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Determination of Lead-Tin Phase Diagram using

Cooling curves
Jason Pechardo

Mary GericcaDol

Department of Mining, Metallurgical, and Materials


Engineering
Philippines, Quezon City
jason_pechardo@yahoo.com

Department of Mining, Metallurgical, and Materials


Engineering
Philippines, Quezon City
violet_chubica@yahoo.com

Melita Sandra Dela Merced


Department of Mining, Metallurgical, and Materials
Engineering
Philippines, Quezon City
msedelamerced@gmail.com

Department of Mining, Metallurgical, and Materials


Engineering
Philippines, Quezon City
arielle_jv@yahoo.com

Ma. Arielle Johnna Veronica G. Del Rosario

Abstract---A phase diagram, which is a collection of several


cooling curves for a system with varying composition, shows
the relationship of temperature and all thermodynamic phases
of a substance. It provides information on different physical
and thermal phenomena that occurs for materials.
Determining cooling curves and phase diagrams are essential
in different industries since these provide necessary
information in investigating the relationship of material
behavior with respect to temperature. In this experiment, the

cooling curves ofPb-Sn alloy system at different


compositions were determined using a thermocouple. From
these cooling curves, the phase diagram of the Pb-Sn system
was established. This diagram determined an experimental
equilibrium freezing temperature of 189 degrees Celsius that
deviated from the theoretical value by 3.27%. Possible sources
of error that contributed to this deviation include inaccurate
measurements and inconsistent working conditions.
Index terms---phase diagram, cooling curves, thermocouple,.

I. INTRODUCTION
A phase diagram is a chart used in various fields of
science and engineering that shows the relationship of
temperature and all the thermodynamically distinct phases
of the substance of interest. Moreover, it is highly helpful as
it provides information about the melting, solidification,
casting and other physical and thermal phenomena of the
material [1].The phase diagram also shows the eutectic
temperature for a mixture of two or more substances. The
eutectic point is important as it shows the composition and
lowest temperature for a mixture to completely melt.
As the phase diagram is essentially a cooling/heating
curve for a mixture of a number of component substances, it
is helpful that a similar curve be observed for each
component as a pure substance. Figure 1 shows the cooling
curve of pure lead (Pb). The horizontal region at 327C
describes the solidification of the liquid Pb. In this region,
the cooling is counterbalanced by the heat release upon
solidification.

Figure 1[2]. Cooling curve of pure Lead

A similar curve is observed if the cooling temperature


is plotted for Tin (Sn) except that solidification occurs at
232C.
The binary phase cooling curve of Pb-Sn (67%-33%)
alloy system at is plotted in Figure 2. The solidification
starts at around 250C where some Pb start forming solid
phases. All of Pb and Sn solidify at 183C which is
comparatively lower as compared to the melting
temperature of the components. If the amount of Sn is raised
to 38%, the start of solidification will coincide with the
horizontal region in the curve. This means that solidification
will start and end at 183C, this behavior is similar to how a
pure substance would behave upon cooling. The mentioned
phenomenon is achieved only when the composition of the
Pb-Sn is 62%-38%, which is the eutectic composition [2].

Figure 2[2]. Cooling curve of Pb-Sn alloy

Pechardo, J., Dela Merced, M.S., Dol, M.G., Del Rosario, M.A.J.V. (2015)

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was plotted and the start and end of the solidification


process was estimated by the changes in the slope of the
curve. Using the data obtained from the curves of the 5 alloy
compositions, the phase diagram of the Pb-Sn alloy system
was determined.
III. RESULTS AND DISCUSSIONS
The experiment dealt with the use of a thermocouple to
determine the cooling rate of different lead-tin mixtures.
These were used to plot their corresponding cooling curves
from which the experimental Pb-Sn phase diagram was
derived.
The following are the cooling curves obtained from the
data.

90:10 Pb-Sn Mixture


Temperature (degree Celsius)

A phase diagram can be obtained by collecting several


cooling curves for a certain system and varying its
composition, Pb-Sn in the given example. Just by plotting
the temperature at the start of solidification and the
temperature at the horizontal region, the phase diagram is
essentially complete.
Determination of the cooling curve and phase diagram
are essential in the industry as it provides information
regarding the behavior of substances and mixtures with
respect to temperature. It is especially important for eutectic
alloy systems which take advantage of the lowered melting
temperature of alloys at eutectic composition. This concept
is used in solder and weld technologies. Another use for
eutectic alloy systems is for sensing temperature changes
and monitoring the temperature. Galinstan, a ternary alloy
of Gallium (Ga), Indium (In), and Sn, is used as
replacement for Mercury (Hg) in thermometers because of
its low melting temperature and non-toxicity. Other
applications include temperature response for fire sprinklers
and coolant system for reactors.
The experiment deals with the determination of the
cooling curves of Pb-Sn alloy system at different
compositions. The compositions to be studied are 90%10%, 80%-20%, 60%-40%, 40%-60% and 20%-80%. A
rough estimate of the Pb-Sn phase diagram is formed using
the cooling curve data. The experiment aims to establish a
phase diagram given the cooling curves of the system of
interest. The use of thermocouple is also part of the
objective.

400
350
300
250
200
150
100
50
0
0

100

II. EXPERIMENT DETAILS

The instant the Pb and Sn metals liquefied completely,


the crucible was transferred into a cooling jacket.
Overheating the alloy was avoided so that oxidation would
be hindered. The formation of an oxide would interfere with
the cooling and would give unnecessary noise in the cooling
curve.
After transferring the crucible to the cooling jacket, the
thermocouple was placed properly, so that the tip touches
the cooling melt. The thermocouple measured the
temperature of the melt as it cooled. Every 5 seconds, the
temperature was recorded.
This procedure was performed for the five (5)
compositions of the Pb-Sn alloy system. The cooling curve

400

80:20 Pb-Sn Mixture


Temperature (degree Celsius)

B. Procedure

300

Figure 3. Cooling Curve of 90:10 Pb-Sn Mixture

A. Materials
In this experiment, the alloy was prepared from Pb and
Sn metal samples. For the 90%-10% Pb-Sn alloy, 9 g of Pb
was weighed and mixed with 1 g Sn. 8 g Pb and 2 g Sn were
mixed for the 80%-20% composition, 6 g Pb and 4 g Sn for
the 60%-40%, 4 g Pb and 6 g Sn for 40%-60%, and 2 g Pb
and 8 g Sn for the 20%-80% composition. The mixtures
were placed in a crucible and heated with a Bunsen burner
until melting.

200
Time (s)

Pechardo, J., Dela Merced, M.S., Dol, M.G., Del Rosario, M.A.J.V. (2015)

400
350
300
250
200
150
100
50
0
0

100

200
Time (s)

300

400

Figure 4. Cooling Curve of 80:20 Pb-Sn Mixture

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In order to derive the phase diagram, the point of


inflection in the cooling curves were estimated. These
points of inflection are the temperatures at which that
particular concentration of Tin in Lead begins to melt.

60:40 Pb-Sn Mixture


Temperature (degree Celsius)

400
350

Table 1. Estimated Melting temperature of different


compositions of Tin.

300
250
200

Sn (%)

Melting
Temperature(C)

Eutectic
point(C)

10

304

183

20

268

181

40

243

187

60

212

189

80

252

189

150
100
50
0
0

200

Time (s)

400

600

Pb-Sn Phase Diagram

Figure 5. Cooling Curve of 60:40 Pb-Sn Mixture

Temperature

Temperature (degree Celsius)

40:60 Pb-Sn Mixture


400
350
300
250
200

350
300
250
200
150
100
50
0
0

150

10 20 30 40 50 60 70 80 90 100

% Sn

100

Figure 8. Experimental Phase Diagram of Pb-Sn Binary system.

50
0
0

200

Time (s)

400

600

Figure 6. Cooling Curve of 40:60 Pb-Sn Mixture

Temperature (degree Celsius)

20:80 Pb-Sn Mixture


400
350
300
250
200
150
100
50
0

Figure 9. Phase Diagram of Pb-Sn

200

Time (s)

400

Figure 7. Cooling Curve of 20:80 Pb-Sn Mixture

600

Comparing Figure 8 and 9, which are the experimental


and theoretical phase diagrams of a Pb-Sn binary system
respectively, it can be seen that the experimental results
agree with the theoretical. There are differences present
however but they are very minimal. First, in figure 6, there
is no information regarding the formation of the alpha and
beta phase because for compositions less than 10% Sn and

Pechardo, J., Dela Merced, M.S., Dol, M.G., Del Rosario, M.A.J.V. (2015)

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greater than 80% tin no data points were obtained


experimentally. The cooling curves of pure lead and tin
were not taken. Second, the line corresponding to the
eutectic temperature is not a straight line as opposed to the
theoretical. This may be attributed to the fact that the
cooling curve of the 90:10 mixture of Lead and Tin (fig.3)
did not exhibit a plateau. Theoretically, the cooling curves
must have a plateau which indicates that there is a decrease
in the rate of cooling of the mixture due to the separation of
the solid phase (solidification). The heat evolved during
this, partly offsets the heat lost by radiation and conduction
to colder surroundings which makes the change in cooling
rate seem negligible, thus, resulting in a straight line in the
cooling curve. The absence of a plateau in figure 1.might be
because the crucible was not fully covered which might
have caused the heat evolved from solidification to be
released to the surroundings. Third, the graph of the melting
point Tin versus composition did not coincide with the
eutectic temperature. This is largely because the number of
data points is not enough to approximate the eutectic point.
Theoretically the eutectic point of Pb-Sn binary system
occurs at 1830C with 68% Sn and 32% Pb as mentioned in
the introduction. The average of the eutectic points
obtained from the experiment is 185.8 0C.
Due to inaccuracies in the cooling curves which may
have been caused by inaccurate weight measurements and
inconsistent working conditions, the experimental phase
diagram deviated from the theoretical although not
significantly. To improve its reliability, parameters such as
room temperature should be kept constant. Moreover, the
system which consists of the solution and the crucible
should be closed, so that equilibrium can be maintained. In
other words, the crucible must be fully covered so that the
heat lost or gained from the reaction would be accurately
recorded. Also a better approximation of the theoretical
phase diagram may be obtained by increasing the number of
data points, specifically the concentrations at which the
cooling curves where determined.

curves exhibited a plateau except for the 90%Pb-10%Sn


composition. This may be due to errors such as inaccurate
weight measurements and inconsistent working conditions.
Also, the crucibles used were not fully covered which might
have caused the release of evolved heat to the surroundings.
From the plotted cooling curves, the derived phase diagram
determined that at 189 degrees Celsius, thermal arrest
occurs. This temperature, also known as the equilibrium
freezing temperature, deviated from the theoretical
temperature of 183 degrees Celsius by 3.27%.

IV. CONCLUSION
In this experiment, the phase diagram of Lead-Tin (PbSn) system of varying compositions was derived from the
different cooling curves that were determined using a
thermocouple. Results showed that most of the cooling

Pechardo, J., Dela Merced, M.S., Dol, M.G., Del Rosario, M.A.J.V. (2015)

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Appendix

Pechardo, J., Dela Merced, M.S., Dol, M.G., Del Rosario, M.A.J.V. (2015)

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