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RUNNING HOT… Sub-topics Fuel cells Casting 1 Solidification
RUNNING HOT…
Sub-topics
Fuel cells
Casting
1
Solidification

CONCEPT OF FUEL CELLS

C ONCEPT OF FUEL CELLS
 

International concerns regarding the emission of greenhouse gases and the trend toward distributed power generation are of current interest to the technical community.

 

A fuel cell is an electrochemical cell that produces electricity from a replenishable fuel tank.

Fuel cells can operate virtually continuously as long as the necessary flows (reactions) are maintained (they consume reactant from an external source, which must be replenished).

 
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FUEL CELL

F UEL CELL

The electricity is generated through the reaction, triggered in the presence of an electrolyte, between the fuel (on the anode side) and an oxidant (on the cathode side). The reactants flow into the cell, and the reaction products flow out of it, while the electrolyte remains within it.

F UEL CELL The electricity is generated through the reaction, triggered in the presence of an
   

Many combinations of fuels and oxidants are possible. A hydrogen fuel cell uses hydrogen as its fuel and oxygen (usually from air) as its oxidant. Other fuels include hydrocarbons and alcohols. Other oxidants include chlorine and chlorine dioxide

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MEMBRANE FUEL CELL 4
MEMBRANE FUEL CELL
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FUEL CELLS DESIGN

 
F UEL CELLS DESIGN

Interconnection

Interconnection Electrolyte Air

Electrolyte

Air

Schematic diagram of a SOFC bundle configuration

Schematic diagram of a SOFC bundle configuration

Electrode

Electrode

Fuel Electrode

Developing the technology for

Developing the technology for
 

Air

producing components that meet

Flow

these property requirements requires

The electrolyte must conduct ions, but not electrons, while the electrodes must conduct the electrons generated by the electrode reactions. In addition, the tubes in

processing schemes that produce specific types of micro- and macrostructures.

structural components must be gastight and mechanically stable at high temperatures.

This requires minimizing thermal expansion differences among the components, and developing gastight seals for the high temperature use.

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FUEL CELLS (CONT) In addition, the composite components must be chemically compatible with each other and
FUEL CELLS (CONT)
In addition, the composite components
must be chemically compatible with
each other and with the fuel.
Recent advances in materials selection
and microstructure, combined with
fabrication of electrode-supported
thin-electrolyte planar geometries, has
resulted in tremendous performance
gains.
In addition to oxide ceramics,
silicon-based ceramics such as
SiC, Si3N4, and sialons
along with other borides,
carbides, nitrides, silicides, and
diamond and diamond-like
materials are now common high T
materials of scientific and
technological interest in both bulk
and coating configurations
Current advanced planar SOFCs
have demonstrated ~2 W/cm2 at the cell
level, at 700°C.
These power densities are greater than previous generation cells at 1000°C,
thus, providing the opportunity to utilize less expensive metal interconnects.
However, the use of metal interconnects brings with it new challenges in
high temperature corrosion prevention.
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HEAT

H EAT
   

What is a heat?

Heat from the sun is the

Heat from the sun is the

Heat is atoms in motion.

In solids, atoms vibrate about their mean position with a frequency v (about 10 13 /second) with an average energy (kinetic + potential), of RT.

driving force of life on Earth.

In physics and thermodynamics, heat is the process of energy transfer from one body or system due to thermal contact, which in turn is defined as an energy transfer to a body in any other way than due to work performed on the body.

Temperature is used as a measure of the internal energy or enthalpy, that is the level of elementary motion giving rise to heat transfer.

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CASTING 9
CASTING
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CASTING PROCESS

Casting

Casting

C ASTING PROCESS Casting
 
C ASTING PROCESS Casting is a fabrication process whereby a totally molten metal is poured into
C ASTING PROCESS Casting is a fabrication process whereby a totally molten metal is poured into

is a fabrication process whereby a totally molten metal is poured into a mold cavity having the desired shape

Casting techniques are employed when

(1)the finished shape is so large or complicated that any other method would be impractical, (2)a particular alloy is so low in ductility that forming by either hot or cold working would difficulties, and (3) in comparison to other fabrication processes, casting is the most economical.

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SAND MOLD CASTING A two-piece mold is formed by packing sand around a pattern that has
SAND MOLD CASTING
A two-piece mold is formed by
packing sand around a pattern
that has the shape of the
intended casting
The sand casting process
involves the use of
a furnace, metal, pattern, and
sand mold.
The metal is melted in the
furnace and then ladled and
poured into the cavity of the
sand mold, which is formed
by the pattern. The sand
mold separates along a
parting line and the solidified
casting can be removed.
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INJECTION MOLDING

I NJECTION MOLDING
 
Injection molding is the most commonly used manufacturing process for the fabrication of plastic parts. The

Injection molding is the most commonly used manufacturing process for the fabrication of plastic parts. The injection molding process requires the use of an injection molding machine, raw plastic material, and a mold.

The plastic is melted in the injection molding machine and then injected into the mold, where it cools and solidifies into the final part.

The common thin-walled products include different types of open containers, such as buckets. Injection molding is also used to produce several everyday items such as toothbrushes or small plastic toys. Many medical devices, including valves and syringes, are manufactured using injection molding as well.

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DIE CASTING Die casting is a process that can produce geometrically complex metal parts through the
DIE CASTING
Die casting is a process that can
produce geometrically complex metal
parts through the use of reusable
molds, called dies.
The die casting process involves the
use of a furnace, metal, die casting
machine, and die.
The metal, typically a non-ferrous
alloy such as aluminum or zinc, is
melted in the furnace and then
injected into the dies. After the
molten metal is injected into the
dies, it rapidly cools and solidifies
into the final part, called the
casting.
Metal housings for a variety of appliances and equipment are often die
cast. Several automobile components are also manufactured using die
casting, including pistons, cylinder heads, and engine blocks.
Other common die cast parts include propellers, gears, bushings, pumps,
and valves.
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CENTRIFUGAL CASTING

C ENTRIFUGAL CASTING
   
Centrifugal casting , sometimes called rotocasting, is a metal casting process that uses centrifugal force to

Centrifugal casting, sometimes called rotocasting, is a metal casting process that uses centrifugal force to form cylindrical parts. This differs from most metal casting processes, which use gravity or pressure to fill the mold. In centrifugal casting, a permanent mold made from steel, cast iron, or graphite is typically used.

The casting process is usually performed on a horizontal centrifugal casting machine (vertical machines are also available).

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WHY IS PROCESS OF SOLIDIFICATION IMPORTANT?

 
W HY IS PROCESS OF SOLIDIFICATION IMPORTANT ?
 
 

Solidification

http://www.youtube.com/watch?v=kJGlg

http://www.youtube.com/watch?v=kJGlg

is an important industrial process since most metals are melted and then cast into a semi-finished or finished shape.

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WHY TO STUDY SOLIDIFICATION?

W HY TO STUDY SOLIDIFICATION ?
   

80% of ALL industry involves a casting and solidification process of materials in various ways

The initial microstructure of the material forms during solidification process where the melted alloy becomes a (crystalline) solid

During the last century, by examining metal alloys with an optical microscope after polishing and etching the surface, it was discovered that the microstructures influenced the material's properties .

Clearly, it is important to understand this subject

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NUCLEATION AND GROWTH OF GRAINS When a liquid solidifies, solid first has to appear from

N UCLEATION AND GROWTH OF GRAINS When a liquid solidifies, solid first has to appear from
 

somewhere, after which the interface between solid and liquid can migrate to enable atoms to switch from one phase to the other at the boundary – the two stages are

nucleation and growth

N UCLEATION AND GROWTH OF GRAINS When a liquid solidifies, solid first has to appear from
N UCLEATION AND GROWTH OF GRAINS When a liquid solidifies, solid first has to appear from

SOLIDIFICATION OF METALS The steps of solidification:

S OLIDIFICATION OF METALS The steps of solidification:
 
S OLIDIFICATION OF METALS The steps of solidification: Thermal gradients define the shape of each grain.
S OLIDIFICATION OF METALS The steps of solidification: Thermal gradients define the shape of each grain.

Thermal gradients define the shape of each grain.

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SOLIDIFICATION: METAL CASTING

S OLIDIFICATION : M ETAL CASTING
   

In casting, a liquid above its melting point is poured into a mold where it cools by thermal conduction – it is relatively cheap and well suited for complex 3-d shapes

New solid forms by nucleation – new crystals form in the melt, on the walls of

New solid forms by nucleation – new crystals form in the melt, on the walls of the mold, or on foreign particles

Crystals grow in opposing directions and impinge on one another to form grain boundaries

Crystals grow in opposing directions and impinge on one another to form grain boundaries
 

FUNDAMENTALS

   
F UNDAMENTALS

Solidification is a change from liquid to solid state Recall the atomic arrangements in a liquid and solid 2 step process of NUCLEATION and GROWTH

 

Solidification - the liquid cools to just below its freezing (or melting) temperature, because the energy associated with the crystalline structure of the solid is less than the energy of the liquid.

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FORMATION OF STABLE NUCLEI

     

Two main mechanisms:

Homogenous and heterogeneous.

Homogenous Nucleation :

Metal itself will provide atoms to form nuclei.

Metal, when significantly cooled (below freezing T), has several slow moving atoms which bond each other to form nuclei.

Cluster of atoms below critical size is called embryo (continuously being formed and re-dissolved in a molten metal) .

If clusters of atoms reach critical size, they grow into crystals. Else get dissolved.

Cluster of atoms that are grater than critical size are called nucleus.

The critical radius is the minimum size of a crystal that must be formed by21 atoms clustering together in the liquid before the solid particle is stable and begins to grow.

The critical radius is the minimum size of a crystal that must be formed by 21

THE RELATIONSHIP BETWEEN FREE ENERGY AND TEMPERATURE

THE RELATIONSHIP BETWEEN FREE ENERGY AND TEMPERATURE
 
At the melting point, both phases have the same free energy and can co-exist

At the melting point, both phases have the same free energy and can co-exist

Above the melting point, liquid is in the state of lower free energy; If a liquid is cooled beyond its melting point, its free energy is greater than that of a solid;

The system can release energy if it solidifies – this is the driving force for phase transformation

Energy difference between the liquid and the solid is the driving force for solidification.

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ENERGIES INVOLVED IN HOMOGENOUS NUCLEATION Two kinds of energy should be considered 23
ENERGIES INVOLVED IN HOMOGENOUS
NUCLEATION
Two kinds of energy should be considered
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FREE ENERGY CHANGE Energy opposing to the formation of embryos, the energy to form Retarding energy
FREE ENERGY CHANGE
Energy opposing to
the formation of
embryos, the
energy to form
Retarding energy
the surface of
these particles ~
specific surface free
energy
Energy is
released by the
Driving energy
liquid to solid
transformation
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TOTAL FREE ENERGY Total free energy associated with the formation of embryo 25
TOTAL FREE ENERGY
Total free energy associated with the formation
of embryo
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CONDITIONS FOR NUCLEATION

     
C ONDITIONS FOR NUCLEATION

Stable cluster

Stable cluster nucleation solidification

nucleation

solidification

Assume spherical cluster of radius R

Total energy = Volume energy (negative) + Surface energy (positive)

Total energy E T = 4/3 R 3 G v + 4 R 2
Total energy E T = 4/3 R 3 G v +
4 R 2
   

dE T /dR = 0 for energy to be minimum dE T /dR = 4 R 2 G v + 8 R =0

 
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r* is the critical radius for a stable nucleus

CRITICAL RADIUS AND TEMPERATURE The greater the degree of undercooling, the greater the change in volume
CRITICAL RADIUS AND TEMPERATURE
The greater the degree of undercooling, the
greater the change in volume free energy.
Surface energy does not change much with T.
Cluster stability depends
on energy:
Energy change is positive:
instable cluster
Energy change is negative:
stable cluster
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CRITICAL RADIUS VERSUS UNDERCOOLING Homogeneous nucleation occurs when the undercooling becomes large enough to cause the
CRITICAL RADIUS VERSUS UNDERCOOLING
Homogeneous nucleation
occurs when the undercooling becomes large enough
to cause the formation of a stable nucleus.
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The latent heat of fusion (entalphy) represents the heat given o¤
during the liquid-to-solid transformation.
UNDERCOOLING The undercooling (T) is the difference between the equilibrium freezing temperature and the actual temperature
UNDERCOOLING
The undercooling (T) is the difference between the
equilibrium freezing temperature and the actual
temperature of the liquid.
As the extent of undercooling increases,
the thermodynamic driving force for the formation of a solid phase from the
liquid overtakes the resistance to create a solid-liquid interface.
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PROBLEM Problem: Calculate the critical radius of a homogeneous nucleus that forms when pure liquid copper
PROBLEM
Problem: Calculate the critical radius of a homogeneous nucleus
that forms when pure liquid copper solidifies. Assume T of
undercooling = 0.2 Tmelt
Calculate the number of atoms in the critical-sized nucleus.
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HETEROGENEOUS NUCLEATION Contact angle between solid and liquid The solid nucleating agent 31 must be wetted
HETEROGENEOUS NUCLEATION
Contact angle
between solid
and liquid
The solid
nucleating agent
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must be wetted by
the liquid metal.
 

DOES WATER REALLY FREEZE AT 0 C?

 
D OES WATER REALLY FREEZE AT 0 C?
 

This process is dependent on the contact angle for the nucleating phase and the surface on which nucleation occurs.

a radius of curvature greater than the critical radius

Relatively few atoms must cluster

together to produce a solid particle that has the required radius of curvature. Much less undercooling

together to produce a solid particle that has the required radius of curvature.

together to produce a solid particle that has the required radius of curvature. Much less undercooling

Much less undercooling is required to achieve the critical size, so nucleation occurs more readily.

is achieved with very little total surface between the solid and liquid.

The rate of nucleation (the number of nuclei formed per unit time) is a function of temperature.

Prior to solidification, there is no nucleation. As T drops, the driving force for nucleation increases; however, as T decreases, atomic

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a typical rate of nucleation

reaches a maximum at some T

diffusion becomes slower, hence slowing the nucleation process.

below the transformation T

 

GROWTH OF CRYSTALS AND FORMATION OF GRAIN STRUCTURE

G ROWTH OF CRYSTALS AND FORMATION OF GRAIN STRUCTURE
   

Nucleus grow into crystals in different orientations.

Crystal boundaries are formed when crystals join together at complete solidification.

• Crystals in solidified metals are called grains.

• Grains are separated by grain boundaries.

• More the number of nucleation sites available, more the number of grains formed.

When will we obtain fine-grained structures?

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SOLIDIFICATION(COOLING) CURVES Pure metal Alloy L Soldification L begins T L L + S L S
SOLIDIFICATION(COOLING) CURVES
Pure metal
Alloy
L
Soldification
L
begins
T
L
L + S
L
S
T m
T
S
Solidification
S
S
complete
Alloys are used in most engineering applications.
• Example:
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Cartridge brass is binary alloy of 70% Cu and 30% Zinc.
Iconel is a nickel based superalloy with about 10 elements.

RATE OF TRANSFORMATION

The rate of nucleation

R ATE OF TRANSFORMATION The rate of nucleation 35
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R ATE OF TRANSFORMATION The rate of nucleation 35
 

(the number of nuclei formed per unit time) is a function of temperature. Prior to solidification there is no nucleation. At T above the freezing point, the rate is zero. As the temperature drops, the driving force for nucleation increases. However, as the temperature becomes lower, atomic diffusion becomes slower, hence slowing the nucleation process. Thus, a typical rate of nucleation reaches a maximum at some temperature below the transformation temperature

COARSE-GRAINED OR FINE-GRAINED?

C OARSE - GRAINED OR FINE - GRAINED ?
   
C OARSE - GRAINED OR FINE - GRAINED ? The size of the particles depends on
C OARSE - GRAINED OR FINE - GRAINED ? The size of the particles depends on
 

The size of the particles depends on transformation temperature.

For transformations that occur at T near to melting point corresponding to low nucleation and high growth rates, few nuclei form that grow rapidly. Thus, the resulting microstructure will consist of few and relatively large phase particles (e.g., coarse grains).

For transformations at lower T, nucleation rates are high and growth rates low, which results in many small particles (e.g., fine grains).

When a material is cooled very rapidly to a relatively low T where the rate is extremely low, it is possible to produce nonequilibrium phase structures

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CAN MATERIALS BE STRENGTHENING DURING SOLIDIFICATION?

       
C AN MATERIALS BE STRENGTHENING DURING SOLIDIFICATION ?
Grain structure of Aluminum cast with and without grain refiners.

Grain structure of Aluminum cast with and without grain refiners.

When a metal casting freezes, impurities in the melt and walls of the mold in which solidification occurs serve as heterogeneous nucleation sites.

 

To produce cast ingots with fine grain size, grain refiners are added.

   

Example: For aluminum alloy, small amount of Titanium, Boron or Zirconium is added.

The greater grain boundary area provides grain size strengthening in metallic materials.

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WHAT IS DENDRITE?

If the liquid is undercooled, a protuberance

If the liquid is undercooled, a protuberance

W HAT IS DENDRITE ? If the liquid is undercooled, a protuberance
 
on the solid-liquid interface can grow rapidly as a dendrite. The latent heat of fusion (enthalpy)

on the solid-liquid interface can grow rapidly as a dendrite. The latent heat of fusion (enthalpy) is removed by raising the temperature of the liquid back to the freezing temperature.

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SOLIDIFICATION IN CASTING Dendritic growth continues until the undercooled liquid warms to the freezing temperature. Any
SOLIDIFICATION IN CASTING
Dendritic growth continues until the undercooled
liquid warms to the freezing temperature. Any
remaining liquid then solidifies by planar growth.
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TYPES OF GRAINS Equiaxed Grains: Crystals, smaller in size, grow equally in all directions. M Formed
TYPES OF GRAINS
Equiaxed Grains:
Crystals, smaller in size, grow equally
in all directions.
M
Formed at the sites of high
concentration of the nuclie.
M
Columnar Grains:
M
Long thin and coarse.
M
Grow predominantly in one direction.
Formed at the sites of slow cooling
and steep temperature gradient.
M
Example: Grains that are away from
the mold wall.
M
Columnar Grains
Equiaxed Grains
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VIEW OF THE SOLIDIFIED INGOTS

 
V IEW OF THE SOLIDIFIED INGOTS
 
The colomnar grains have grown perpendicular to the mold faces since large thermal

The colomnar grains have grown perpendicular to the mold faces since large thermal

gradients are presented in those directions

gradients are presented in those directions

 
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SOLIDIFICATION OF SINGLE CRYSTALS The most widely used technique for making single-crystal silicon is the Czochralski
SOLIDIFICATION OF SINGLE CRYSTALS
The most widely used technique for making single-crystal silicon is the
Czochralski process,
in which a seed of single-crystal silicon contacts the top of molten silicon.
As the seed is slowly raised, atoms of the molten silicon solidify in the
pattern of the seed and extend the single-crystal structure.
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