Table of Contents

1. Aims and Objectives 2

2. Introduction 2
3. Computational Software and Methods 4
4. Results and Discussions
4.1 Task 1 5
4.2 Task 2 7
4.3 Task 3 11
5. Conclusions 14
6. References 15

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1. Aims and Objectives
Through this assignment, Thermo-Calc software is introduced to the students. This aims to
make them familiar with computational materials engineering and how its transforms the
conventional way in which Engineers approach material design, research and processing. This
report focuses on some of the features of Thermo-Calc software like plotting a binary phase
diagram and thermodynamic functions like enthalpy and Gibb’s free energy of different phases,
and calculation of mass fractions and their composition as a function of temperature. All three
tasks in the assignment is based on one of the most commonly used alloy in aerospace industry,
Al-Cu alloys (2.XXX series).

Also, the plots obtained using Thermo-Calc software are analysed thoroughly and is related
with the theory studied in the lecture as part of this module.

2. Introduction
Aluminium is the most abundant metal, comprising 8% of Earth’s crust. In 1808, Sir Humphry
Davi identified the presence of metal aluminum in alum, which IUPAC later renamed as
aluminium. Aluminium and its alloys are used in industries such as packaging, transport,
construction, electrical transmission, marine and aerospace. The wide applications of
aluminium can be tied directly to its extensively properties such as high strength to weight
ratio, non-toxicity, corrosion resistance, electrical and thermal conductivity and ease of
recycling.

Aluminium is mainly alloyed with elements such as copper, manganese, magnesium, silicon
and zinc. Tin, iron, lithium, zirconium and chromium are also added in small quantities in some
families of aluminium alloys.

The aluminium alloys were used in the aircraft industry from the beginning. In 1903, Wright
brothers used Al-9%Cu cast alloy for the crank case of their flight engine[1]. Even in the
present day, aluminium alloys are extensively used in aerospace industry, an example of which
is Al-Li alloy used in Space X’s Falcon 9 rocket. The 2xxx series of aluminium alloys is mainly
alloyed with copper(2-6%), although magnesium may be added in small quantities. This series
of aluminium alloys is mainly used in the aerospace industry due to their high strength to weight
ratio. Al-Cu, Al-Cu-Mg alloys in 2xxx series are heat treated to obtain optimum properties[2].
Although, titanium and composites are extensively used nowadays, 70% of civil aircraft frames

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are made using 2xxx series aluminium alloys and without them commercial civil aviation
would not be economically viable.

Age hardening, or precipitation hardening, is a heat treatment technique that increases the
strength of the alloy by secondary phases pinning dislocations. Age hardening is mainly
implemented for aluminium and magnesium alloys. Three steps involved in age hardening are:

1. Solution heat treatment: The alloy heated to a temperature above solvus temperature and
held at this temperature until a solid solution (α) is produced and any precipitate is dissolved.

2. Quenching: The alloy is quenched to form supersaturated solid solution; the atoms do not
have time to diffuse to potential nucleation sites and form precipitates. Excess solute is in super
saturated solid solution and not an equilibrium structure.

3. Ageing: Heated to a temperature below solvus; atoms diffuse.

For Optimum Strengthening, the precipitates should be hard and brittle, round, small,
numerous and discontinuous. In Al-Cu alloys, Al2Cu is formed as a precipitate dispersed in
the FCC aluminium matrix.

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3. Computational Software and Methods
In the age of high-performance computing, computational models and simulations can be used
to solve complex physical problems arising in engineering analysis and design. Computational
software is used in every discipline from trajectory calculation of satellites to Monte Carlo
simulations. In thermodynamics, computational software was first developed for the
calculation of phase diagrams. Now there are software like Thermo-Calc, DICTRA, JMatPro,
FactSage, Pandat, and MTDATA, which solves many complex materials related engineering
problems.

The development of Thermo-Calc can be contributed to Prof.Mats Hillert of Royal Institute of

Technology, Sweden and his three students(1981). Thermo-Calc is based on
CALPHAD(Calculation of PHAse Diagrams) approach, a self-consistent, phase-based
approach that relates the underlying thermodynamics and phase equilibria of chemical systems
by capturing the composition and temperature dependencies[3]. Thermo-Calc reduce the
dependence on trial and error approach and not eliminating experiments. It helps in predicting
how a specific alloy at a specific composition will behave at different temperatures. Using
Thermo-Calc, we can predict solvus temperature, phase transformation temperature, micro
segregation during solidification and volume fraction and stability of precipitates. Since 1997,
Thermo-Calc has been cited in over 12,000 peer reviewed publications and over 1000 patent
applications.

In this assignment, Thermo-Calc Academic limited version is used, which can handle three
components or fewer, whereas the full version of Thermo-Calc can handle up to 40
components. The user interface of Thermo-Calc is quite simple. To get familiarized with the
software, online tutorials on Fe-C binary system is practised. The main templates of Thermo-
Calc required to complete this assignment was Binary Systems and Property Diagram. Then
using the System Definer, we choose the elements in our system, the phases that we are
interested in, etc. Then in Equilibrium Calculator, we input the physical conditions about the
system we intend to study. We can select Plot Render or Table Render at this stage based on
our requirement. In Plot Render, we can define the axes based on our requirement, choose its
units and also we can opt to have more plots in the same graph just by defining more axis here.
Also, we can find tools to limit the numerical value of properties and to plot logarithmic, linear
or inverse graph, etc in the Plot Render.

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4. Results and Discussion

4.1 Task 1

The first task is to plot Al-Cu phase diagram between 0 to 40% mass Cu content. This can be
obtained in Thermo-Calc by using Binary calculation tool. The elements and the conditions as
given in the task can be given as per the task and the result is given below:

Fig 2: Al-Cu phase diagram (0 to 40 wt% Cu)

The phases present in the diagram are labelled accordingly and the phase diagram obtained
seems to be coherent to the one discussed in lecture. At 0 wt% Cu, from the phase diagram, we
can infer the properties of pure aluminium. The melting point of aluminium is around 660°C,
above which it becomes liquid. The maximum solubility of copper in aluminium can be
inferred from the graph to be at 548°C, for a composition of 6.3 wt% Cu. From the graph, it is
clear that the eutectic point in the graph is at 33.2 wt% Cu and 548°C. Above the eutectoid
line, there are two mushy zones- a hypo eutectoid mushy zone with FCC-Al and liquid, and
hyper eutectoid zone with liquid and Al2Cu. Below the eutectoid line, the alloy exists as solid
with two different phases-Al2Cu and FCC-Al.

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A suitable temperature and composition to solution heat treat alloy can be suggested based on
the following facts:

1.Composition should be less than the maximum solubility(5.65 wt% in this case).

2.Solution heat treatment temperature should be above solvus temperature(548°C in this

case).

Based on this, alloys with 2 to 5 wt% Cu can be heat treated at temperature between 550°C and
580°C based on the composition. For example, alloy with 4wt% Cu can be solution heat treated
to 550°C and then quenched to room temperature and then age hardened at about 150°C for
few hours. Excess time heat treatment during age hardening may lead to overageing, the
precipitates becoming larger and subsequent losing hardness.

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4.2 Task 2

Various thermodynamic functions are to be plotted for the Al-Cu system. First, Gibb’s free
energy of the liquid phase, FCC and Al2Cu phases are plotted as a function of composition
(in a single graph) at 800, 600, 400 and 200°C. The graphs are obtained in Thermo-Calc
using Property Diagram tool. The plots obtained are given below:

[a]Temp=800°C [b]Temp=600°C

[c]Temp=400°C [d]Temp=200°C

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The above figures represent the Gibb’s energy [per mole] of various phases like FCC, Liquid
and Al2Cu plotted against weight percentage of copper at different temperatures. Gibbs energy
curves can be used to construct phase diagram because it predicts which phase is stable at a
given temperature and composition. The phase with lowest Gibb’s energy will be the one which
is stable and thermodynamically preferred at a given temperature. At 800°C we infer that only
liquid phase will be present in the system between 0 to 40 wt% Cu, as FCC and Al 2Cu curves
are above the liquid curve. If the system is cooled down to 600°C, we note that the liquid and
FCC curves are intersecting. As the free energy curve of Al2Cu is above both, there is no chance
of having a stable Al2Cu phase at this temperature. Drawing a tangent between the liquid and
FCC curve will be the best possible way to determine the phases present at each composition.
From 0 wt% Cu to the corresponding composition at the point where the tangent meets FCC
curve, only FCC phase will be present. Between compositions corresponding to the points
where the tangent meets the FCC and liquid curves, the equilibrium state will be a mushy zone
with liquid and FCC phases present. In compositions between the point of intersection of
tangent to the liquid curve and 40 wt% Cu, a mushy zone with liquid and Al2Cu phases is
stable. On further reducing temperature to 400°C, the liquid curve seems to be running on top
of FCC curve in a somewhat parallel manner and also the Al2Cu curve seems to intersect the
FCC curve at a composition greater than but near to 40wt% Cu. So we can follow the same
method of drawing tangent, which will give us the stable phases at a given composition. From
0 wt% Cu to the composition corresponding to the point where the tangent meets FCC curve,
FCC will be the stable phase. Above that composition until 40wt% Cu, the equilibrium
structure contains both Al2Cu and FCC phases. At 200°C, the FCC and Al2Cu curves intersect
in the composition range under study, which means the point at which the tangent touches FCC
curve is shifted to left, narrowing the composition range at which FCC is stable. Above that
composition till 40wt% Cu, both phases FCC and Al2Cu are present.

The second part of Task 2 is to plot enthalpy of FCC, liquid and Al2Cu phases as a fuction of
composition at different temperatures: 800,600, 400 and 200°C. This is done using the same
Property Diagram tool, and the results are as follows:

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 [a] T=200°C [b] T=400°C

[c] T=600°C [d] T=800°C

Enthalpy, H= E + PV

Where E is the internal energy, P is the pressure and V is the volume.

Here we have plotted enthalpy per mole of FCC, liquid and Al2Cu phases at a constant pressure
as a function of composition at different temperatures. From the 4 plots obtained, we can notice
that any particular phase have similar curves at different temperatures. Also note that the
numerical value of enthalpy is increasing for any phase while increasing the temperature. This
can be attributed to the increase in internal energy with temperature.

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The effect of enthalpy on the Gibb’s energy can be studied by understanding the following
equation:

G= H- TS

Where H is the enthalpy, Tis the temperature and S is the entropy.

For a reaction, Go = Ho - T So

The change in Gibb’s free energy should be negative for the reaction to be spontaneous. Being
the only positive term in RHS, if H is negative change in free energy will be always negative.
If H is positive, T So should be higher than the former for the reaction to be spontaneous,
which means that the reaction will be favourable at higher temperatures.

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4.3 Task 3

The task is to plot the activities of Cu and Al for an Al-Cu binary alloy with 4 wt% nominal
composition of Cu. The plot is obtained using Property Diagram tool of Thermo-Calc by
specifying the composition of the alloy and physical conditions. The result obtained is as
follow:

Note the numerical values of activities of copper and aluminium. The activity of copper in all
phases are very less compared to that of aluminium. This is because in the alloy weare
analysing, the wt% of copper is 4%, which is less compared to 96% aluminium. And the nature
of the plots is as predicted based on the phase diagram. Activity is a measure of
the effective concentration of a species under real conditions. Chemical potential of a species
depends on the activity in real solutions, rather than like concentration(mole fraction) in ideal
solution. Activity is related to chemical potential by the equation:

a=eμ−μo/RT

where a is the activity, μ is chemical potential (dependent on standard state) which is Gibbs
Energy per mole, μ0 is the standard chemical potential, R is the gas constant and T is the
absolute Temperature.
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Activity is a dimension less quantity which depends on concentration, temperature, pressure
and interaction between chemical fields.

The next task is to calculate the mass fraction of different phases in the overall alloy as function
of temperature and draw the curves in a single graph. The below graph is obtained in Thermo-
Calc using the Property Diagram tool and specifying the required conditions and required
variables in both axes:

The result is in agreement with the phase diagram obtained in task 1. At 500K, the system
contains 95% FCC in terms of moles, and 5% Al2Cu phase. As the temperature increases, mole
fraction of FCC increase and that of Al2Cu decreases until around 775K. At 775K, the system
contains 100% FCC and no. This trend is continued till around 840K, after which we can note
an exponential increase in mole fraction of liquid and an exponential decrease in the mole
fraction of FCC. This means that the solid which exists in FCC phase is slowly melting. From
the graph, we can note that the system becomes liquid at around 920K, where the mole fraction
of liquid is 1 and that of FCC is 0.

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The last task is to calculate the solidus, liquidus, & solvus temperatures of the alloy, and output
the values to a table. This is performed in Thermo-Calc using the same tool used above, by
adding a Table Output. The table obtained in this analysis is:

From this table, it is clear that the liquidus temperature for the Al-Cu 4wt% alloy is at 922.96K,
solidus temperature at 844.76K and solvus temperature at 775.75K. These temperatures can
also be taken from the plot in the previous task.

Solvus, solidus and liquidus temperatures are very important in heat treatments, especially, age
hardening for this family of 2xxx Al-Cu alloys.

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5. Conclusion
In this assignment, Thermo-Calc was used to calculate few thermodynamic properties. Firstly,
the phase diagram of the Al-Cu binary system is plotted for a composition between 0 to 40
wt% Cu. The different phases present at different compositions are studied thoroughly and a
suitable temperature and composition for solution heat treatment is estimated. This is one of
the most important information that we can draw from a phase diagram. The microstructure of
the alloy at different compositions and temperatures can also be predicted from the phase
diagram, which is not required in the assignment.

Then thermodynamic properties like Gibb’s energy and enthalpy were plotted against
composition at different temperatures for composition between 0 to 40wt% Cu. In the lecture,
we plotted Gibb’s energy curves and derived phase diagram from those. In this assignment, we
related energy curves with phase diagrams and established why a particular phase is more
stable at a given composition and temperature. Also, the enthalpy curves are analysed and how
it affects Gibb’s energy has been discussed in the report. In tasks 1 and 2, temperature in Celsius
is used in plots and explanations, as the temperatures are defined in task 2 question in Celsius.
In task 3, SI unit of temperature Kelvin is used , as it is the standard one, and no specifications
is mentioned in question.

The final task was focused on an Al-Cu alloy with 4wt% Cu. The activity of aluminium and
copper in different phases is plotted as a function of temperature in a single graph. As per the
guideline, Activity referred to a phase is plotted in Y axis and activities of aluminium and
copper in Al2Cu is not considered. A detailed discussion is made on the concept of activity and
it’s importance in thermodynamics. Then, the mass fraction of different phases in the overall
alloy as function of temperature is plotted in the same graph for the given alloy and its physical
meaning is interpreted. Also, from the above graph the solvus, liquidus and solidus
temperatures are calculated and the results are tabulated.

The assignment aided in familiarizing with Thermo-Calc software and made us realize the
advantages of using a computational software to solve complex systems, with a practical
engineering problem. It also inspires me to explore other features and modules of Thermo-
Calc, which is not utilised in this assignment. It also gave an insight on how to apply theoretical
knowledge from lectures into a real situation.

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6. References
[1] W.M. Griffith: Adv. Mater. Process., 2003, vol. 161, pp. 21–24

[2] ASM Specialty Handbook: Aluminium and Aluminium Alloys, J.R. Davis, Ed., ASM
International, 1993

[3] T. Software, “THERMO-CALC & DICTRA, Computational Tools For Materials Science
J-O Andersson, Thomas Helander,Lars Hdghmd, Pingfang Shi, Bo Sundman,” vol. 26, no. 2,
pp. 273–312, 2002.

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