively become
more brittle – Rather than
making pure carbon itself, it
makes a rich and enriched
iron phases, firstly iron-3-
carbide, also known as Cementite. This is a ceramic so it is stronger but
also more brittle
 High carbon steels are stronger and brittle but low carbon steels are
tougher
  Grain boundaries are useful places to nucleate change processes. We
have a set of ferrite crystals growing out of the grain boundaries.
 Ferrite pushes out excess carbon to either side which naturally forms
cementite
 Pearlite which is a eutectoid mixture of ferrite and cementite
 Phase transformations occur at a energetically favourable site, in this
case at the grain boundaries of the austenite
Non-equilibrium/Shear Transformations
 The equilibrium phase diagram (EPD) is a map that tells you what
phases to expect for a given set of circumstances (temp and alloy
content)
 You can drive the material off the EPD by changing the cooling rate
(allows diffusion to take place because cooling is slow)
 Fast cooling does not allow equilibrium to be achieved i.e. you deprive
the system of heat energy before diffusion can physically occur
 Instead we fall into a metastable state with metastable phases (Stable
enough that it exists at a low temp but it is unstable enough that if we
were to provide the material with some heat, it would try to get back to
the equilibrium state)
 We use a different diagram to work out where we are under these
circumstances called Isothermal Transformation Diagram (ITD) and
Continuous Cooling Transformation (CCT) Diagram, both of which cover
equilibrium and non-equilibrium transformations
Isothermal Transformation Diagrams
 Top-dotted line is austenite
temp, everything above is
austenite.
 The time shows how quickly the
temp drops
 Slow diffusion forms pearlite
 Fast diffusion forms either
Bainite which is the metastable
phase or Martensite which is the
BCT (body centered tetragonal)
phase.
 To be used with heat treatments
that include dwells (horizontal lines) to find the optimum way to get
what we want out of the material
 A dwell is holding at a specific temp to allow a particular
transformation to occur, normally after a quenching used to avoid a
different transformation. Allows bainite to form.
  Below the dotted line is the
metastable phases and
above it is the equilibrium
phases
 The dotted line curving
down the middle of the
path represents the half
complete process that
takes time
 Different rules:
o Metastable phases do
not transition to each
other, you must go
back to austenite and
start again
o Once you start a
transformation (cross
a red line) it is not
reversible unless you re-austenitise.

Continuous Cooling Transformation (CCT) Diagram

 Most time when quenching something it
is fairly massive, if it has any measure of
sectional thickness to it and we quench it,
exposing the surface to a cooler medium
(air/water/oil), the surface will cool more
quickly than the centre as the centre is
more insulated from the quenching. So
we get a range of cooling rates
 Potentially at the surface we can have a
metastable transformation going on
(martensite) but at the centre we can have an equilibrium phase going
on. It is advantageous if we want something hard like a roller, a hard
surface is good but also fairly tough as martensite is brittle.
 Used for cooling treatments (Furnace cooling/Quenching). Useful for
assessing the effect of a quench on a thick section.
 Transformation 2
Degradation
 From an abstract perspective any engineering component achieves a
balance between cost and performance:
o Costlier materials and better processes result in an enhances
performance capacity
o A more demanding function and harsher environment results in
a shorter component lifespan.
 This sets up a battle between us as engineers and our abilities to
improve the endurance of materials, and the varied ways in which the
environment damages the material.
Surface Corrosion
 Corrosion is mainly considered to be
driven by moisture
 The classic example is a water drop
on a mild steel where corrosion is
driven by the variation in oxygen in
the water
  Stainless steel is not immune to corrosion. Its weakness is where water
Sub-surface corrosion
 Intergranular Corrosion affects steels with high
chrome content
 Chromium carbide particles can form at the grain
boundaries of the steel that has been welded
 Welding allows carbon to migrate to grain
boundaries and form carbides with chromium,
depleting the region around the grain boundary of
its protective element. Any strong chemical will preferentially eat away
at these regions, penetrating into the steel
o Adding Ti, Zr, Nb to the steel reduces the migration of carbon as
mitigated the effect
o Alternatively use a low carbon steel if possible
Wear
 Wear is an inevitable
consequence of machinery
 There are several mechanisms,
adhesive, fatigue and abrasive
being the most common.
 Wear is not always bad.
Without it grit blasting would
be pointless. We just need to
be in control of it.
Fracture
 Fracture can be ductile (slow) or brittle (fast)
 More often than not it is preceded by fatigue
failure, a progressive growth of small cracks until
their effects are overpowering
 Fracture is the complete failure of a component as
it breaks the pathway for mechanical and electrical
energy
 Brittle fracture is less predictable and absorbs less
energy, so is the worse of the two types
Aging
 Aging is a key aspect of the
strengthening of aluminium but
overaging can occur where the
strength begins to decrease
 Aging can be used to describe the
gradual formation of grain boundary
precipitates in some metals when
exposed to prolonged high
temperatures.
o If the precipitates are brittle,
then they will form easy paths
for cracks to follow
 For plastics aging is of particular issue
for those that are exposed to UV light
or rely on plasticisers to remain durable
o UV can break bonds on the molecular chains, causing the plastic
to weaken
o Plasticisers can become volatile or be leached out by exposure to
some chemicals, causing embrittlement in the plastic
Strengthening of Metals
 Grain Size
o Hall-Petch
 Phase Balance
o E.g. more C-rich phases = Stronger steel
 Solution Strengthening
o Alloy elements with dissimilar sized atoms distort the lattice and
make it harder for slip planes to operate
 Work Hardening
o Increase dislocation numbers and entangling them with plastic
deformation
 Precipitation Hardening
o Controlled growth of secondary phase precipitates adds obstacles
to dislocation flow
Grain Size
 The Hall-Petch relationship relates the average diameter of a metal
crystal (Average grain size) to the yield stress using two material
parameters
o It is valid for most grain sizes of interest but is not universally
applicable
 The smaller the grain the greater the number of grain boundaries
o Grain boundaries slow down dislocation movement and so
inhibit material flow
o More mechanical energy is required to move the dislocation and
so bulk yield occurs at a higher stress
o In essence the stress at
which yield is observed is
raised because of the
increased energy
requirement to move
dislocations through the
interfaces between crystals
Phase Balance
 In steels, an
increase in
carbon
content leads
to the
formation of
more carbon-
rich areas
 More carbon-
rich phases
are stiffer,
stronger and
less ductile
(becoming
more ceramic)
 As the proportion of carbon-rich phases increases, the properties of
the steel becomes more influenced by the properties of these phases
Solution Strengthening
 The presence of alloy elements in either lattice positions
(substitutional) or as interstitials causes the crystal lattice to distort
 This makes it much harder for slip planes to operate and for plastic
deformation to take place
o Dislocations are harder to move along uneven slop planes and
more energy is required to do so
o This raises the stress at which yield occurs
 This effect is reduced if dissolved solute is subsequently precipitated as
solute rich phases
o The rich phases drain the lattice of the atoms causing the
distortion and return the symmetry to the lattice
Work Hardening
 Deforming a metal causes the number of dislocations by several orders
of magnitude
 The frequency at which dislocations cross each other increases
exponentially
 They become entangled, pinning each other. More energy is required
to move them when entangled and so the stress to cause flow gets
progressively higher with the amount of working done on the metal
Precipitation Hardening
 Precipitation
hardening is the
main reason for
alloying aluminium.
It enables a useful
but soft metal like
aluminium to
become a useful and
strong alloy
 Precipitation is
controlled by a
careful heat
treatment that first
dissolves the solute
atoms. They are
then held in solid
solution by using a
quench (rapid
cooling)
 Subsequent heating provides the energy to generate many small
precipitated all through the microstructure
 The small precipitates delay dislocation movement by requiring energy
to either push past (looping) or through (cutting) the precipitate
Transforming Toughening of Ceramics
 If transformations can be
stalled, they become
metastable
o Yttria additions have
this effect on zirconia
 The metastable structure is
triggered to transform
through shear by
mechanical stress fields
o This transformation is
accompanied by an
increase in volume
 Compressive forces are thus
generated by the stress
concentrations caused by a
crack, pushing the fracture
surfaces back together
o This in turn stalls
failure for a bit
 Metals 1
Introduction
 Metals have an extremely useful mix of properties. To a first
approximation they sit between polymers and ceramics from a
mechanical perspective
 Earliest adopters would have first appreciated the aesthetic quality of
shiny metals, followed by the appreciation of an easily maintainable
sharp edge
 Today the four principal properties are formability, strength,
hardenability and conductivity:
o Formidability is primarily concerned with easy of manufacture
but also implies ductility and toughness
o Strength is primarily considered with mechanical performance
but also implies the ability to maintain a shape
o Hardenability provides an opportunity to shape the material
when formidable and then strengthen for service
o Conductivity pertains to several forms of transmission – thermal,
electrical and sound
 Metals also score reasonably well in other categories like stiffness, and
number amongst their membership those who are lightweight,
corrosion-resistant and those who possess hot hardness (refractory
metals)
 As a family their real strength is in the depth and breadth of their
collective properties
Ferrous Alloys
 The pre-eminent metal clan are the ferrous alloys = Cast Iron and
Steels. The most flexible and populous of these are steels
 The basic recipe is an iron lattice and interstitial alloy of carbon atoms
 As carbon content increases an intermetallic/ceramic Fe2C (cementite)
begins to form and complex microstructures can be formed
 When the carbon content is high enough then pure carbon (graphite)
appears in the microstructure, which is characteristic of cast irons
 Alternatively, phases can be formed in the microstructure by cooling so
quickly that diffusing can’t occur. These are metastable phases and
form a corrosion resistant skin on the steel like aluminium does
 Other alloying elements include Manganese. These create MnS
precipitates with Sulphur which can strengthen the steel. MnS also acts
as a sink for dissolved Hydrogen
Steel Stress-Strain Curves
 Carbon content affects the as-formed
properties
 As carbon content increases, strength
increases and ductility decreases. This
changed the shape of the stress-strain curve
 Stiffness of steels fairly uniform as Fe-Fe bond
is dominant. For cast iron, presence of
significant graphite content reduces stiffness

Effect of Carbon Content (Phase) on Properties (Phase Balancing)

Heat Treatment of Steels
 To strengthen
o Rapid cooling aka quenching
 To make metastable phases like martensite by depriving
diffusion processes of their energy
 Can be used to harden the surface of a large component
 Must be careful not to cause cracking if quench is too
severe
 To toughen (usually by reducing strength)
o Annealing (high temperature heat treatments)
 A number of heating processes that refine or recover the
microstructure after the effects of rolling or quenching
 Relieves stress, makes sharp crystals rounder, reduces
grain size by recrystallisation
o Tempering
 At low temperatures (cf. anneal), designed to soften
metastable phases and sacrifice some of the strength to
make the ductility high enough for the application
Grain Size Control
 How is grain size altered?
o By control during processing
(casting, rolling, extrusion,
heat treatment, etc.)
 For example, plain hot rolled steel
will have a grain size of about 30
microns whereas controlled rolled
steel can have a grain size of
around 7-10 microns
 Cold working will strengthen the
material by dislocation production
and entanglement
o Annealing and the associated
recovery, recrystallisation
 and grain growth will undo this strengthening effect by
“overwriting” the microstructure
Productions of Cast Irons
 The carbon content
in cast iron is
enough for it to
occur as graphite
(pure carbon)
 The carbon can also
be shuttled around
by heat treatments
to remove the
brittleness of cast
iron
 The excessive
cementite
formation in white
cast iron makes it brittle. Subsequent heat treatment allows the
formation of graphite and/or pearlite from the cementite to improve
properties
Types of Cast Iron:
 Gray Iron
o Graphite flakes
o Weak and brittle in tension
o Stronger in compression
o Excellent vibrational dampening
o Wear resistant
 Ductile Iron
o Add Mg and/or Ce
o Graphite as nodules not flakes
o Matrix often pearlite – stronger but less ductile
 White Iron
o < 1 wt% Si
o Pearlite + Cementite
o Very hard and brittle
  Malleable Iron
o Heat treat white iron at 800-900 degrees Celsius
o Graphite in rosettes
o Reasonable strong and ductile

Metals 2
Aluminium and its Alloys
 Aluminium and its alloys have a relatively low density (c. 2.7g/cm3 as
compared to 7.9g/cm3 for steel)
 Excellent specific strength (strength-to-weight ratio)
 FCC crystal structure, its ductility is retained even at very low
temperatures. Shape into complex forms
 High electrical and thermal conductivities
 Resistance to corrosion in some common environments, including the
ambient atmosphere
 Major limitation of aluminium is its low melting temperature of 660
degrees C, which restricts the max temperature at which it can be used
Aluminium Coding Series
Aluminium Alloy Uses