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# MAT E FINAL EXAM PREPARATION NOTES

## Section 6- Plastic Deformation

-Plastic deformation occurs when applied stress resolve into a shear stress large enough
to induce dislocation motion.
-Dislocation motion can change via: Grain boundary strengthening, solid solution
strengthening, strain hardening and particle strengthening.
-These are all ways to increase yield strength (provide obstacles for dislocation motion.
-They are influenced by: Grain size, dislocation density, size of precipitates, chemical
composition and crystal structure.

-Ceramics and polymers dont experience plastic deformation through dislocation motion
only for metals
-Plastic deformation is produced through relative motion of one part of a material to
another
-A block of atoms sliding past one another is called slip. This slip occurs along the close
packed plane since there is the least amount of disturbance. But why is yield stress so
high in metals? Whats making them so strong and against dislocation motion?
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-When viewing the slip, 2 angles are created: The angle from the stress-axis to the slip
direction () and the angle from the stress-axis to the normal to the slip plane ().
-Dislocations move under shear stress. Applied stress must be resolved into a slip plane
along a slip direction.

## R = resolved shear stress to cause slip

= applied tensile stress
= angle between the slip direction and the stress axis
= angle between the normal to the slip plane and stress axis
Schmid factor = coscos

The critically resolved shear stress is the shear stress required to cause a dislocation to
move in a pure single crystal in a metal (o, or CRSS). This value varies for different
crystal structures. It is lower in FCC and higher in BCC (because there is a close packed
plane in FCC for easy dislocation and only a closest packed plane in BCC). The higher
the planar density, the least resistance and the easier dislocations move.
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Ductile metals have many slip systems and a small CRSS. A slip system is one
direction on one plane. For multiple directions on multiple planes, we reduce the
numbers to get the smallest number of distinct (independent) directions and planes. We
then multiply the # of slip directions by the # of slip planes to find the # of slip systems.
-For HCP, if the slip plane is perpendicular to the applied stress-axis then the Schmid
factor can be 0 so it will not slip.
-For FCC, slip will always occur since there are so many slip systems and the metals are
ductile.
-For BCC, it has the same number slip systems as FCC but not as high ductility and
there isnt a close packed plane so CRSS is higher.
-Note that we need about 5 slip systems for good ductility.
To strengthen a material is to provide obstacles for dislocation motion. Thus strength is
equal to a combination of intrinsic strength + additional strength from a mechanism. That
is ys = + . Yield strength is then usually the applied stress to be resolved into shear
stress required for dislocation motion and provide a Schmid factor. o = critical resolved
shear stress in a pure single crystal (flow stress).

Grain-boundary strengthening
-Grain boundaries act as barriers to dislocation motion
-Slip planes are discontinuous across the boundary
-Each grain is orientated differently from its neighbor

The Hall-Petch relation describes how a decrease in grain size results in strength
increase. = + //

is the Hall-Petch coefficient (MNm^(-3/2)) and d is the grain size (diameter in m). ys
is the new yield strength and is the original strength.

## Solid Solution Strengthening

This form of strengthening works by adding solutes of different size to a metal and
placing the solutes on the lattice (substitutional solid solution) or between lattice points
(interstitial solid solution) and this increases strength due to interactions with
dislocations. It works because the solutes create a strain field around itself and distorts
the lattice and therefore distorts the dislocation motion. Since dislocations have strain
fields around themselves as well, this interaction causes an attraction and interruption.

= +

## Where B is a property of the solvent/solute combination, G is the shear modulus [GPa]

and c is the concentration of solute (usually atomic percent). Small interstitials in host
lattices can also move around quickly, and they are attracted to the strain field of
dislocations, and as such will diffuse to the dislocation core and interfere with the
bonding and thus prevent the dislocation from moving.

Interstitial solute atoms can raise the shear strength by hundreds of MPa whilst
subtitutional solute atoms are not as effective in strengthening.

Strain-hardening (cold-working)
This is a process where a material is plastically deformed to increase its strength. It is
similar to increasing dislocation density via plastic deformation. Yield strength and UTS
increases but in varying amounts. Ductility decreases as strain hardening increases.

There are a few techniques to cold work a metal but we will focus on cold rolling. It is
called cold because it operates at less than 0.4Tmp. The rolling reduces the area to
increase strength. The equation for % reduction in area is the same as % cold worked:

% = 100%

The reason the metal becomes stronger is because dislocation density increases
greatly. The dislocations interfere with the motion of the other dislocations (traffic jam)
and if its harder to move dislocations, the metals yield strength and UTS increases but
it becomes more brittle.

Note: If no dislocations exist, this is called dislocation starvation and plastic deformation
never occurs. This is if grain sizes are really small (nano-sized material).

Intersection points between boundaries and dislocations are called jogs. Dislocations
must bypass these jogs and the shear stress needed to bow a dislocation through a
radius R is = /2 and R is 1/ ^(1/2) so this gives us the equation:
= +
= Typically 0.2-0.5
G = Shear modulus (GPa)
b= Burgers vector of a dislocation (m)
= Dislocation density (m/m^3)

Cold-rolling usually results in the metal having anisotropic properties due to changes in
grain size/shape. Before cold-rolling, the grains are isotropic and after they are
anisotropic. The stretching on these grains creates longer boundaries to stop
dislocations.

Precipitation Hardening
-This kind of strengthening works by growing precipitates locally or by adding very small
and very hard (strong) precipitates or particles to an alloy
-The advantage of this mechanism is that you can control the properties of your metal
because you can add different amounts; different precipitates in any way you choose to
produce drastically different properties for different applications.
-The main disadvantage is that if you use very small precipitates, the intermetallic
compounds can be sheared by dislocations. And at high temperatures, precipitates
become larger and can decrease strength.

## So how does it work?

1. Choose an alloy system that will react to form small intermetallic precipitates (Cu-
Al)
2. Heat treat the system in such a way to nucleate and grow very small precipitates
3. The size, spacing and inherent shear strength of the precipitates will determine
the strength of the alloy. We assume that if precipitate size increases, then
spacing increases too to account for constant volume.

## 2 possible interactions exist when precipitates are formed:

a. The precipitates shear when the dislocation passes because they are too small
to cause the dislocation to change its shape to bypass. This still results in some
strengthening.
b. The precipitates dont shear and the dislocations have to move around them. The
smaller the radius of particle, the more particles you can fit in and the higher the
needed to move the dislocation, thus increasing strength.
The competition between cases a and b results in this peak where the precipitates are
large enough to avoid shearing but close enough to interfere with the dislocations the
greatest.

The above equation is for case a. Increasing both the precipitates radius and volume of
precipitates will increase strength.

For case b, a certain amount of energy is needed for a dislocation to move around a
precipitate. It is associated with a unit length of a dislocation line. To bow through a
small radius (particles are close together) there is a large increase in the proportional
length of the dislocation line, which costs a lot of energy. This means more applied
stress is needed to move the dislocations along hence higher strength of the metal!

Peak strength occurs when shearing and bowing intersect in terms of particle radius.

Notice that as the precipitate radius gets smaller, then the strength increases. This is
opposite from case a where the radius increasing results in increased strength hence the
competition between the 2 shear and bowing.

Section 7- Annealing
Annealing is a high temperature process that is used to counter (reverse) the effects of
cold working in order to restore ductility and decrease strength. It occurs by 3 steps:
recovery, recrystallization, and grain growth. These steps lower the energy by
rearrangement of dislocations to minimize residual stress, growth of new dislocation-free
grains, and decrease of grain-boundary area. They are affected by time, initial %CW,
and temperature of annealing.

Recovery:
-Occurs first because it requires the lowest activation energy
-Recovery always occurs in annealing whereas recrystallization and grain growth do not.
-It isnt visible since its the rearrangement of dislocations.
-The thermal energy added triggers diffusion and some dislocation motion could occur to
either reduce strain energy or even reduce the number of dislocations.
-The properties dont really change at this stage
-Important as a stress relief anneal where the strength is retained but internal stresses
are removed
-Used to prevent stress corrosion cracking and eliminate distortion

Recrystallization:
-Will not occur unless a certain amount of %CW occurred before (~5% for iron but it
ranges from 2-20% depending on grain size and alloys involved)
-New equiaxed grains (typically smaller than original grains) replacing the heavily
deformed and elongated ones from cold working
-Hardness and strength decreases while ductility increases. Dislocation density is
lowered.
-It is thermally activated and obeys Arrhenius equation for its rate
-The higher the temperature, the faster recrystallization occurs
-Recrystallization temperature (Tr) is the T at which heavily a cold work sample (>50%
CW) will fully recrystallize in one hour. Typically this lies between 0.3-0.7 Tmp in Kelvins.
-Tr is influenced by small amounts of impurities so care must be taken when determining
its value when a metals composition is not known entirely
-We anneal to avoid cracking when a metal has been cold worked and we combine CW
+ Annealing to get desirable properties

Grain Growth:
-Grain growth is the final step and is driven by reduction in grain boundary area
-Large grains grow and the smalls disappear
-There is a drop in strength as grain sizes grow proportional to 1/sqrt(d) (Hall-Petch
equation)

Hot Working
Hot working is a process similar to cold working but it operates at T>0.4Tmp in Kelvins.
Dislocation density doesnt really increase with hot working due to recrystallization
occurring almost immediately. So hot working is like a shortcut to annealing. Less
energy is required to plastically deform a metal but the surface oxidizes quickly and it
must be cleaned or dissolved (not aesthetically pleasing and not dimensionally
accurate). Hot working can produce large reductions in area (much more than cold
working) because yield strength is so much lower at higher temperatures. As the metal is
rolled in high temperature, recrystallization occurs and the grain sizes dont elongate but
rather can be smaller or larger than original depending on temperature. Unlike cold
working, the final material is relatively dislocation free. The yield and UTS can then be
altered through other processes so hot working is often used as an intermediate step.

## Section 8- Phase Diagrams

Component a chemical constituent of an alloy.
Solute the component of a solution present in a minor concentration.
Solvent the component of a solution present in the greatest amount.
Solubility Limit- the maximum concentration of solute that may be added without
forming a new phase.
Phase-a homogeneous portion of a system that has uniform physical and chemical
characteristics.
Metastable- non-equilibrium state that may persist for a very long time.
Isomorphous- having the same structure. In the phase diagram sense, isomorphicity
means having the same crystal structure or complete solid solubility for all compositions.
Solvus line- the line on a phase diagram representing the limit of solid solubility as a
function of temperature.
Solidus line- the line on a phase diagram at which solidification is complete upon
equilibrium cooling, or at which melting begins upon heating.
Liquidus line-The line indicating above which melting of a solid is complete upon
heating or at which solidification begins upon cooling.
Invariant point-a point on a phase diagram at which three phases are in equilibrium
Proeutectic (or primary denoted as 1) the first phase to start solidifying from the
liquid upon cooling for a hypo or hypereutectic overall composition. Forms at
temperatures above the eutectic temperature (Te) but below the liquidus.
Eutectic- structure formed at the eutectic temperature.Based on alloy compositions
Hypereutectic refers to the range of compositions above the eutectic composition up
to the solid solubility limit of A in B at the eutectic temperature i.e. to the right side of the
diagram. (hyper means more, or concentrated so it may help to think of a child who
eats too much sugar they become hyper or hyperactive or overly active).
Hypoeutectic refers to the range of compositions above the solid solubility limit of B in
A at the eutectic temperature, up to, but less than the eutectic composition, i.e. to the left
side of the diagram. (hypo means less, or dilute so it may help to think of jewellery that
is hypoallergenic, in that it has low concentrations of metals that cause allergic
reactions).

## Section 9- Phase Transformations

-If equilibrium were to be reached instantaneously, we wouldnt have the diverse
properties of materials such as steel
-Eutectoid reactions can result in pearlite, bainite, martensite or spheroidite
-Lowering the total free energy is the driving force for a phase transformation.
-For solid-solid transformations, the driving force is undercooling.
-Undercooling is the Delta Temperature between the temperature of
transformation and temperature of interest
-But undercooling isnt always enough to cause rapid phase transformation so
the actual temperature of interest that affects the rate of diffusion matters too (for
diffusional phase transformations)
-Kinetics tell us that phase transformations take a certain amount of time (phase
transformation rate)

## Diffusion dependent (diffusional) transformation

a. Doesnt involve a change in composition/number of phases (solidification of a
pure metal, recrystallization, grain growth)
b. Involving a change in composition and/or number of phases (eutectic/eutectoid
reactions)

## 2 stages to diffusional transformations:

1. Nucleation: Which is the formation of very small particles or nuclei of a
new phase which are capable of growing
2. Growth: Growth of the nuclei until equilibrium is obtained
*The amount of undercooling affects the number of nuclei that form and the
growth. In some systems, they are rate limiting.

## Lets take a look at nucleation in the solidification process first. Homogenous

nucleation is when the nuclei formed in the bulk of liquid metal require
supercooling or undercooling (80-300 C). The formation of the solid sphere
lowers the energy of the system by producing volume of a stable phase, but
costs energy through the creation of a new surface or interfacial area. Such
energy terms oppose each other and lead to an energetic barrier for the
occurrence of the phase transformation. To form a stable nucleus that will grow,
we require a balance of two types of energy: surface energy and volume energy.
If the equilibrium thermodynamics tell us that we are at a temperature, pressure
and composition that should result in a phase transformation then we should be
able to lower the total free energy G by nucleating and growing the new phase.
The volume energy is the most effective way for achieving such a goal (volume
energy is deemed negative because it lowers the total energy of the system)
because it is the best way to reduce total energy. The energy holding back the
transformation is surface energy. It costs energy to create a new surface (the
nuclei) thus surface energy opposes the volume energy and we have a net result
of the barrier for transformation- a critical radius. If growth is to occur, critical

## VOLUME ENERGY STABLIZIES THE NUCLEI BY RELEASING ENERGY.

SURFACE ENERGY DESTABILIZES BECAUSE IT USES ENERGY.

## For a homogenous nucleation, critical radius of a stable solid particle nucleus

2
= and activation free energy required for the formation of a stable nucleus

163
is = where:
3( )^2

gamma=surface tension
Tm=melting temperature
Delta Hf=latent heat of solidification
Delta T=Tm-T=undercooling

## The above equations describe the formation of a solid in a bulk liquid

(homogenous nucleation). But a nucleating phase growing on the sides of a
container (surfaces) is called heterogeneous nucleation because if a phase
nucleates on another surface, then there is less surface in need of creation and
thus less energy opposes the transformation. As a result, the energy barrier is
less for heterogeneous than for homogeneous.
Heterogeneous nucleation
This is much easier since stable nucleus is already present. Could be a wall of
mold or impurities in the liquid phase, which allows solidification with only 0.1-10
C supercooling needed.

## Nucleation is a temperature dependent process. The lower the temperature, the

higher the number of stable nuclei but lower the frequency of attachment. But the
overall curve has a maximum rate of nucleation at intermediate undercooling that
is a middle temperature. The barrier for nucleation at low temperature is due to
much lower rates of diffusion necessary for nuclei formation.

## Overall Transformation Rate

Growth of a phase depends on the amount of material able to reach the surface
and attach to it in the correct composition. Thus, growth depends exponentially
upon temperature. Growth rate is high at high temperatures while nucleation rate
is low at high temperatures. Overall transformation rate is the balance between
the 2.

Now lets see how these ideas can be applied to steels. For eutectoid steels,
solid-state eutectoid reaction is important (Austenite Ferrite and Cementite).
Austenite decomposes in lamellar structure (alternating plates) because the
transformation is diffusion limited. Nucleation of ferrite and cementite crystals
starts at austenite grain boundaries; carbon is rejected from the austenite and
ferrite forms, and the rejected carbon diffuses to form cementite. Depending on
the cooling rate (which ultimately affects the magnitude of the undercooling delta
T) the interlamellar spacing will change. For rapid cooling (large delta T) the
pearlite spacing will be very small (fine) because the carbon diffusion distance
will be shorter. For rapid cooling, there will also be more nuclei but less diffusivity
for growth so the spacing is small.

## Rapid cooling FINE pearlite

Slow cooling COARSE pearlite

Diffusionless transformations?
-These require nucleation but no growth in order to have a phase transformation.
-They dont need diffusion over large distances.
-Involve a reordering of the atoms (diffusion occurs over very small distance)
-Need to consider surface energy and the pressure the phases induce in each
other
-Can produce metastable phases (austenite transforming into martensite)

## Martensite is a body centered tetragonal metastable phase of iron and

carbon. There is a high concentration of carbon trapped in the lattice,
resulting in very high hardness.

## Equilibrium Phase Transformations

These are those that yield what the phase diagram tells us should be present
with an infinite time for achieving equilibrium. For a two-phase field, the
equilibrium microstructure would have no concentration gradients, and would
form a single sphere of one phase in the other and be a perfect single crystal.
This can never happen with engineering materials. The phase diagrams we study
can show us the phases present but not the structure of the phases because
microstructure is cooling and path dependent so instead, we need to know phase
constitution and phase morphology to be able to correlate certain properties.

## Rate of Phase Transformation

Kinetics- measure approach to equilibrium vs. time if you hold the temperature
constant and measure conversion vs. time.
Time-Temperature-Transformation (TTT curves)
-Isothermal transformation diagram
-Show how long it takes austenite to transform into ferrite and cementite at
different temperature
-For other compositions, the curves are different

## TTT curve for Fe-C eutectoid composition (Why is C shape?)

-Just below 727 C, transformation is slow because nucleation is difficult.
-Around 550 C (the nose), transformation is quick because nucleation and
growth rate are both favorable.
-Around 250 C, transformation is slow, because driving force for nucleation is
large but diffusion for growth is slow.
Product #1: Pearlite
Pearlite is produced above the nose of the curve
-Just below 727 C, coarse pearlite due to fewer nucleation sites but faster
growth
-Around the nose, fine pearlite due to more nucleation sites but slower growth

## Product #2: Bainite

-Bainite is produced below the nose of the curve
-Bainite is still -Fe + Fe3C, but appears plates or needle like morphology.

## Product #3: Spheroidite

-Spheroidite is produced by heating bainite or pearlite for long time.
-Carbon diffusion: driving force is the reduction in -Fe3C phase boundary area

## QUENCHING: Cool Austenite microstructure in no time to very low temperature

(usually water)
-We can bypass transformation of A to ferrite and cementite and get a new
metastable phase called Martensite
-Martensite is not ferrite and cementite and transformation does not involve
diffusion
-Austenite to Martensite transformation is rapid
-% Transformation depends on temperature only!

## TEMPERING: Re-heat steel to an intermediate temperature below 727C for

phase transformation

## Lets talk about Martensite (M)

-M has a BCT structure with saturated C trapped in voids between Fe-atoms
-M is the hardest and strongest and most brittle
-Large internal stresses exist in quenched steels since there is a net volume
increase when austenite is transformed into martensite
-You can only go from Austenite to Martensite, not Bainite/Pearlite/Spheroidite to
Martensite

## Pure martensite cannot be used for most applications.

-However, the ductility and toughness of martensite may be enhanced and the
internal stresses relieved by a heat treatment known as tempering
-Tempering is a heat treatment in which martensitic steel is held at a temperature
below the eutectoid reaction temperature for a specified time period.
-Tempering allows, by diffusion processes, the formation of tempered martensite,
according to the reaction: Martensite (BCT, single phase) Tempered
Martensite (-Fe + spherical Fe3C)
-Similar to Spheroidite, but with extremely small Fe3C particle surrounded by -
Fe: -reduces brittleness of martensite reduces internal stress caused by
quenching. Decreases TS, YS but increases %RA

rate = faster)

## As t Diameter of cementite increases strength ductility . (More time for

diffusion)=
Ranking of hardness/strength (weakest to strongest):
Spheroidite, Coarse pearlite, Fine pearlite, Bainite, Tempered Martensite,
Martensite.

## Ranking of %RA for fine, coarse and sphere:

Fine pearlite < Coarse pearlite < Spheroidite

## Cooling rate mechanisms

Full Anneal- Starting with 100% austenite, cooling very slowly (either control the
rate or turn off furnace and leave the door closed to cool naturally)-turning off the
oven and letting the cookies cool inside the oven.
Normalize-Starting with 100% austenite, cool moderately slowly then air cool.
Take cookies out of the oven and leave outside to cool.
Quench- Starting with 100% austenite, cool very quickly (plunge sample in
water, oil, brine..etc). Toss the cookies in water to cool them!

Tempered Martensite
-Properties depend on size of cementite carbides formed during tempering
-Smaller carbides mean the more interfacial areas present and dislocation
motions are interrupted
-Size of the carbides increase with temperature and time when tempering

## Hardenability- the ability to form martensite

Cooling rate varies with position.
Section 11- Polymers
Thermoplastics Contains parts made from engineering thermoplasts like
polycarbonate or nylon. The structure consists of long chain molecules
(covalently bonded) held together with secondary (Van der Waals or hydrogen)
bonds. (Plate of spaghetti analogy) Because these bonds are weak (10% of
primary bonds) the materials melt at low temperatures, since materials melt
about when the thermal energy kT becomes equal to the bond energy (low
modulus of elasticity as well). These polymers can be melted and re-used.
Examples would be polyethylene (PE), used in disposable grocery bags;
polyvinylchloride (PVC), used in water plumbing, and polypropylene (PP) used in
many food containers such as yogurt. Thermoplastics are linear or branched
polymers.

Thermosets
These are polymers like epoxy and bakelite (phenol formaldehyde) that form
primary bonds between the molecules when they polymerize so the whole
structure is held together by a three dimensional network of primary covalent
bonds. Once these polymers are set they cannot be melted. Thus when we mix
the components of epoxy, they link together chemically and polymerize
essentially into one giant molecule. These polymers are stronger and more
stable than thermoplasts, but cannot be formed after setting and cannot be
recycled. A common example is a two-part epoxy (a resin and a hardener). When
mixed the hardener initiates the polymerization reaction to form a high density of
polymers. Network polymers start out as branched mer units, which are then

Elastomers
An important class of polymers, which can elongate more than 100% and will
recover their original length quickly and completely (think of elastic bands). They
have important applications as hoses, and seal rings and of course in tires for
transportation vehicles of all kinds. Original elastomer was natural rubber that
was created by Charles Goodyear when he crosslinked the isoprene (natural
rubber from the tree) with sulfur, so that the molecules were tacked together with
primary bonds (a crosslink). This meant they could uncoil on application of load
but the molecules would not slide permanently past one another (as thermoplasts
tend to do). When the load is removed the molecules recoil to their low energy
configuration. These polymers have very low stiffness

## Decreasing T is equivalent to increasing strain rate (shorter loading time)

-Increases E and TS
-Decreases %EL
-Usually shift from rubbery to glassy regime