Deriving the Phase Diagram of Lead-Tin Mixture

Using Cooling Curve

de Guzman, J.R., Labarez, K.H., Yap, J.O.

Department of Mining, Metallurgical and Materials Engineering

College of Engineering
University of the Philippines Diliman
Quezon City 1101, Metro Manila, Philippines
jsyap.11@gmail.com

Abstract Phase diagrams play an extensive role in studying

alloy properties by providing information about phase
composition and phase stability as a function of temperature,
pressure and composition under equilibrium conditions. The
objective of this experiment is to illustrate the use of cooling
curves using thermocouple and to establish the phase diagram
for a Pb-Sn binary system. Five mixtures of Pb-Sn by weight
percent were made in the experiment: 90:10, 80:20, 60:40, 40:60
and 20:80. Cooling curves of the different mixtures of Pb-Sn
showed stagnant temperatures from 183-190C, the longest time
being at 188-190C. Experimental phase diagram derived was
similar in form to the to the reference phase diagram, suggesting
correctness of theoretical concepts. The eutectic temperature was
determined to be between 188-190C. Deviations obtained in the
experiment could be due to impurities in the Pb-Sn mixtures.

I. INTRODUCTION
Binary phase diagrams show the equilibrium phases of a
binary system (usually an alloy) at given temperature and
composition [1]. They are important because they describe the
effects of temperature on a binary system, manipulate nonequilibrium microstructures and the properties of the material
[2]. They show what phases are present, what are the
composition of the phases, and what are the percentages of
these phases [1]. They usually help determine the process and
parameters to achieve certain properties in metal alloys.
When temperature is plotted against time, cooling rates are
nearly linear, but during a phase transformation, like the
formation of a solid from a liquid, the cooling rate is no longer
linear as heat is lost to the surroundings. Therefore it is
possible to generate a phase diagram of a binary system using
a thermocouple [3].

Figure 1. Theoretical phase diagram of lead-tin solders [4].

de Guzman, J.R., Labarez, K.H., Yap, J.O.

Fig. 1 shows the phase diagram of the lead-tin system. Leadtin solders account for 95% of all soldered joints [5]. Their
composition, melting points and phase transformation are
important in the bonding of soldered parts, and the reliability
of interconnections. It is therefore crucial to study the phase
diagram of lead-tin alloys in specific contexts, especially in an
industry with high reliability standards.
Binary phase diagrams can show some critical information
like liquidus temperature and solidus temperature. Liquidus
temperature is the temperature above which the system is
completely liquid. This is the lines right underneath the region
labelled L for liquid in Fig. 1. Solidus temperature below
which, the system is completely crystallized. This is
represented the horizontal solid line in Fig. 1.
Cooling curves are commonly used to generate phase
diagrams, mainly because of the simplicity and easy of the
process. Other known bases in generating phase diagrams are
the following: equilibrated alloys and diffusion couples. In
equilibrated alloys, constituents are heated to equilibria, and
their phases are determined by charactized by techniques like
thermal analysis, metallography, x-ray diffraction, or magnetic
analysis methods. Diffraction couples involve the study of the
phases of interfaces at diffusion zones [6]. Reliability of a
phase diagram can be compared between different diagrams,
but the scope of this study is limited to phase diagrams
generated by cooling curves.
The objective of this experiment is to generate the phase
diagram of a lead-tin system using cooling curves measured
by a thermocouple.
II. METHODOLOGY
With the use of the analytical balance, five mixtures of leadtin mixture was prepared with the following amounts in
weight percent: 90:10, 80:20, 60:40, 40:60 and 20:80. The
mixture of metal was placed in a crucible and was heated
using a Bunsen burner. The crucible was heated until the lead
and tin has melted completely. Once completely melted, the
crucible was immediately transferred to the cooling jacket.
Temperature was recorded using a thermocouple every five
seconds until the metal has cooled to 150C. The same
procedure was done to the remaining four Pb-Sn mixtures.
III. RESULTS AND DICUSSION
1! of 4

The results of the Experiment can are shown in Figure 1.

20:80

188

182

3.1915

TABLE 3. TEMPERATURES INDICATING PHASE CHANGE

Fig. 2. Time-Temperature curves of different alloying percentages of PbSn mixtures

By inspection of these graphs, cooling rate slows down but

remains constant over a certain period. Interpretation of a
cooling curve is done by finding the range of times where
temperatures is constant. [TLP Library] The derivative of the
Temperature (T) vs time (t) curve gives the slope of the curve.
Slopes (T/t) equal /close to zero indicate that temperature
stagnated.
For this analysis, T/t = +0.2 was arbitrarily chosen to
mean the temperature was stagnantthat thematerial
underwent phase change. If the measurement uncertainty of
the thermocouple is known, then T/t can be made to be +
uncertainty. The temperature where the slope was zero or near
zero was identified and summarized in Tables 1 and 2. In
addition, Table 3 summarizes the temperature at which phase
change occured for each Pb-Sn mixture.

TT/t

TT/t
range

Tt

tT (sec)

90:10

159, 165, 171, 184,

306, 307

148

n/a

n/a

80:20

153, 164, 185, 186,

187, 188, 396

243

185-187

30 5

60:40

152, 180, 183, 184,

185

33

183-185

65 5

40:60

150, 187, 188, 189,

190, 194, 200

50

187-190

155 5

20:80

188, 189, 190, 193,

201, 202, 212, 215,
221, 226, 227, 417

229

188-190

50 5

The phase diagram from previous studies is given in

Figure 3.

TABLE 1. HIGHEST TEMPERATURE WHERE SLOPE IS ZERO OR

NEAR ZERO
Experimental

Theoretical

% error

90:10

307

300

2.2801

80:20

396

305

22.979

60:40

185

222

-20

40:60

200

219

-9.5

20:80

417

192

53.956

TABLE 2. LOWEST TEMPERATURE WHERE SLOPE IS ZERO OR

NEAR ZERO
Experimental

Theoretical

% error

90:10

159

150

5.6604

80:20

153

272

-77.778

60:40

-20

152

185

40:60

150

182

-21.333

de Guzman, J.R., Labarez, K.H., Yap, J.O.

Fig. 3. Reference Pb-Sn Phase Diagram [Callister 2007]

Based on the results from the experiement, a similar phase

diagram (Figure 4) can be made.

2! of 4

the invariant point, since solid Pb and solid Sn solidify

supportively, a similar volume fraction of both elements
causes both Pb and Sn to solidify at the same temperature,
with no liquid phase left. [Campbell 2012] The behavior of
alloys and invariant points is demonstrated by this experiment;
however, the specific temperatures differ. The wide
divergence suggests that either data is not interpreted correctly
or other chemicals are at play. This may be a result from
oxidation (respective oxides having a much higher melting
point) from the air cooling because it is open to the
atmosphere. Gas quenching with inert gases like N2 can be
done as opposed to air quenching to avoid oxidation.
[Chandler 1995, 87][Sungil et. al. 2005] Other
recommendations may be to use software for smaller time
increments. Smaller time increments lead to more correct
slope determination, and the correct time and temperature of
solidification can be determined.
Fig. 4. Experimental Phase Diagram

From all of these data, some observations are:

1.
The temperature stagnated at multiple points
and at a wider range in near-pure alloys but
narrowed down near 50-50 alloys.
2.
Similarly, more time was spent near a small
range of temperatures for 50-50 alloys.
3.
The reference and experimental graphs are
similar in shape, but the specific data points vary
widely.
Invariant points are points where more than one phases
transformations at a specific temperature, alloying percentage
and temperature. [Callister 2007] For instance, the eutectic
point (38.1%Pb 61.9%Sn) of Lead-Tin according to the
reference graph occurs at 183C. In the context of this
experiment, the longest times at singular temperature coincide
with uniform melting point; the eutectic point should be found
in this area, where solid Pb and Sn phases are formed from the
liquid alloy.
Theoretically, the eutectic temperature (temperature at
which all the liquid solidifies) is at 183C. Based on the timetemperature curves, most of the time was spent in the
188-190C temperature, which would be the experimental
eutectic temperature.
Connecting the highest and lowest points where slopes
were near zero would form the liquidus and solidus line
respectively. [TLP Library] It can be observed that onset of
solidification begins at a higher temperature when only a
small amount of impurity exists (e.g. 90% Pb 10%Sn, 20%
Pb-80% Sn), but as we move to the centerwhere the eutectic
point should liethe onset begins at a lower temperature.
Studies show that metal alloys with similar crystal
structures (Pb and Sn) solidify supportively together. In the
reference phase diagram, Greek letters (Pb) and (Sn) are
solid phases and L is the uniform liquid phase. Solid Pb forms
near pure Pb melting point, while solid Sn does not, liquid Sn
is diffused away due to surface tension. This means that the
unequal melting points hinder solid formation. However, at
de Guzman, J.R., Labarez, K.H., Yap, J.O.

IV. CONCLUSION
Tracking of temperature of different compositions of PbSn alloy during cooling showed stagnant temperatures from
183-190C; the longest time being at 188-190C. Some
stagnation occurred near 300C for 90-10Pb-Sn, 400C for
80-20 and 20-80 Pb-Sn. Experimental eutectic temperature
was found out to be between 188-190C. Experimental phase
diagram derived was similar in form to the to the reference
phase diagram, suggesting correctness of theoretical concepts.
However, measured temperatures diverged widely from
reference temperatures, suggesting mistaken analysis/data
measurement, or presence of external factors such as
impurities. Cleaner experimental conditions are
recommended.
V. REFERENCES
[1] Binary Phase Diagrams. Accessed April 21, 201. http://
people.virginia.edu/~lz2n/mse305/notes/PD-Binary.pdf
[2] Engineering Materials. Phase Diagrams. Accessed April
21, 2015.
http://people.uwplatt.edu/~mirth/me3040ch9.htm
[3] Humpston, Giles Jacobson, David M.. (2004). Principles
of Soldering. ASM International.
[4] Carter, Giles F. Paul, Donald E.. (1991). Materials Science
and Engineering. ASM International.
[5] Carter, G., Donald, E., Materials Science ang Engineering.
ASM International, 1991. http://app.knovel.com/hotlink/

toc/id:kpMSE00001/materials-science-engineering/
materials-science-engineering

[6] Campbell, F., Phase Diagrams - Understanding the Basics,

ASM International. http://app.knovel.com/hotlink/toc/
id:kpPDUB0003/phase-diagrams-understanding/phasediagrams-understanding
[7] TLP Library Phase Diagrams and Solidification. Accessed
April 19, 2015. http://www.doitpoms.ac.uk/tlplib/phasediagrams/cooling.php.

3! of 4

[8] Callister, William D. Materials Science and Engineering:

An Introduction. 7th ed. New York: John Wiley & Sons, 2007.
258.
[9] Campbell, F.C.. (2012). Phase Diagrams - Understanding
the Basics - 5. Eutectic Alloy Systems. ASM International.
[10] Chandler, Harry. (1995). Heat Treater's Guide - Practices
and Procedures for Irons and Steels (2nd Edition) - 3.2 Air
Quenching Process. ASM International.
[11] Cho, Sungil, Jin Yu, Sung Kang, and Da-yuan Shih.
"Oxidation Study of Pure Tin and Its Alloys via
Electrochemical Reduction Analysis." Journal of Electronic
Materials 34, no. 5 (2005).

de Guzman, J.R., Labarez, K.H., Yap, J.O.

4! of 4

APPENDIX A
40% Pb 60% Sn

525

Temperature (C)

Temperature (C)

90% Pb 10% Sn

425
325
225
125

525
425
325
225
125

100

200

300

400

100

Time (seconds)

200

300

400

500

Time (seconds)
Fig. 4. Plot of temperature vs. time of 40% Pb and 60% Sn mixture

80% Pb 20% Sn

20% Pb 80% Sn

525
Temperature (C)

Temperature (C)

Fig. 1. Plot of temperature vs. time of 90% Pb and 10% Sn mixture

425
325
225
125

425
325
225
125

100

200

300

400

Time (seconds)

60% Pb 40% Sn
525
425
325
225
125
0

100

200

300

100

200

300

400

Time (seconds)

Fig. 2. Plot of temperature vs. time of 80% Pb and 20% Sn mixture

Temperature (C)

525

400

500

Time (seconds)
Fig. 3. Plot of temperature vs. time of 60% Pb and 40% Sn mixture

Fig. 5. Plot of temperature vs. time of 20% Pb and 80% Sn mixture

APPENDIX B
0

-1 0

100

200

300

400

0
-1

-3

dT/dt

dT/dt

-2
-4
-5
-7

-5
-6

Time (seconds)

200

300

400

Time (seconds)

0
0

100

200

300

-0.5

400
dT/dt

-0.5
-1

100

200

-1
-1.5
-2

-1.5

-2.5

-2

-3

Time (seconds)

0.5
0
-0.5 0

100

200

-1

dT/dt

400

0.5

-1.5
-2
-2.5
-3
-3.5
-4

300

-3
-4

0.5

dT/dt

100

-2

-6
-8

Time (seconds)

300

400

Time (seconds)

APPENDIX C

TT/t highest

TT/t

TT/t lowest

Experimental

Reference

relative
error %

Experimental

Reference

relative
error %

90% Pb10% Sn

159, 165,
171, 184,
306, 307

307

300

2.2801

159

150

5.6604

80% Pb 20% Sn

153, 164,
185, 186,
187, 188, 396

396

305

22.979

153

272

60% Pb40% Sn

152, 180,
183, 184, 185

185

222

-20

152

40% Pb60% Sn

150, 187,
188, 189,
190, 194, 200

200

219

-9.5

20% Pb80% Sn

188, 189,
190, 193,
201, 202,
212, 215,
221, 226,
227, 417

417

192

53.956

TdT/dt = T where slope was near zero

Tt = T where slope was near zero for a long time
tT = amount of time at Tt

TT/t
range

Tt

tT (sec)

148 n/a

n/a

-77.778

243 185-187

30 + 5

185

-21.711

33 183-185

65 + 5

150

182

-21.333

50 187-190

155 + 5

188

182

3.1915

229 188-190

50 + 5