A Comparison of Computational and Experimental Methods for Constructing Phase Diagrams

Introduction Phase diagrams are very important from a materials engineering perspective. They contain information about how the phase of a material varies with composition, temperature and pressure. This allows us to predict how materials will behave under various circumstances and so enable us to choose the best material for a particular application. Phase diagrams can be constructed both experimentally and computationally. Computational methods generally construct phase diagrams from databases of the Gibbs free energy for the materials in question. In order to do this, the program uses the free energy curves for the solid and liquid phases to minimise the overall free energy for each composition, as shown in figure 1.

Figure 1: Minimisation of the free energy of a system at a given composition1

The resulting equilibrium compositions for each temperature can then be plotted onto a phase diagram. This computational method is convenient but relies on having an accurate database, and so may not be useful when investigating unusual systems.

One of the most common ways of experimentally determining a phase diagram for a system is by measuring cooling rates of various compositions. The data obtained can then be used to construct cooling curves, which can then be analysed to obtain the liquidus and solidus temperatures for each composition. The liquidus is the temperature at which solidification starts, and the solidus is the temperature at which the entire material is in the solid state. In the region between these two points, the material exists as a mixture of solid and liquid phases. The solidus and liquidus can be

seen on each cooling curve as inflexion points, where the rate of cooling changes. In order to construct the phase diagram, these points are then plotted on a graph of composition versus temperature.

In this experiment, phase diagrams for a Bi-Sn alloy were constructed using both experimental and computational methods. The results obtained using each method were then compared to investigate which method, if either, is more reliable. A secondary aim was to determine the composition of an unknown sample, X, from the experimentally derived phase diagram.

Experimental For the phase diagram derived computationally, the ThermoCalc program was used. For the experimental derivation, the cooling rates of eleven Bi-Sn alloy samples with different compositions were measured. Each sample was heated above the melting point, to around 300C in a furnace. The samples were removed from the furnace and a thermocouple was inserted into a glass tube that was stood upright in each sample. The glass tube was clamped so that the thermocouple did not touch the bottom of the crucible. Each sample was then allowed to cool to around 80C, and the temperature was recorded every two seconds by a computer linked to the thermocouple. The data was then plotted to obtain a cooling curve for each sample, from which the liquidus and solidus temperature for each was estimated. A phase diagram was then plotted using these data.

Results When the cooling curves were plotted, it was seen that there were three types of curve, examples of which are shown in figures 2-4 below.
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Figure 2: Cooling curve for pure Sn

Figure 2 shows the cooling curve for pure Sn, and is similar to that obtained for pure Bi. The liquidus and solidus temperature are equal to the melting point, and so only one inflexion point is seen. Undercooling can be observed at the beginning of the phase transition.

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Figure 3: Cooling curve for Sn-Bi mixture

Figure 3 shows a typical cooling curve for the Sn-Bi mixture. Two inflexion points can be seen, which correspond to the liquidus and solidus temperatures for the given composition.
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Figure 4: Cooling curve for eutectic composition

Figure 4 shows the cooling curve for a 43:57 Sn:Bi mixture. This is the eutectic composition, where there is no intermediate mixture of liquid and solid phases. This is observed on the graph as a single inflexion point followed by a long temperature plateau. The cooling curve for sample X was seen to be of the second type, showing that it is a non-eutectic mixture of bismuth and tin. From analysis of all the cooling curves, the following table was obtained (Table 1), and the phase diagram plotted (figure 5).

Sample A B C D E F G H I J K X

Wt% Sn Wt% Bi Liquidus Temp (C) Solidus Temp (C) 100 0 228 228 90 10 219 128 80 20 194 111 70 30 196 129 60 40 189 131 50 50 141 120 43 57 130 130 30 70 134 120 20 80 228 136 10 90 234 129 0 100 264 264 ? ? 209 126

Table 1: Liquidus and solidus temperatures for all samples

Phase Diagram for Bi-Sn Alloy

300

250

200 Temperature/C

150

Liquidus Solidus

100

50

0 0 20 40 60 80 100 Weight Percentage Sn

Figure 5: Experimentally derived phase diagram for Bi-Sn alloy

As it is known that sample X contains less than 50% bismuth by weight, the composition of X is estimated at around 87% tin and 13% bismuth by weight.

The phase diagram obtained using computational methods is shown in figure 6.

THERMO-CALC (2011.10.11:11.09) : DATABASE:SSOL4 P=1E5, N=1 300

250

TEMPERATURE_CELSIUS

LIQUID

200
LIQUID+RHOMBOHE LIQUID+BCT_A5 RHOMBOHE

150
BCT_A5

100
BCT_A5+RHOMBOHE

50
BCT_A5+DIAMOND_

0 0 10 20 30

DIAMOND_+RHOMBOHE

40

50

60

70

80

90

100

MASS_PERCENT SN

Figure 6: Computationally derived phase diagram for Bi-Sn alloy

Discussion The cooling curves for both pure tin and pure bismuth show undercooling, where the temperature of the liquid phase falls to a minimum below the melting point before a slight increase to a temperature plateau. This phenomenon can be explained by considering the Gibbs free energy curves for the solid and liquid phases (figure 7). At the melting point, the Gibbs free energies of the two phases are in equilibrium and so no phase transformation can occur. In order for solidification to occur, a driving force is needed. This force is provided by cooling the liquid below its melting point, which results in a difference in free energy between the phases. The energy provided in this way is called the entropy of fusion. As the equilibrium has been disturbed, the system can return to the melting temperature until the phase transformation is complete.

Figure 7: Free energy curves for solid and liquid phases1

2011-10-11 11:12:33.57 output by user ali from CATS-PC

The two phase diagrams obtained during this experiment can be plotted onto the same set of axes and compared (Figure 8).

THERMO-CALC (2011.10.13:12.02) : DATABASE:SSOL4 P=1E5, N=1 300

250

TEMPERATURE_CELSIUS

200

150

100

50

0 0 10 20 30 40 50 60 70 80 90 100 MASS_PERCENT SN

Figure 8: Comparison of experimental (triangles) and computational phase diagrams

Comparing the diagrams, it can be seen that the experimental solidus temperatures are around 10C lower than those given by the computer-generated diagram. This is probably due to the thermocouple being separated from the alloy sample by the glass tube, which acts as an insulator. Although a number of the liquidus temperatures are in fairly close agreement between the two methods, a significant number of experimentally obtained values for the liquidus are lower than the corresponding solidus point obtained computationally. This shows that some of the experimental data are not very accurate. Possible reasons for these errors include improper mixing of the samples at higher temperatures, samples with inexact compositions and impurities in the samples. From this, it can be surmised that the computationally obtained diagram is probably the most accurate in this case. The database used to generate this phase diagram is the result of both theory and many experimental results. The accuracy of the experimental phase diagram would be improved by repeating the experiment a number of times to compensate for these errors.

As the liquidus and solidus points were obtained visually from the cooling curves, they are dependent on the observers interpretation. This means it is difficult to consistently estimate the temperatures where phase transformations occur. Consequently, the temperatures plotted on the phase diagram will not have a very high degree of accuracy. The composition of sample X was determined by drawing a rough trendline on the experimental phase diagram. The liquidus and solidus composition values obtained were then averaged to find a value the percentage of tin present in sample X. This was found to be about 87% by weight. This determination can be said to be fairly accurate as using the same method with the computed phase diagram gives a similar answer.

Conclusions In conclusion, it was found that the computationally derived diagram was most accurate in this case. The experimentally derived phase diagram was of limited usefulness, but could be improved by repeating the experiment a number of times.

References 1. Introduction to thermodynamics; MOLE Portal; accessed 13/10/11 https://docs.google.com/a/sheffield.ac.uk/viewer?a=v&pid=gmail&attid=0.1&thid=132fc976 e9322288&mt=application/msword&url=https://mail.google.com/mail/?ui%3D2%26ik%3D2 444ff56a2%26view%3Datt%26th%3D132fc976e9322288%26attid%3D0.1%26disp%3Dsafe% 26zw&sig=AHIEtbRGbC9Vr9WUHIdwlZosdts7-T6Hxg&pli=1