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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
Each sample was then allowed to cool to around 80°C. For the experimental derivation. A phase diagram was then plotted using these data. these points are then plotted on a graph of composition versus temperature. the cooling rates of eleven Bi-Sn alloy samples with different compositions were measured. In order to construct the phase diagram. to around 300°C in a furnace. and the temperature was recorded every two seconds by a computer linked to the thermocouple.seen on each cooling curve as inflexion points. X. The results obtained using each method were then compared to investigate which method. from which the liquidus and solidus temperature for each was estimated. 350 300 250 200 150 100 50 0 200 400 600 800 1000 Figure 2: Cooling curve for pure Sn . Each sample was heated above the melting point. is more reliable. examples of which are shown in figures 2-4 below. The glass tube was clamped so that the thermocouple did not touch the bottom of the crucible. The samples were removed from the furnace and a thermocouple was inserted into a glass tube that was stood upright in each sample. phase diagrams for a Bi-Sn alloy were constructed using both experimental and computational methods. it was seen that there were three “types” of curve. Results When the cooling curves were plotted. The data was then plotted to obtain a cooling curve for each sample. from the experimentally derived phase diagram. where the rate of cooling changes. if either. In this experiment. Experimental For the phase diagram derived computationally. A secondary aim was to determine the composition of an unknown sample. the ThermoCalc program was used.
The liquidus and solidus temperature are equal to the melting point. Undercooling can be observed at the beginning of the phase transition. 350 300 250 200 150 100 50 0 0 200 400 600 800 1000 Figure 3: Cooling curve for Sn-Bi mixture Figure 3 shows a typical cooling curve for the Sn-Bi mixture. which correspond to the liquidus and solidus temperatures for the given composition. 350 300 250 200 150 100 50 0 200 400 600 800 1000 1200 1400 Figure 4: Cooling curve for eutectic composition . and is similar to that obtained for pure Bi. Two inflexion points can be seen.Figure 2 shows the cooling curve for pure Sn. and so only one inflexion point is seen.
the following table was obtained (Table 1). This is the eutectic composition.Figure 4 shows the cooling curve for a 43:57 Sn:Bi mixture. where there is no intermediate mixture of liquid and solid phases. 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 . showing that it is a non-eutectic mixture of bismuth and tin. The cooling curve for sample X was seen to be of the second type. This is observed on the graph as a single inflexion point followed by a long temperature plateau. and the phase diagram plotted (figure 5). From analysis of all the cooling curves.
the composition of X is estimated at around 87% tin and 13% bismuth by weight.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. .
In order for solidification to occur. At the melting point.11:11. Figure 7: Free energy curves for solid and liquid phases1 2011-10-11 11:12:33. This phenomenon can be explained by considering the Gibbs free energy curves for the solid and liquid phases (figure 7). the system can return to the melting temperature until the phase transformation is complete.The phase diagram obtained using computational methods is shown in figure 6. As the equilibrium has been disturbed. the Gibbs free energies of the two phases are in equilibrium and so no phase transformation can occur. The energy provided in this way is called the entropy of fusion. 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. which results in a difference in free energy between the phases. THERMO-CALC (2011. where the temperature of the liquid phase falls to a minimum below the melting point before a slight increase to a temperature plateau. This force is provided by cooling the liquid below its melting point.57 output by user ali from CATS-PC . a driving force is needed.09) : DATABASE:SSOL4 P=1E5.10.
This is probably due to the thermocouple being separated from the alloy sample by the glass tube. it can be surmised that the computationally obtained diagram is probably the most accurate in this case. samples with inexact compositions and impurities in the samples. a significant number of experimentally obtained values for the liquidus are lower than the corresponding solidus point obtained computationally. The database used to generate this phase diagram is the result of both theory and many experimental results. Possible reasons for these errors include improper mixing of the samples at higher temperatures. which acts as an insulator. From this.13:12.02) : DATABASE:SSOL4 P=1E5. Although a number of the liquidus temperatures are in fairly close agreement between the two methods. THERMO-CALC (2011.10. This shows that some of the experimental data are not very accurate. 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 10°C lower than those given by the computer-generated diagram. The accuracy of the experimental phase diagram would be improved by repeating the experiment a number of times to compensate for these errors.The two phase diagrams obtained during this experiment can be plotted onto the same set of axes and compared (Figure 8). .
The liquidus and solidus composition values obtained were then averaged to find a value the percentage of tin present in sample X. This determination can be said to be fairly accurate as using the same method with the computed phase diagram gives a similar answer. they are dependent on the observer’s interpretation. This was found to be about 87% by weight. accessed 13/10/11 https://docs.google. it was found that the computationally derived diagram was most accurate in this case. This means it is difficult to consistently estimate the temperatures where phase transformations occur.ac. Conclusions In conclusion.com/a/sheffield. The experimentally derived phase diagram was of limited usefulness.uk/viewer?a=v&pid=gmail&attid=0.com/mail/?ui%3D2%26ik%3D2 444ff56a2%26view%3Datt%26th%3D132fc976e9322288%26attid%3D0.As the liquidus and solidus points were obtained visually from the cooling curves.1&thid=132fc976 e9322288&mt=application/msword&url=https://mail. but could be improved by repeating the experiment a number of times. The composition of sample X was determined by drawing a rough trendline on the experimental phase diagram. Introduction to thermodynamics.1%26disp%3Dsafe% 26zw&sig=AHIEtbRGbC9Vr9WUHIdwlZosdts7-T6Hxg&pli=1 . the temperatures plotted on the phase diagram will not have a very high degree of accuracy. Consequently. References 1.google. MOLE Portal.