MatE 25 San J ose State University Lab Notes

Rev. 4.0 6 - 1 Phase Diagrams

Lab 6: Pb/Sn Phase Diagram
1.0 Learning Objectives
After successfully completing this laboratory workshop, including the assigned reading, the lab
worksheets, the lab quizzes, and any required reports, the student will be able to:
Define component, phase, phase diagram, and cooling curve.
Describe the phase change taking place at different points on a cooling curve.
Construct a phase diagram from cooling curves.
Define microstructure and sketch the predicted microstructure from a phase diagram.
2.0 Resources
[1] Callister, Materials Science and Engineering: An Introduction, (J ohn Wiley and Sons,
New York, 2000), Ch 9.1-9.12.
[2] Phase Diagram Tutorial: http://www.soton.ac.uk/~pasr1/
[3] MATTERs Interactive Tutorial on Steel: http://www.matter.org.uk/steelmatter/
[4] Another Interactive Phase Diagram Tutorial:
http://www.eng.usf.edu/~campbell/ThermoI/Proptut/tut1.html
3.0 Materials Applications
Equilibrium diagrams (or phase diagrams) are graphs of the relationships between the primary
externally controllable factors (e.g., pressure, temperature and composition) and phases present
in the material at equilibrium. These relationships, which are governed by principles of
thermodynamics, have vast practical applications in many areas of science and engineering. The
engineer needs to understand the principles of equilibrium diagrams to recognize and solve
problems in many industrial processes such as annealing, zone refining, carburizing,
semiconductor processing and many others. An understanding is also needed of how to infer the
microstructure of a material from the equilibrium diagrams. This will then allow you to
determine how processing (such as changing the temperature or composition) will change the
microstructure and ultimately the properties of the material.
4.0 Phase Diagrams
A phase diagram is a plot of the equilibrium (lowest free energy) state of a system. The state of
the system is the phases present, such as solid, liquid, or gas. And a solid may have multiple
phases of crystal structures. In metallurgical and ceramic engineering, the most important
processes are assumed to occur at or near atmospheric pressure. With the assumption of constant
pressure conditions we take temperature and composition as the primary variables to be plotted
with respect to each other. Attention is usually focused on the two-component (binary) or
sometimes three-component (ternary) systems. Read Chapter 9 of Callister for more in depth
discussion of phase diagrams.
A number of methods exist for determining the equilibrium phases and phase compositions at
temperature, and then develop a phase diagram. One of the oldest and simplest methods of phase
MatE 25 San J ose State University Lab Notes
Rev. 4.0 6 - 2 Phase Diagrams
diagram determination is by studying a cooling curve. This experiment introduces us to the
cooling-curve method of constructing equilibrium diagrams for a binary alloy system.
Whenever a phase change takes place in a metal or alloy, the total energy content changes, and
this is revealed during cooling or heating by evolution or absorption of heat. If a pure metal is
cooled under near equilibrium conditions from the liquid state, and its temperature plotted as a
function of time, the resulting cooling curve will show a plateau, or thermal arrest, at a given
constant temperature, the ends of which correspond to the beginning and end of solidification
(Figure 1).

Figure 1. Near equilibrium cooling curve for a pure metal or a eutectic alloy. Solidification
takes place at a single temperature. Supercooling may occur if nucleation is difficult.
Actually, the liquid may cool to a temperature below its freezing point before crystallization
occurs; this is called supercooling. Once solidification begins, the temperature will rise to the
freezing point and remain there until solidification is complete. Most alloys will solidify from the
molten state over a range of temperatures. The cooling curve will thus have liquid-solid
transition points at two different temperatures representing the beginning and end of
solidification (Figure 2).
The binary system to be studied in this experiment is that of Pb-Sn. The phase diagram for this
alloy is shown in Figure 3. This system is characteristic of eutectic alloy systems, in which the
two components are completely soluble in each other in the liquid state, but only partially soluble
in the solid state.
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Rev. 4.0 6 - 3 Phase Diagrams

Figure 2. The cooling curve characteristic of a binary alloy where solidification takes place
over a range of temperatures.

Figure 3. The Pb/Sn Phase Diagram. (Callister, Materials Science and Engineering: An
Introduction 7
th
edition, (John Wiley and Sons, New York, 2000), Ch 9. Fig 9.8.
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Rev. 4.0 6 - 4 Phase Diagrams
In a eutectic system, the "eutectic alloy" composition has the lowest melting point in the system;
lower than the melting points of either of the pure components. This is useful in many
applications, for example common solder metal.
Any liquid-to-solid transformations for alloys in this type of system can be determined by
plotting points taken from their cooling curves. Alloys in which solid-to-solid transformations
take place are usually analyzed for phase diagram preparation by some means other than the
cooling curve method of thermal analysis. That is because solid state transformations are often
sluggish and the heat change is too small to be readily detected by cooling curves. For this
experiment all alloys studied have compositions between the points of maximum solubility of
lead-in-tin and tin-in-lead respectively.
Other methods which may be used for equilibrium diagram determination are: electrical
resistivity, X-ray diffraction, microstructure examination, differential scanning calorimetry,
magnetic susceptibility, density, and thermal expansion measurements.
5.0 Principles of Thermocouple Operation
A critical parameter in this experiment is temperature. A device called a thermocouple senses the
temperature. A thermocouple consists of two wires made of different alloys. When a temperature
gradient is present along each wire an EMF (voltage) is developed. The EMF is a function of the
temperature difference and the alloy. Since each wire is made of a different alloy, there is a
different EMF developed along the length, and that results in a voltage between the two wires.
The voltage is read by the computer, converted to temperature, and conveniently displayed.
6.0 Experiment
Important notice: Pregnant students should not attend this laboratory because of the danger of Pb
vapors causing birth defects. However, a report is still required. Contact your lab instructor.
There are no health risks to careful adults.
6.1 Equipment and Materials
Electrical resistance furnaces
temperature controllers
temperature recorders
thermocouples
test tubes
tongs
cooling blocks
Pb/Sn alloys
Pb/Sn mounted alloy samples
Optical microscopes
6.2 Procedures for Pb/Sn Cooling Curves
1. Place the test tubes containing the alloys in the furnaces, and heat above the liquidus
temperature as shown on the equilibrium diagram.
MatE 25 San J ose State University Lab Notes
Rev. 4.0 6 - 5 Phase Diagrams
2. When the alloy has reached the molten state, transfer the test tube containing the
thermocouple to the cooling block. Use tongs and gloves when transferring the hot
crucibles. Observe the cooling curve on the computer screen until it indicates that
solidification is complete. Record the temperature(s) of phase change(s).
3. Repeat step 2-4 for all the remaining samples.
4. Observe and record the thermal arrest temperatures for each alloy and the pure metal
samples on the data sheet.
5. Observe and identify on the data table those alloys that exhibit supercooling.
6.3 Procedures for Water Heating Function
This is an exercise in taking fairly simple data. However, there are a number of thermodynamic
phenomenon going on, including whether the components are in equilibrium or not. So this is
also an exercise in having keen observations and taking good notes on what you observe.
1. Place ~6 ice cubes and 70-100 ml of cold water in a beaker.
2. Place digital thermometer into ice water bath let temperature equilibrate (5 min).
3. Place beaker/thermometer on hot plate.
4. Set hot plate to medium temp (about 60 %).
5. Record temperature every 30 seconds. You only need 5 points beyond boiling, so you
may not fill the entire table. Record any observations you have during this procedure.
6. Graph data. Dispose of the hot water carefully.
6.4 Procedures for Examining Microstructures
1. Examine two of the prepared Pb/Sn samples under the optical microscope. One of
samples will be chosen by your instructor. You are free to choose the other sample.
2. Observe the microstructure, identify phases, and make a drawing.


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Rev. 4.0 6 - 6 Phase Diagrams
Worksheet 1: Pb/Sn Phase Diagram Data
Key Member (Encourages all team members to participate, ensures everyone understands the material, and
organizes/divides the tasks amongst the team members):
Other Group Members:
Perform the solidification experiments following the procedure in 6.2. Use the printed graphs to
find inflections in the cooling curves. Interpret the inflections based on the slope of the curves
before and after, and enter the data below in the table.
Alloy
Composition
Alloy
Number
Solidus
(C)
%
Error
Liquidus
(C)
%
Error
Supercooling
Observed?
100% Sn
20%Pb -
80% Sn

38%Pb -
62% Sn

60%Pb -
40% Sn

80%Pb -
20% Sn

100% Pb
Below, generate a sketch of the Pb-Sn phase diagram. Show where your inflection points
indicate phase changes, or beginning and end of phase changes.

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Rev. 4.0 6 - 7 Phase Diagrams
Worksheet 2: Water Heating Curve Data
Time (s) Temp (C) Time (s) Temp (C) Time (s) Temp (C)
30 600 1170
60 630 1200
90 660 1230
120 690 1260
150 720 1290
180 750 1320
210 780 1350
240 810 1380
270 840 1410
300 870 1440
330 900 1470
360 930 1500
390 960 1530
420 990 1560
450 1020 1590
480 1050 1620
510 1080 1650
540 1110 1680
570 1140 1710

1. What observations would you expect when ice is in equilibrium with the water?

2. What observations would you expect when ice is not in equilibrium with the water?

3. List as many observations as you can while conducting this experiment.











MatE 25 San J ose State University Lab Notes
Rev. 4.0 6 - 8 Phase Diagrams
Worksheet 3: Water Heating Curve


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MatE 25 San J ose State University Lab Notes
Rev. 4.0 6 - 9 Phase Diagrams
Worksheet 4: Microstructure Diagrams
Draw your two Pb/Sn microstructures.
1.















2.











Alloy Compositions : 1.

2.

Based on the composition given, can you identify what phase is Sn, and what phase is Pb?
Make your sketches and label which phase is which.