LAB REPORT ON LEAD-TIN PHASE EQUILIBIRUM

Harsh Menon

The purpose of this lab was to study lead-tin phase equilibrium. This was accomplished
by mixing different amounts of lead and tin, heating them to about 800˚F and then letting
them cool exposed to air. Once the cooling process had begun, the temperature was
recorded every 5 seconds, until the temperature went below 200˚F. The data was then
used to generate cooling curves for the different composition alloys. The temperatures at
which the slopes of the cooling curves changed were then plotted on the phase-
equilibrium diagram.

The different compositions tested in the lab were:

1. Pure Lead
2. 10% Tin
3. 20% Tin
4. 40% Tin
5. Eutectic (61.9% Tin)
6. 80% Tin
7. Pure Tin

The table below lists the different weights of lead and tin used to make the compositions
listed above:

Table 1: Weights of lead and tin used in the experiment.

Composition of Composition of
Composition Weight of Lead Weight of Tin Lead Tin
(g) (g) % %
Pure Lead 10 0 100 0
10% Tin 10 1.11 90 10
20% Tin 10 2.5 80 20
40% Tin 10 6.67 60 40
61.9% Tin 10 16.25 38.1 61.9
80% Tin 2.5 10 20 80
Pure Tin 0 10 0 100

The table above lists the weights of lead and tin required to make the necessary
compositions. However, since we did not restart the experiment every time (i.e., once we
had heated and cooled pure lead, we added 1.11g of tin and continued the experiment),
we had to ensure that we added the right amount of tin to the specimen. For example, for
the 20% tin specimen, since we already had the 10% Tin specimen, we just had to add
1.39 g to the 10% tin specimen to get the required weight of 2.5g.

The lead-tin phase-equilibrium diagram is shown on the next page.

 Figure 1: Lead-tin equilibrium phase diagram
(Chung, 2002).

The figure above can be used to predict the form of the cooling curves of the different
compositions of tin. In the figure above, the alloys with different compositions of tin will
show changes in their slopes whenever they cross one of the blue boundaries – which
physically represents a change in the phase of the alloy. A change in slope occurs at the
liquidus as primary alpha microstructure begins to form. The formation and growth of
primary alpha results in the evolution of latent heat of fusion which in turn slows the
cooling rate. Therefore, the slope decreases across the liquidus. At the eutectic
temperature, a thermal arrest takes place. This happens because the eutectic reaction
(which converts the liquid to alpha and beta) takes place at a constant temperature of
183˚C or 361.4˚F. Thus we can predict that both hypoeutectic and hypereutectic alloys
will have a change in slope at the liquidus, and the new slope will be followed by an
invariant temperature region and then followed by another change in slope. The eutectic
alloy’s cooling curve will have a decrease in slope with temperature, followed by the
eutectic invariant temperature and then followed by another change in slope.

Pure lead and tin will also have an invariant temperature region. However, for pure lead
and pure tin, the invariant temperature region corresponds to a melting region. The
corresponding temperature is the melting temperature. Consider the cooling curves of
pure tin and pure lead shown on the next page.
 Figure 2: Cooling curves for pure lead and pure tin.

The melting temperatures of pure lead and pure tin are determined from investigating the
invariant temperature region in the figure above. For pure lead, the melting temperature
was determined to be 611˚F and for pure tin, the melting temperature was determined to
be 447˚F. In the pure tin cooling curve, there appears to be an initial change in slope at
around 658˚F. However, this change in slope is probably an inflexion in the data.

The cooling curve for the 10% alloy is shown below:

Figure 3: Cooling Curve for 10% Tin alloy.

We know that the 10% alloy starts off in a liquid phase, goes to a liquid + alpha mixture,
then to an alpha phase and finally to an alpha + beta mixture. Thus, there should be four
separate slopes in the figure above, but there are five. This could imply an inflexion in the
data at the 350˚F region, since the 10% alloy does not undergo the eutectic reaction
(which takes place at 361.4˚F). If this was so, then the first line would represent the liquid
phase, the next the liquid + alpha mixture, the third long region would represent the pure
alpha phase and the last slope would represent the alpha + beta phase. The experimentally
determined transition temperatures are listed below and compared with book values from
Askeland & Phulé (2006):

Table 2: Experimental temperatures versus book temperatures for 10% tin alloy.
 Experimental Book Temperature (F) Percent
Temperature (F) Difference (%)
Liquid to Alpha + 611 644 5.1
Liquid
Alpha + Liquid to 611 554 10.3
Alpha
Alpha to Alpha + 352 284 23.9
Beta
The table above shows that the experimentally determined values are close to the book
values with a maximum percent difference of 23.9%. Possible reasons for deviations
from the book values could be due to experimental errors in mixing the lead and tin and
uneven heating and cooling.

Consider the cooling curves for the 20% alloy and the 40% alloy shown below:

Figure 4: (a) Cooling Curve for 20% alloy and 40% alloy

The figures above show the same general behavior. Both alloys, start from the liquid
phase, and continue in that phase till about 600˚F for the 20% alloy and 480˚F for the
40% alloy. Some of the liquid then precipitates into alpha and the alloys enter an alpha +
liquid mixture. The decrease in slope is due to the evolution of latent heat due to the
formation and growth of primary alpha microstructure. This continues until the eutectic
temperature, which is about 350˚F for both alloys. At this temperature, two solid
solutions - alpha and beta, begin to form from the liquid. This continues till all the liquid
has been transformed into a mixture of alpha and beta. In terms of microstructure, at the
end of the eutectic reaction, there exists primary alpha and the eutectic. The
experimentally determined transition temperatures are listed below and compared with
book values from Askeland & Phulé (2006):

Table 3: Experimental temperatures versus book temperatures for 20% and 40% tin alloy.

20% alloy 20% Percent 40% alloy 40% Percent

Transition alloy Difference Transition alloy Difference
Temperature Book (%) Temperature Book (%)
(F) value (F) (F) value (F)
Liquid to 600 554 8.3 480 464 3.4
Liquid +
Alpha
Liquid + 350 361.4 3.1 350 361.4 3.1
Alpha to
Eutectic
Eutectic 350 361.4 3.1 350 361.4 3.1
to Alpha
+ Beta
The table above shows that for both hypoeutectic alloys, the transition temperatures are
close to the book temperatures with a maximum percent difference of 8.3%. The eutectic
temperature of 350˚F is also very close to the book value of 361.4˚F.

Now consider the eutectic alloy with 61.9% tin. The cooling curve of the eutectic alloy is
shown below:

Figure 5: Cooling curve for eutectic alloy.

The cooling curve of the eutectic alloy should be similar to that of a pure metal since
eutectics freeze or melt at a single temperature (as can be seen from Figure 1). The figure
above shows a few inflexion regions in the eutectic cooling curve. However, the general
form of the curve is similar to that of a metal. There is an initial decline, followed by a
region of almost constant temperature, followed by another region of decline. The first
region corresponds to the pure liquid phase, the second to the eutectic temperature where
all the liquid solidifies to alpha and beta, and the third corresponds to the mixture of
alpha and beta. The eutectic temperature determined from the above cooling curve ranges
between 410˚F and 350˚F. An average temperature would be 380˚F, which is a 5.1%
difference from the book value of 361.4˚F. The inflexions exist at 612˚F, 378˚F, 361˚F
and 350˚F.

Finally, consider the cooling curve for the hypereutectic alloy with 80% tin as shown
below:
 Figure 5: Cooling curve for 80% tin alloy.

The hypoeutectic alloy goes from a liquid phase to a beta + liquid phase, then undergoes
the eutectic reaction and turns into a mixture of alpha and beta. There is a gradual change
in the first slope of the cooling curve at around 390˚F, followed by an inflexion point and
a much lower slope. The first slope corresponds to the liquid phase. This slope is a
composite of two slopes with a transition temperature of 607˚F. However, this change in
slope is gradual and is probably an inflexion point. The next smaller slope is due to the
beta + liquid phase. Right after the beta + liquid slope is the nearly horizontal line
corresponding to the eutectic reaction. The final slope is that of the alpha + beta mixture.
The experimentally determined transition temperatures are listed on the next page and
compared with book values from Askeland & Phulé (2006).

Table 4: Experimental temperatures versus book temperatures for 80% tin alloy.
 Experimental Book Temperature (F) Percent
Temperature (F) Difference (%)
Liquid to Beta + 378 410 7.8
Liquid
Beta+ Liquid to 361 361.4 0.1
Eutectic
Eutectic to Alpha 350 361.4 3.1
+ Beta
The table above shows that the experimental values are close to the book values with a
maximum percent difference of 7.8%.

The transition temperatures from all the different compositions of lead-tin alloys were
then plotted on the lead-tin phase equilibrium diagram as shown below:

Figure 6: Transition temperatures on the lead-tin phase equilibrium diagram.

The figure above shows the different transition temperatures and their locations on the
phase diagram. Ideally, the data points would lie exactly on the green lines. However, the
data points are shifted either forward or back of the green lines. The 10% alloy points (in
blue) are ahead of the green curves. In case of the 20% and 40% specimen, the initial data
point is ahead of the liquidus, but the second data point is almost on the eutectic
temperature line. The eutectic composition has some anomalous data points as well as a
data point very close to the eutectic. The hypereutectic alloy has most of its data points in
between the green lines, which is unlike those of the other alloys. The pure lead and tin
have melting temperatures which match the temperatures on the phase diagram. Some
possible reasons for the deviations from the green lines could be incorrect measurement
techniques, contamination of specimen, variation of slope with altitude, or a combination
of the three.

Further analysis was done on the 40% tin, eutectic and 80% tin alloys by observing them
under a scanning electron microscope. The surface of the 40% tin alloy is shown below
as seen from the scanning electron microscope:
 Figure 6: 40% tin alloy under a scanning electron microscope.

The image above shows certain bright regions that stand out from the rest. The brighter
regions represent regions of higher atomic mass, and therefore, represent the lead-rich
phase, or the alpha phase. In terms of microstructure, the 40% alloy has primary alpha
and eutectic (lamellar) microstructure. Lamellar microstructure is formed by plates of
alpha and beta stacked on top of one another. The bright spotted regions represent regions
of lamellar microstructure. However, not much can be discerned from this picture.

An image of the eutectic under the microscope did not reveal any useful results either. It
can be seen on the next page.
 Figure 7: Eutectic alloy under a scanning electron microscope.

The eutectic alloy should have shown the dominant lamellar microstructure formed after
undergoing the eutectic reaction. However, none can be seen in the figure above. The
80% tin alloy showed a few bright regions, where lamellar microstructure might have
existed. The image can be seen below:

Figure 8: 80% tin alloy under a scanning electron microscope.

The figure above shows certain bright regions. However, the dominant feature of the
image appears to be holes or sandpaper particles deposited on the surface of the alloy
during grinding.

The 40% tin and 80% tin images were then analyzed to determine the percentage of alpha
and beta present in them. Prior to the experiment, calculations were done using the tie
line rule on the lead-tin equilibrium phase diagram. The theoretically determined
percentages of the alpha and beta in the two specimen are tabulated below:

Table 5: Calculated percentages for 40% and 80% tin alloys.

 40% tin alloy 80% tin alloy
Percentage of alpha 73.2% 22.3%
 Percentage of beta 26.8% 77.7%

The images were then analyzed using a software program called SCANDIUM to
determine the percent area that each phase occupied in the image. In the case of the 40%
tin alloy, the image was cut and reduced to the small region where the spots were the
brightest. The figures below show the spotted region of Figure 6 in green and yellow –
green representing beta and yellow representing alpha:

(a) (b)
Figure 9: (a) 40% tin alloy with original color scheme (b) with tweaked color scheme

The figure to the left shows the alloy with the intensity levels adjusted so that there was a
sharp difference between the alpha phase and the beta phase and so that the colors
accurately represented the two phases. However, the percentage of alpha and beta
obtained from that image were not consistent with the data shown in Table 5. The
percentages obtained were 41.3% alpha and 58.70% beta. Therefore, readjustments in the
intensity levels were made until the percentages were the same as those in Table 5. The
result of this is shown in the figure to the right. The figure to the right has a lot more dark
spaces in it than the figure to the left, and this might be a plausible reason why the
percentages did not meet up in figure (a).

The same process was repeated for the 80% tin alloy. The images obtained are shown on
the next page.

(a) (b)
Figure 9: (a) 80% tin alloy with original color scheme (b) with tweaked color scheme
The figure to the left represents the original color scheme, with the team eyeballing what
they thought was the best way to adjust the intensity levels so that the two colors
accurately represented the phases. However, this yielded an alpha percentage of 13.2%
and a beta percentage of 86.8%. The percentages were then tweaked to obtain the same as
those in Table 5. The difference appears to be in intensity threshold levels. The image to
the right has a few brighter regions than the image to the left. However, trying to adjust
the intensity levels and not take the holes in the background is quite a challenge.

References

Chung, D.L. (2002). Retrieved from the State University of New York at Buffalo,
Mechanical and Aerospace Engineering website:
http://www.mae.buffalo.edu/courses/mae381/lecturenotes/