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Complex Phase Diagram construction using

Free Energy vs. Composition Curves


• To construct free energy vs. composition curves given a complex phase
diagram and vice versa.
Learning Objectives :
After going through this learning aid ,user will be able to:
 Construct a phase diagram given free energy vs. composition curves at different
temperatures.
 Draw the schematic free energy vs. composition curves at different temperatures
given the phase diagrams.
 State and interpret the Gibbs Phase Rule.
Author:
Kartikay Agarwal Shrey Singh
10D110030 10D110010
UG sophomore year UG sophomore year
Dept. of ME & MS Dept. of ME & MS

Mentor:
Prof. M. P. Gururajan
Dept. of ME & MS
Glossary
Phase Diagram - Phase Diagrams are charts which give the information
regarding the equilibrium phases in a system under the given thermodynamic
constraints.

Gibbs Phase Rule – At constant pressure P+F-C=1


where C=no. of components,
F=no. of Degrees of freedom, P=no of phases.

Eutectic Point - The point at which liquid phase tranforms into two solid
phases.

Peritactic Point – The point at which a liquid and a solid phase transforms
into another solid phase.

Eutectoid Point - The point at which solid phase tranforms into two solid
phases.
Explanation
Phase Diagrams are a way of cataloguing the information regarding the
equilibrium phases in a system under the given thermodynamic
constraints.
In this learning object, we will consider a system of a binary alloy at
constant pressure and different temperatures . So the phase diagram is
a plot of composition vs. temperature with the equilibrium phases
marked at different combinations of these two parameters.
Specifically in this animation we consider a system that shows the
existence of one ,two and three at any temperature and composition.
We will show that the equilibrium phases are a result of the
minimization of the free energy of the system.
G 0β
β

G0α G 1β G(α + β)
Gα G 1α G β

G1 Gα α

A α 1 X0 β1 B A XBα XB0 X Bβ B
Figure 1 Figure 2

In figure 1, we show the free energies of two different phases called alpha and beta. If G α
is the free energy of the alpha phase (per mole) and G β is the free energy of the beta phase
(per mole) then a mechanical mixture of XBα moles of alpha and XBβ moles of beta will have a
free energy of (XBα Gα + XBβ Gβ ). That is as shown in figure 2 , for any composition between XBα
and XBβ the total free energy of the mechanical mixture lies on the straight line that connects
Gα and Gβ. Hence from figure 1, it is clear that an alpha phase or a beta phase of uniform
composition x0 will have higher free energy as compared to a mechanical mixture of
compositions alpha1 and beta1 for the alpha and beta phases respectively.
Taking the argument further it is
clear that for any composition
between αe and βe ,a mechanical
mixture of alpha and beta phases
G β
Gα of equilibrium compositions αe
and βe will have the lowest free
G0β energy. Pictorially the equilibrium
compositions of the phases that
G 0
α G eβ form the mechanical mixture are
Ge α
D given by the common tangent
C G e
constructed to the free energies
where they are concave.
A αe X0 βe B Conversely any region of a phase
diagram where a mechanical
mixture is seen the free energy
vs. composition curve will have a
concave curvature.
Similarly ,for a binary system with two solid phases ,the eutectic point, the
eutectoid point and the peritactic point exist at the temperature at which the
three free energy curves of the two solid and one liquid phase will share a
common tangent with each other and the composition will be the one
corresponding to the contact point of the common tangent with the free
energy curve of liquid phase.
Slide Slide
1 2
Introduction Glossary Tab 03 Tab 04 Tab 05 Tab 06 Tab 07

Binary Phase Diagrams

Instructions/ Working area

Credits
Action/Description Audio Text to be displayed
narration

Show the animation


description and the
learning objectives from
slide 1.
Show the glossary from
slide 2
Slide 3,4 and 5

Introduction Glossary Explanation Tab 04 Tab 05 Tab 06 Tab 07

Binary Phase Diagrams

Instructions/ Working area

Credits
Action/Description Audio Text to be displayed
narration

As the user clicks on the Explanation ,the whole


slide 3 appears on the screen at the same time

Now as the user clicks the next button (present


at the right bottom corner of the slide)
Text on Text on the slide 3
The figures on slide 4 appears on the screen the slide 3
Now as the user clicks the next button (present
at the right bottom corner of the slide)
Text on slide Text on slide 4.
The figure on slide 5 appears on the screen 4.
Next slide

Introduction Glossary Explanation Animation Tab 05 Tab 06 Tab 07

Binary Phase Diagrams

Instructions/ Working area

Credits
Master Layout 1
The Animator has to
make diagrams by
Figure
himselfA of all the
figures in the image
alongside in the
current slide .All the
dotted lines needs to
be completely
horizontal or vertical in
the figures made by
the animator .For
Figure two the dotted
horizontal line in the
Figure b
l+α region needs to lie
above the point c .So
all the figures used
ahead will the ones
made by the animator
The Animator has to
make diagrams by
himself of all the
figures in the image
alongside.All the
dotted lines needs to
be completely
horizontal or vertical in
the figures made by
the animator .For
C Figure two the dotted
horizontal line in the
l+α region needs to lie
above the point c .So
all the figures used
ahead will the ones
made by the animator

Figure 1
Figure 2
The Animator has to
make diagrams by
himself of all the
figures in the image
alongside .All the
dotted lines needs to
be completely
horizontal or vertical in
the figures made by
the animator .So all
the figures used
ahead will the ones
made by the animator

Figure 3 Figure 4
The Animator has to
make diagrams by
himself of all the
figures in the image
alongside .All the
dotted lines needs to
be completely
horizontal or vertical in
the figures made by
the animator .So all
the figures used
ahead will the ones
made by the animator

Figure 5
displayed
The Slide Master Layout 1 will appear on the screen in this tab The system will exist in liquid Same as
but the figure in the layout will be figure 1 instead of what is phase until melting temperature Audio
shown in the master layout slide of pure A is reached. Narration
As soon as melting point of A is
reached ,a mixture of liquid and
α phase will exists in the region
between the points where
common tangent touches the
two free energy curves

The figure will change from figure 1 to 2(figure 1 and 2 needs As the eutectioid temperature is Same as
to be made by the animator as been described in the previous reached i.e., the temperature at Audio
which there will be common Narration
slide) tangent to the three free energy
curves there will be a mechanical
mixture of all the three
phases(liquid ,α & β) at the
eutectoid composition

Similarly, figure will change from 2 to 3. As the temperature is further


decreased there will be two Same as
common tangents in the free Audio
energy vs composition curves Narration
and hence there will be two
regions in the phase diagram
where a mechanical mixture of
two phases will exist i.e., of β &
α and liquid & β

.
Action/Description Audio narration Text to be
displayed

Figure A will change from 3 to 4. As the temperature is further Same as


decreased there will be three Audio
common tangents in the free
energy vs composition curves Narration
and hence there will be three
regions in the phase diagram
where a mechanical mixture of
two phases will exist i.e., of β &
α and liquid & β and liquid + ϒ.

Now the figure will change from figure 4 to figure 5 As soon as the eutectic Same as
temperature is reached, there
will be a mechanical mixture of Audio
three phases l, beta and gama at Narration
the composition where the
common tangent to the three
free energy curves of the same
During transition curve α & β & ϒ will move downward and l touches the liquid free energy
will move upward gradually relative to each other. curve Also there exists a
mechanical mixture of alpha and
beta in the region of common
tangent between alpha and beta
free energy curves

Click on Next for next


Next Button Appears on the Right Bottom animation
Master Layout 2
The
The Animator
Animator has has to to
make
make diagrams
diagrams by by
himself
himself of of all
all the
the
figures
figures in in the
the image
image
alongside
alongside in in the
the
current
current slide .All the
slide .All the
dotted
dotted lines
lines needs
needs to to
be
be completely
completely
horizontal
horizontal or or vertical
vertical in in
the
the figures
figures mademade by by
the animator
the animator .For .For
Figure
Figure two two thethe dotted
dotted
horizontal
horizontal line line in
in the
the
l+α
l+α region
region needs
needs to to lie
lie
above
above the the point
point cc .So.So
all the figures
all the figures used used
ahead
ahead will will the
the ones
ones
made
made by by the
the animator
animator
Figure 1 Figure 2
The Animator has to
make diagrams by
himself of all the
figures in the image
alongside in the
current slide .All the
dotted lines needs
to be completely
horizontal or vertical
in the figures made
by the animator .For
Figure two the
dotted horizontal
line in the l+α region
needs to lie above
the point c .So all
the figures used
ahead will the ones
made by the
Figure 3 Figure 4 animator
The Animator has to
make diagrams by
himself of all the
figures in the image
alongside in the
current slide .All the
dotted lines needs to
be completely
horizontal or vertical in
the figures made by
the animator .For
Figure two the dotted
horizontal line in the
l+α region needs to lie
above the point c .So
all the figures used
ahead will the ones
made by the animator

Figure 5
displayed

The Slide Master Layout 1 will appear on the screen in this tab but the For region above melting Same as
figure in the layout will be figure 1 instead of what is shown in the temperature of A, No of Phases is audio
master layout slide just 1 i.e., solid and components
are 2 so by Gibbs Phase Rule narration
degrees of freedom will be 1
which means that we can obtain a
particular composition of liquid
phase by varying temperature and
composition simultaneously.

At the peritactic temperature and


The figure will change from figure 1 to 2(figure 1 and 2 needs to be composition ,three phases exists
made by the animator as been described in the previous slide) which gives out degrees of Same as
freedom to be 0 from Gibbs Phase audio
Rule which means that for a narration
system at constant pressure,
peritactic point exists at a fixed
temperature and composition.

Similarly, figure will change from 2 to 3. The region where exists a


mechanical mixture of two phases
(β+α or l+β), F comes out to be 1
which means that in order to
obtain a particular composition of
a phase we can chose either one
of temperature or composition
independently but the other one
needs to be fixed.
Action/Description Audio narration Text to be
displayed

Figure A will change from 3 to 4. On going below melting Same as


temperature of B, There will audio
three regions with 1 degree narration
of freedom(β+α or l+β or l+ϒ)

At the Eutectic point and


composition ,three phases Same as
Now the figure will change from figure 4 to figure 5 exists which gives out audio
degrees of freedom to be 0 narration.
from gibbs phase rule which
means that for a system at
constant pressure ,eutectic
point exists at a fixed
During transition curve α & β & ϒ will move downward and l temperature and
will move upward gradually relative to each other. composition. Although there
Will a region where the
degree will be two
representing a mixture of
β+α .

Click on Next for next slide.


Next Button Appears on the Right Bottom
Next Slide

Introduction Glossary Explanation Animation Questionnaire Tab 06 Tab 07

Binary Phase Diagrams

Instructions/ Working area

Credits
Questionnaire
I. What is the no of regions that will exist in the
phase diagram at the temperature at which
the free energy
vs. composition curve is
 5

al. What will be those regions?


 α, α+β, β, β +l, l This diagram needs to be
made by the animator
Identify the points a, b and c.

(a)

(b)
Ans.
(a).Peritactic
(b).Eutectic
(c).Eutectoid
(c)
Action/Description Audio Text to be displayed
narration

As the user clicks on the Questionnaire Same Same as


tab ,the questions written in black color
appear on screen along with the as on on the
figure(to be made by the animator as
described in the previous slide) at the the slide
same time .Then on selecting the
answers tab made at the bottom of
slide
screen, the answer, i.e. text written in
red color appears in the same format as
shown in previous slide.
Next Slide

Introduction Glossary Explanation Activity Area Questionnaire Summary Tab 07

Binary Phase Diagrams

Instructions/ Working area

Credits
Summary
By the interpretation of free energy vs. composition
curves ,we can estimate the phase diagram and also
the free energy vs. composition curves can be
estimated on the basis of phase diagrams. Free energy
vs. composition curves explain the reason behind the
existence of multiple phases at different temperatures
and compositions.
The phase or a mixture of phases with the lowest free
energy will exist at all combination of temperatures
and compositions in order to attain equilibrium.
Action/Description Audio Text to be displayed
narration

Show the summary Same


from previous slide as on
the
slide
Next Slide

Introduction Glossary Explanation Activity Area Questionnaire Summary Further Reading

Binary Phase Diagrams

Instructions/ Working area

Credits
Further Reading
Books
• Phase Transformations in Metals and Alloys by David A Porter
K.E. Easterling Published by Chapman & Hall, 2-6 Bormdary
Row, London
SEl 8HN, UK

Links
• http://
www.sv.vt.edu/classes/MSE2094_NoteBook/96ClassProj/analy
tic/anmeth.html
• http://www.matter.org.uk/matscicdrom/manual/td.html
• http://en.wikipedia.org/wiki/Phase_diagram
Action/Description Audio Text to be displayed
narration

Show further reading Same


from previous slide as on
the
slide

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