The application of thermal analysis in the study of metallic

materials

Ángel Varela and Ana García

Esculea Politécnica Superior, Universidade da Coruña
Mendizábal s/n, 15403 Ferrol. Spain.
anvalaco@cdf.udc.es

1. Introduction
The first commercial TGA equipment appeared in 1945 and was followed by
DTA in 1960 and DSC in 1964. The Journal of Thermal Analysis appeared for the first
time in 1969 and Thermochimica Acta came out the following year.
In the seventies, when thermal analysis methods started to be generally applied,
major advancements in scientific research related to metallic materials’ behaviour had
already occurred. This was especially true in the case of alloys with greater industrial
demand, such as steel, or alloys with greater future expectations, such as light alloys and
mainly aluminum alloys. In the first half of the past century, famous metallurguists
such as Bain, Davenport, Grossmann, and Jominy, amongst others, carried out a very
important task. These scientists, along with institutions like the A.S.M. (American
Society for Metals) and the IRSID in France, led to the creation of the Atlas of T.T.T.
and C.C.T. curves of commercial steels, applying techniques like dilatometry, which
measures the dimensional variation of the tested sample according to the temperature,
and metallography, which freezes the structure after an isothermic period of a different
duration at various temperatures.
All this led to thermal analysis methods not initially being applied to metallic
materials, but to other materials that were being discovered and were practically
unknown in their properties and characteristics. This was due to the limitations of the
methods used, especially with respect to the range of working temperatures, whose
application to metallic materials was not very useful at that time.
Nevertheless, metallic materials, upon conditioning their microstructure not only
by temperature, but also by conditions of the process (speed of heating and cooling),
could be treated with these analysis methods. As a result, fusion temperatures and the
latent heat of fusion, allotropic transformations, transformations with a phase change in
solid state in which diffusive phenomena can intervene, equilibrium diagrams,
transformation kinetics, changes in magnetic behaviour, behaviour with respect to
oxidation at high temperatures, the coefficient variation of thermal expansion, the
variation of specific heat, and thermal stability could be determined using these
methods. In general, any process that could be activated thermally can be studied with
DSC. In addition, it can characterise transformation kinetics. Similarly, all those
processes involving a modification in the mechanical properties can be studied using
DMA or TMA. Examples of these phenomena include the precipitation processes of
intermetallic compounds in some alloys that involve amplification in the elastic
modulus and phase transformations.
Some specific applications of thermal analysis methods on metallic materials are
pointed out below.
88 ANGEL VARELA AND ANA GARCÍA

2. Shape memory materials

There are metallic materials known as shape memory materials because they
present the special feature of undergoing a transformation in the solid state known as
martensitic. It generally occurs at low temperatures and diffusive phenomena do not
intervene. When these materials are plastically deformed at a temperature below the
final temperature of martensitic transformation, they can later recuperate the original
shape by heating the material above the final temperature of the reversible
transformation.
Due to their shape memory effect, their superelastic distribution, their absorption
capacity, their change of resistance, and their good mechanical properties, shape
memory materials tend to be used as fire detectors, muscles in robotics, mechanical
sensors (for example, for the opening of windows for ventilation), and dental prosthesis,
amongst other uses.
In the past years, different works have appeared in which the application of the
DSC method is used for the determination of characteristic temperatures and of enthalpy
changes associated with endothermic and exothermic processes that occur during the
controlled heating and cooling of these types of materials [1-7].
)
[mW ]
H eatFlow (

Temp [°C ]
Figure 1. DSC curve showing the martensitic transition reversibility in a shape memory
alloy
 APPLICATIONS OF THERMAL ANALYSIS TO THE STUDY OF METALS 89

10
8x10

10
110 ºC
7x10
100 ºC
10
6x10 90 ºC

10
5x10
80 ºC
E' ( )

10
[Pa]

4x10
70 ºC
10
3x10
60 ºC
10
2x10 50 ºC

10
40 ºC
1x10
30 ºC

0.0
-2 -1 0 1 2
10 10 10 10 10
Frequency [Hz]

Figure 2- Determination of the martensitic transition temperature with DMA.

According to reference [15]

The transition temperature for this class of alloys can also be determined
employing DMA methods. In Figure 2, the elastic modulus obtained for an equiatomic
alloy of nickel and titanium according to the frequency of nine different temperatures is
shown. The martensitic transition temperature can be determined observing the
separation between curves which increase around that temperature. In addition, it is
possible to observe how the curve for the transition temperature presents a greater slope
than the rest, which indicates the modulus’s dependence on the frequency is increased
for the martensitic transition temperature.
A third way to study martensitic transformation temperatures of shape memory
alloys is through the use of TMA. In Figure 3, the deformation that is tested on a wire of
the same alloy is shown. In the previous example, it was deformed according to time
when the temperature varied and when it was subjected to a constant force.
90 ANGEL VARELA AND ANA GARCÍA

7.0 130.0
strain
6.0 Constant stress of 2.3 e08 Pa 120.0
Constant stress of 8.0 e06 Pa
110.0
5.0
100.0
4.0
90.0
)

Temp (
3.0 80.0

[°C]
[% ]
strain (

2.0 70.0

60.0

)
1.0
50.0
0.0
40.0
-1.0
30.0

-2.0 20.0
0.0 500.0 1000.0 1500.0 2000.0 2500.0 3000.0
time [s]

Figure 3. Determination of the martensitic transformation temperature with TMA.

According to reference [15]

In Figure 3 a sharp increase in the elastic modulus’s value is observed when the
transformation temperature is reached. As this transformation temperature shifts
towards higher values, the applied force increases from 8.0 MPa to 2300 MPa.

3. Determination of the progress of metal and alloy solidification.

If the alloy’s solidification is studied using the DSC curve, as in the example of
an alloy of lead-tin, and if the solidification’s interval is centred, the evolution of the
liquid phase percentage according to the temperature can be traced. [8-9].
 APPLICATIONS OF THERMAL ANALYSIS TO THE STUDY OF METALS 91

-2
HeatFlow (mW)

-4

-6

-8

-10

-12

-14
0 50 100 150 200 250 300 350
Temperature (ºC)

100% 2

100% Liquid 0
80%
-2

Melting progress (------)

HeatFlow (mW) (-------)

-4
60%

-6

40%
-8

-10
20%
100 % Solid
-12

0% -14
150 170 190 210 230 250
Temperature (ºC)

Figure 4. DSC curve, endothermic fusion and variation of the liquid phase percentage
determined using the Borchardt and Daniels method [16]

4. Determination of equilibrium diagrams.

If we obtain the curves for different alloys of binary [10] or ternary [11] systems
with DSC, the liquidus and solidus temperatures as well as those temperatures
corresponding to transformations in solid states can be determined. These curves are
created from all the information obtained in the analysis of the same temperatures with
respect to the appropriate equilibrium diagrams.
In the following example, we notice how the diagram structure of the
appropriate phase corresponding to a lead-tin system is carried out step by step. From
92 ANGEL VARELA AND ANA GARCÍA

the DSC curves obtained during the solidification, the appropriate temperatures at the
beginning of solidification (point of the liquidus line) and the eutectic transformation’s
temperature for alloys with different proportions of lead and tin are determined.

25.0

20.0
Eutectic transformation
)

15.0
[mW ]
HeatFlow (

10.0

Solidification beginnig

5.0

0.0
100.0 150.0 200.0 250.0 300.0
Temp [°C]

Figure 5. DSC curve obtained during the solidification of an alloy with 30% tin and
70% lead

If points for the different alloys of lead and tin are determined, it is possible to
begin the construction of the phase diagram, as can be seen in Figure 6. In this figure,
the alloy’s composition with respect to the temperature is shown. We are able to see
each one of the DCS curves obtained for the different alloys with their liquidus and
solidus lines’ appropriate points. We also can see the points of fusion of the two metals
in pure state and the way of tracing the lines of the phase diagram.
 APPLICATIONS OF THERMAL ANALYSIS TO THE STUDY OF METALS 93

100.0

80.0 0 % Sn
30 % Sn
50 % Sn
61.9 % Sn
60.0
70 % Sn
% Sn 90 % Sn
100 % Sn (inverted)
40.0

20.0

0.0
100.0 150.0 200.0 250.0 300.0 350.0
Temperature (ºC)

Figure 6. Pb-Sn phases diagram construction

In order to establish the point of maximum solubility and the eutectic alloy’s
composition, should it not be known, the Tamman triangle, which shows the appropriate
peak’s area for the eutectic transformation, is constructed. For those alloys that are
tested on the basis of the alloy’s composition, see Figure 7.
Eutetic composition
61.9
Eutetic transformation peak area

Solubility maximun
of Sn in Pb
18.3
Solubility maximun
of Pb in Sn
18.3

0 20 40 60 80 100
% Sn

Figure 7. Determination of the points of maximum solubility and of the eutectic

composition for the Pb-Sn system
94 ANGEL VARELA AND ANA GARCÍA

5. Measurement of heat capacity.

Using DSC, the variation of the heat flow with the temperature of the tested
sample is obtained. The results are compared with the base line of synthetic sapphire
that is taken as normal specific heat and allows the apparatus’s software to determine
the specific heat’s variation with the temperature [12-13].

Y = 4E-17x6-2E-13x5+4E-10x4-5E-07x3+0.0003x2-0.0990x+12.125
0.8 R2= 0.9992

0.6
Cp (J/gK)

0.4

0.2
400 600 800 1000 1200 1400
Temperature (K)

Figure 8. Variation of Cp with the temperature in a nickel-based superalloy. According

to reference [13-14]

6. Transition temperatures: magnetic change or Curie’s temperature, allotropic

transformations, fusion temperature, transformation with phase change in
solid state.
Using DSC, all these temperatures as well as the energy associated with the
appropriate transformations can be detected.
 APPLICATIONS OF THERMAL ANALYSIS TO THE STUDY OF METALS 95

200.0

150.0
Curie Temperature
771.85 °C Gamma-Delta transition
100.0 1393.0 °C
)

50.0
[mW ]
HeatFlow (

0.0

-50.0
Alpha-Gamma transition
911.26 °C
-100.0

-150.0
700.0 800.0 900.0 11 00.0 1300.0 1500.0
Temp [°C]
Figure 9. Allotropic transformations of pure Fe

5.0

0.0 156.2 °C

-5.0
)

-10.0
[mW ]
HeatFlow (

-15.0

-20.0

-25.0

-30.0
100.0 120.0 140.0 160.0 180.0 200.0
Temp [°C]
Figure 10. Determination of the fusion temperature of pure indium
96 ANGEL VARELA AND ANA GARCÍA

In addition, by means of TMA, it can be suggested that dimensional change,

either contraction or expansion, is associated with crystalline structure changes in
transformations with phase changes in the solid state.

Pearlite to austenite
)
D imens ional C hange (
[(mm)]

Austenite to Martensite

Temperature [°C ]

Fig. 11. Dimensional changes that are produced in steel subjected to heating and then
to cooling

7. Behaviour with respect to oxidation at high temperatures

Using TGA and regulating the nature and atmospheric pressure in the
thermobalance’s interior, the material’s behaviour with respect to the time periods at
various temperatures can be measured.
 APPLICATIONS OF THERMAL ANALYSIS TO THE STUDY OF METALS 97

50.0 1500.0

40.0 22.273 %
1400.0
1500 min
30.0 3.841 %
625 min
)

20.0 1300.0

Temp (
10.0
W eight increment (

1200.0

[°C]
0.0
[% ]

1100.0
-10.0

)
-20.0 1000.0

-30.0
900.0
-40.0

-50.0 800.0
0.0 400.0 800.0 1200.0 1600.0
time [min]
Fig. 12. Oxidation at high temperatures of stainless steel in the air’s atmosphere

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