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1st March

Casting Quality slide 39

The aim of the engineer would be to reduce defects during casting. Diffficult to get defect
free casting. Many castings had lower rating because of presence of porosity within
microstructure. These types of porosities can exist either on the micro level (tiny porosities
viewed by microscope), still detrimental but not as detrimental as macro porosities (visible
by naked eye) which result from either excessive gas evolution during solidification (eg
hydrogen in aluminium) or due to inadequate design in casting – blockage of feed liquid that
is required to compensate for shrinkage on solidification – build up of residual tensile
stresses resulting in large porosities.

Inclusions such as non metallic inclusions eg sand particles that can end up in casting during
filling of mold. Inclusions that are poorly wetted by liquid are very detrimental – facilitate
formation of porosity – growth of pores, in casting. Inclusions can also promote corrosion
due to different chemical nature from the surrounding material. Defects are typically
related to poor practices – misalignment of mold house, introduction of foreign particles
(leads to primary inclusions), intro of gas bubble due to turbulent filling of mold. Intrinsic
defects – evolution of insoluble gases in the solid case (eg hydrogen in aluminium), or due to
shrinkage in micro level (certain types of growths – dendritic growths, tiny spaces between
dendrites contain solidifying liquid – end up with micro porosity), or macro level (problems
in design of feeding system).

Nucleation of solids - slide 41


Liquid eventually transforms into a solid – when we have a metal which is heated to above
the melting temperature, the material will exist as a liquid because the free energy of the
liquid state at a temp higher than melting, will be lower than the free energy of same
material in solid state, so when the temp reaches melting, free energy of liquid and solid is
equal. Every system will try to go from state of high to low energy, so liquid at temp lower
than melting temp will have a higher thermodynamic driving force to transform into a solid.
But this does not generally happen spontaneously. In order for the solid to start to form –
need to form stable nuclei – collection of atoms grouped together in sold state that can acct
as basis for further growth of material. For these to form we need to supply energy because
these nuclei that form in the liquid will have a surface and associated with that surface
there will new energy – surface energy of that nuclei. This nucleation of solid cannot happen
spontaneously as temperature goes just below melting temp, but have to be cooled several
degrees below melting temp, sometimes even few hundreds of degrees to ensure that
nuclei that form are stable and grow. If they are not stable, they will redissolve back to
liquid. So when these nuclei become stable and grow, eventually transform liquid to solid.
Very common in polymeric materials -> during cooling – not enough sufficient time for
nuclei to form , temp keeps dropping until atoms/molecules won’t have sufficient energy to
flow in a liquid – will eventually still turn into solid – without going through nucleation and
growth temperature – cooled below GLASS TRANSITION temp – solid which forms will be
non crystalline – amorphous . This is very difficult to achieve with metals, to cool below GT
temp without nucleation – VERY high cooling rates, but much easier in polymeric materials,
especially with complex repeat units to solidify as amorphous
Homogenous Nucleation of Solids slide 42
Occurs if all the liquid was at the same temp – no preferred sites for nucleation. Assume
liquid, no container walls, no solid particles, if liquid is all at same temp – homogenous
nucleation. Typically nucleation will require cooling for several hundred degrees below
melting point. The stable nucleus that forms is typically few hundred atoms. Quite difficult
to form – not many will form. This is because energy released by liquid to form solid is offset
by formation of nucleus.

Slide 43
Both types of free energy both go down as temp increases, but liquid with steeper gradient.
There is a point where free energies of liquid and solid are equal -> MELTING
TEMPERATURE. Below melt – solid more stable, higher than melt – liquid more stable. As
temp drops further below Melting temp – Delta T increases – the difference between free
energies of liquid and solid gets bigger and bigger – increasing the amount of energy that
will be released as liquid transforms into a solid – increasing the driving force to transform
to solid – increasing delta G with delta T. Nuclei can never form at temp above melt temp.
Below Melt temp, only nuclei that are large enough to tip the energy balance in favour of
solidification (more energy lost than gained) will become stable and grow.

Slide 44 diagram
Depicting energy gained/lost which is plotted against radii of nuclei for given temp below
the melt temp. As the radius of nucleus increases, amount of delta G (energy lost by transf
of liquid to solid) gets bigger. But at the same time as this nucleus is getting bigger – bigger
interfacial area between nucleus and surrounding area – system is also gaining energy
through bigger interface. If substract black and red = blue. For nuclei with radius smaller
than critical radius (rc), increasing radius of nucleus, will be energy unfavourable – will
dissolve back to liquid. Any nucleus with radius larger than rc – will become stable – because
as it grows, overall energy of system goes down. Typically for spontatnuos homogenous
nucleation – this rc should preferably by a small nucleus with few atoms. We can make rc
smaller and smaller by increasing delta T – degree of undercooling – which increases
amount of energy liberated as liquid transforms into solid – black curve steeper downwards
– and interfacial energy is minimally effected – shifting maximum rc to the left – smaller
stable nucleus. For nuclei which can form by interacting atoms/ molecules we would require
very large delta Ts. The smaller rc, easier for a nucleus to form, and more nucleation sites
form, and grow, result in finer structure. If we want fine microstructure want to have small
rc. When nuclei start to form energy is being liberated, but also enery gained by creation of
new interface. For nuclei to be stable, energy created larger than gained. Typically for nuclei
to be stable and grow – very large degree of delta T – undercooling.

Slide 45
As temp of melt falls further below melting temperature – delta T increases – delta G
(energy released ) increases – interfacial the same – rc becomes smaller smaller as delta T
increases. For spherical nucleus at melt temp T, relationship between rc and delta T can by
estimated: see equations of slide 45

Slide 46
The entropy change which is typically measure of disorder in system – mostly due to change
from amourpohus liquid to arranged crystalline solid – approximately equal for solidification
at Tm. Delta G are equal for liquid and solid at melting temperature. See derivation of slide
46.

Slide 47
What about energy gained by system? Equal to area of sphere multiplied by surface energy
of solid liquid interface – therfor – net change in energy as the nucleus grows – equal to
energy gained by new surface minus energy lost ( computed before ). At the turning point –
maximum (rc) the differential of energy is equal to zero (2nd equation on slide 47). Last
equation – rc will be smaller with increase of delta T, increase of amount of energy released
(hm), decreasing interfacial energy (ysl). This is what happens for homogenous nucleation –
no sides. Rarely occurs – our liquid contained in a mold and mold walls will act as
heterogeneous sites for nucleation – also many times, because we would want nucleation at
many sites for finer structure – we add nucleating agents on purpose to reduce degree of
undercooling for nucleus to be stable and grow by few degrees

Slide 48
Nucleation happens usually on existing solid – eg mold wall which is a heterogeneous site.
Liquid will start solidifying – nucleating on heterogeneous site which is wetted by liquid, is
easier than homogeneous nucleation – in this case nucleus is forming cap rather than
sphere - which has less atoms – much easier to form – making nucleation easier. For that
cap to become stable and grow. Energy losses – latent heat + energy in destruction of
original nucleant liquid interface. Energy gains – formation of new solid liquid interface and
creation of nucleant interface. Losing liquid nucleant interface and gaining solid liquid +
solid nucleant . Only become stable if energy losses smaller than gains. Typically we can
know how easy for a solid to form by measuring contact angle, the smaller the contact
angle( the better wettability)…. ??? we can design nucleants which will make It easier for
the solid to form and to make that, we have to ensure that the liquid of the melt wets that
nucleant well, in other words, the surface energy of the liquid should be less than the
surface energy of the nucleant . Imagine having a drop of water on 2 different surfaces, on 1
surface drop spreads to film, on the other stays as a sphere- doesn’t wet the surface. This
happens because on surface A the surface tension of the liquid is smaller than the surface
energy of the solid, by spreading it creasted new surface with lower surface energy – by
destroying interface and creasting new one. Example non stick pan – very low surface
energy, so won’t spread. In this case for nucleant to be suitable to facilitate nucleation,
nucleant properly wetted by the liquid, promoted heterogeneous nucleation, if not, it will
act as nucleation site but instead for solid, for pores which is very detrimental. The nucleant
that we shall use should be wetted by melt, and 2. Nucleant should have at least one of the
crystal dimensions which is similar to the solid being nucleated – which means that when
solid nucleated, there will be less cohesive strain, hence energy gained small – favour
nucleation. Solid particles in melt can act as nucleation sites – requiring only few degrees of
undercooling for caps to form and grow. Liquids are always in contact with mold, in the case
where mold surfaces are not very good heterogenous nucleation sites, solid will still tend to
nucleate there, because liquid will have higher delta T, because of cooler mold surface.
Slide 50
Nucleation of solids only at temperatures below melting temperature, because there can
never be favourable energy balance above. However, we want to suppress the nucleation
and growth of porosity inside our castings. Porosity can be facilitated when we get
heteregoneous sites, which are not very well wetted by the liquid. These sites, will make it
easy for pores to become stable and grow. Similar to nucleation of solids, we can have the
nucleation of pores, and can also be described in terms of free enrgy changes. In this case,
however, we will not talk about latent heat, but energy within a pore (multiplication of
change in pressure and volume of the pore and interface energy). In this case the free
energy of the system, when we have the formation of a pore inside a liquid, is going to be
equal to the surface energy between the liquid and gas multiplied by area, plus change in
pressure multiplied by volume of the pore. Delta p positive when pressure compressive on
pore. When delta p is positive (outside larger than inside pore), gamma lg always positive,
and therefore pores cannot grow, since delta G will increase with 2 positive terms. Pores
only grow when pressure inside pore is greater than pressure outside, achieved by gas
evolution which build up pressure inside the pore ,making delta P more negative. The delta
P can also become negative, by surrounding liquid is solidyfing and not being fed by extra
liquid, building up hydrostatic tension inside this liquid, which will trigger a negative delta P,
and that will trigger poor nucleation growth. In erms of porosity , we can find different
types., especially when we have this hydrostatic tension. Solidification cracking and hot
tearing typically happen in areas of the casting where there is a bigcross sectional change
between areas – differential contraction – stresses- crack. Layer porosity typically is viewed
in a casting, as a layer within a casting, with a lot of porosity in curved shaped, happens with
build up of hydrostatic tension, to relieve it, pore grows into a layer. Sometimes we also end
up – hydrostatic tension is released by pulling casting inwards – surface porosity or surface
sink. This hydrostatic tension does result in formation of porosity, so in order for porosity to
form – hydrostatic tension or gas evolution which both result in negative delta P. Can use
same curves as slide 44 for nucleation of solids. As pore grows, larges interfacial energy, and
as delta P increases, the bulk energy by energy growth, will be steeper downwards. As
negative delta P increases the critical radius so that a pore will become stable to grow, will
become smaller and smaller.

Slide 51
For critical radius, differentiate and equate to zero the expression for delta G. answer rc = 2
gammaLG/(-delta p). For homogenous nucleation of pores, it is pretty difficult.

Delta p = -2 gamma lg / r
Since r is very small – delta p needs to be 10^7 pascals – very difficult. Problems arise when
we end up with inclusions or with other heterogenous sites which will facilitate pore
nucleation, since this lowers the necessary delta p.

Slide 52
We have seen that pores cannot nucleate under positive delta p, and that gas realeased or
hydrostatic tension are required for negative delta p. Very high delta p is required for
homogenous pore nucleation. Poorly wetted surfaces facitiltate pore formation.
Polyurethane mixed with calcium carbonate particles that are poorly wetted – results in
formation of pores – foam – sometimes useful, but many times heterogenous sites that
facilitate pore are not wanted.

Slide 53
In order for the nucleant to keep growing, we have to maintain a certain degree of
undercooling at the growth liquid interface, so the energy being dissipated/released by the
system, through the conversion of liquid into a solid has to be dissipated into the
surrounding environment in order for that solid to continue growing, If the liquid is enclosed
in a jacket that does not allow heat transfer, the energy of system goes up and conversion
won’t be able to continue. So maintain growth, maintain degree of undercooling and rate of
solid growth is dependent on efficiency of transferring that heat generated during
solidification out of the system So the greater the degree of undervooling, the faster the
growth. The growth rate is going to depend on temp at interface, and faster latent heat is
removed. Temperatuere gradient in the melt affects how material ???

Slide 54
Scenario a) – normal temperature gradient – liquid and solid, vertical line – intergace
between solid and liquid. Solid is growing, and releasing energy in the system, and that
energy being released, is being preferentially conducted through the solid, so heat is
preferentially extracted through the solid. The liquid will experience a positive temp
gradient. As we move away from solidifying interface, the temperature of the liquid is
increasing. For the solid to grow, the actual temp of the melt should be lower than the
melting temperature. The degree of undercooling at the interface (delta T) gets smaller as
we move away from the growing solid. If I get some asperities which form above the
solidying interface will find themselves in a region where degree of undercooling (delta T) is
smaller – the growth rate of asperities goes down, and overall, the growth of solid in a
planar fashion. All the interfaces grow together, plane by plane because roots of asperities
catch up.

Casting in open molds results in negative temp gradient scenario b). Majority of heat lost
through liquid to surrounding. In this case for solidification to continue, delta T at
solidification front gets bigger when moving away from it. Any protrusion will find itself in a
region of increased undercooling which favours a more rapid growth , leading to growth of
parallel arrays which will be referred to as cellular growth. Many cases , the same happens
on sides of these cells as int diagram for dendritic growth, the crystals will not grow in
planar fashion, but dendritic which is more susceptible to porosity on micro level, due to
channels that compensate liquid for shrinkage, liquid will be more difficult to reach -> forms
micro porosity so for a pure metal,

under a positive temp gradient – planar


Negative tmep gradient – dendritiv type growth (steep temp gradient) or cellular type
growth (not very steep)
This is what happens for solidification of PURE METALS (constant Tm)

Slide 55
Growth in alloys
For alloys we will only consider the normal temperature gradient (scenario a)) Considering
solidification of single phase alloy – build up of solute rich layer which depresses the melting
temperature, and therefor the melting temperature profile will not be linear. See slide 57
Solute enriched zone lowers the melting temperature at solidificiation front, as we move
away from it, the degree of undercooling gets bigger, not because of negative temp
gradient, but because of solute enriched which reduces melting temperature. This
phenomena – CONSTITUTIONAL UNDERCOOLING. For this phenomena to happen we
require, solute depresses melting temp and that the solidification rate has to be fast enough
to allow for build up of this solute layes, else it will have time to diffuse.

Slide 56
Single phase alloy. Liquid with composition C0, the temp starts dropping, hits liquidus, first
solid starts forming – will have composition C1 s. Diffusion in solids is very slow, no time to
allow excess A atoms to diffuse back to liquid – end up with coring – solute in front of
solidification front – richer in B. ???? can lead to constitutional undercooling.

Slide 57
Protrusion on surface – degree of hhigher undercooling – favouring dendritic type growth.
In single phase alloys dendritic growth is also find when temp gradient is positive, not only
negative like in pure metals. The conditions for constitutional undercooling, solidification
rate fast enough and solute must depress freezing temperature and actual temperature of
the melt ahead of interface must be less than equilibrium liquidus temperature.

Slide 58
If positive temp gradient is very steep, we don’t get constit. Undercooling zone –planar
growth.
If constit zone small area – cell growth
If larger zone – dendritic growth.

If you want single crystals we tend to favour a steep temp gradient to avoid const.
undercooling and a very slow interface velocity, so as not to allow build up of solute.

Slide 59
Dendrites experience const undercooling, secondary possibly tertiary arms. Arms which
have been grown from same nucleation centre will grow into one single grain. The small
misalignment can be accommodated by generating dislocations. Between dendrites, there
we form the grain boundaries. If we want a fine grain size, what we want, is high nucleation
centres. The more nucleation sites, the more dendrites growing at same time. Fast
solidification rate, will tend to make dendrite arms finer and typically it also has an effect of
refining the grain size, can break off form new nucleation sites. For casting, the properties
are more controlled by the spacing of the arm spaces than grain size. The inter dendritic
spacing sometimes solidify as secondary phase, can act as very strong strengtheneing
mechanincs. Reifing dendritic arm spacing will give us better properties, given that it does
not trigger micro porosity. Big challenge to feed to compensate for shrinkage. The finer the
dendrites, the larger the challenge.

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