E 45 Laboratory Manual

Laboratory 3
Binary Alloy Phase Diagrams
Objectives
1. To understand how phase diagrams are constructed from cooling curves
2. To compare the as-solidified microstructures of different alloys in a binary alloy system

Overview
This lab is designed to illustrate the experimental determination of binary alloy phase diagrams. Students generate
cooling curves from a series of lead-antimony alloys to establish phase field boundary temperatures and compare this
data to as-solidified microstructures to establish compositions.

Equipment
Thermal Processing

1. Pyrex glass tube, 15 125 mm, containing Pb-Sb alloy, labeled, with lava plug
2. Pyrex glass tubing, 4 mm diameter, 5 long, sealed on one end, to serve as thermocouple sleeve, with brass
stop collar
3. Chromel+Alumel thermocouple
4. Coil furnace with power-control rheostat
5. Aluminum mold, glass slide in mold, with individual mold heater assembly
6. Safety gloves, goggles, tongs
7. Computer data acquisition equipment
Metallography

8. Optical microscope with 100 and 500 objectives; Stereo microscope with 7 and 30 objectives
9. Microscope slides, plasticene mounting aid
10. Etching reagent: 16 parts glycerol; 1 part acetic acid; 1 part nitric acid

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Copyright 2014, Berkeley

Professor Lane W. Martin

Laboratory 3: Binary Alloy Phase Diagrams

Background
Phase Diagrams

Phase diagrams are used to depict the equilibrium state of a multi-component system, normally as a function of temperature and composition. For example, solid water (ice) and liquid water are two different phases that have the same
composition, but differ in atomic arrangements at their respective equilibrium temperatures. Tin has two distinct solid
state phases with different atomic structures. Brine (a liquid solution of water and salt) has a different composition
and structure than a mixture of solid salt and ice. The set of curves in a phase diagram delineate the temperature and
composition boundaries within which specific phases will exist. For points on the curves, the two (or at the eutectic
temperature, three) phases that are separated by the curve coexist in equilibrium.
Cooling Curves

Pure elements have well-defined single melting temperatures, whereas alloys (materials containing more than one element) do not. If heat is applied to a pure metal, its temperature will rise as heat is absorbed until the melting point is
reached. Then the heat will be absorbed at a constant temperature until melting is complete, after which the temperature will again begin to rise. The heat absorbed during the melting process is called the heat of fusion. Cooling the
metal to the melting point will result in the release of the heat of fusion, which will halt the cooling until solidification
is complete. This is apparent in the cooling curve for pure Pb shown in Fig. 1.

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Temperature (C)

400
Pb
328
300

200

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time

Figure 1 Schematic cooling curve for pure lead. The thermal arrest occurs at the melting temperature, lasting as long as the two phases coexist in equilibrium.

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Laboratory 3: Binary Alloy Phase Diagrams

By contrast, an alloy melts over a range of temperatures. Cooling to the liquidus (the curve in the phase diagram
above which only the liquid phase is stable) causes solidification of a small amount of the alloy and the release of a
small amount of heat, which retards but does not halt the cooling rate. Cooling at this slower rate continues while the
solid phase particles continue to grow until solidification is complete (a solidus line is reached) or until a reaction
isotherm, such as a eutectic or peritectic transformation temperature is reached.
These temperature-invariant reactions cause a halt in cooling, whereas crossing a solidus line merely causes another
change in cooling rate. A change in cooling rate is detected as a change in slope of the temperature vs time curve.
Transformations involving only solid phases may also produce changes in cooling rate, but these will not be considered in this experiment.
Cooling curves for a series of alloys in the Pb-Sb system with increasing solute content are shown in Figs. 2 and 3.
Some of these curves show an obvious thermal arrest like that exhibited by pure Pb above, but in addition, there are
locations where a more subtle change in slope occurs. From these curves you can construct part of the Pb-Sb phase
diagram (Fig. 4), keeping in mind that the exact phase diagram cannot be determined solely from such a small number
of curves.
Look closely to compare the curves for the 7.5% Sb and 15% Sb alloys. Note that they are nearly the same, in that
both have a change in slope near 275C and halt at 251C. This shows that the cooling curves by themselves do not
always provide enough evidence to determine the composition of an alloy even in a known alloy system. While conducting this experiment, you must also examine the microstructure of your alloy to establish its composition. This is
especially true because the change in slope in the 15% Sb alloy is very small and may go undetected if your cooling
curve data is not sufficiently accurate.

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Laboratory 3: Binary Alloy Phase Diagrams

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400

Pb-2.5%Sb

325
300 305

200
400

Pb-5.0%Sb

Temperature (C)

300 295
251
200
400

Pb-7.5%Sb

300
275
251
200
400

Pb-10.0%Sb

300
258
251
200

time

Figure 2 Schematic cooling curves for four (4) lead-antimony alloys with lower Sb composition. Note how
the changes in slope and broad thermal arrests correlate with the phase diagram presented in Fig. 4.

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Laboratory 3: Binary Alloy Phase Diagrams

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400

Pb-12.5%Sb

300
257
251
200
400

Pb-15.0%Sb

Temperature (C)

300
275
251
200
400

Pb-17.5%Sb

300 305
251
200
400

Pb-20.0%Sb
325

300
251
200

time

Figure 3 Schematic cooling curves for four (4) lead-antimony alloys of higher Sb composition. Note both
the changes in slope and broad thermal arrests correlate with the phase diagram presented in Fig. 4.

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Laboratory 3: Binary Alloy Phase Diagrams

Thermocouples

A thermocouple is a temperature-measurement device that exploits the Seebeck Effect, the voltage difference induced
in a conductor by a temperature gradient. It uses a couple consisting of two conductors, joined at one end, to probe
the difference in potential between the open ends (the cold junction) as an indicator of the temperature at the hot
junction. The potential difference is measured with a voltmeter, and converted to degrees using conversion tables.
Unfortunately, the conversion tables usually assume a cold junction reference temperature of 0C. This requires a
correction procedure that adds an amount of potential to represent the actual temperature of the cold junction (usually
nearer to room temperature) while the reading is made. The corrected potential is the one converted to degrees.
The microcomputer-controlled thermocouple meter used in this laboratory will do this conversion for you.
Although any pair of conductors can be used in a thermocouple, the most common ones (the ones for which conversion tables are available) are the following: iron+constantan; copper+constantan; chromel+alumel; and
platinum+platinum/rhodium (alloy).

Experimental Procedures
Remote Preparation

Compare the Pb-Sb phase diagram in Fig. 4 with the above cooling curves in Figs. 2 and 3. Do this before coming to
the laboratory to prepare for your identification of the unknown alloy in this experiment. Pay special attention to the
clues revealing the location of the liquidus lines, the solidus lines, and the eutectic isotherm. Convince yourself that
you understand the relationship between the cooling curves and the phase diagram before attempting a cooling curve
from your unknown alloy.
Lab samples were made in crucibles containing a 1500 gm charge of lead and antimony (amounts of both constituents were varied to yield different alloy compositions) that were rapidly melted to reduce loss of Pb by oxidation.
The crucibles were removed from the furnace, stirred well, and, as soon as a dull film formed on the surface, their
contents were poured into labeled test tubes for the experimental portion of this lab.
The following alloy compositions were prepared:
[a] 95.0%Pb-5.0%Sb;
[b] 88.2%Pb-11.2%Sb; and
[c] 85.0%Pb-15.0%Sb.
Each lab station is supplied with a test tube containing a lead-antimony alloy, to be set up as shown in Fig. 5.

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Laboratory 3: Binary Alloy Phase Diagrams

700
630.7
600

Temperature (C)

L
500
400
327.5
300

251.2

Pb
3.5 11.2

95.5

Sb

200
100 0.44
Pb
10

20

30

40
50
60
70
Weight Percentage Antimony

80

90

Sb

Figure 4 Pb-Sb binary alloy phase diagram, from the Metals Handbook, 8th Edition, Volume 8, American
Society for Metals, Metals Park, Ohio (1973), p. 329.

Thermocouple wire
Thermocouple sleeve

Lava
plug

Brass stop
collar

Pyrex
tube

Alloy
charge

Set collar
to give 0.5
in. clearance here

Collar limits
penetration of
thermocouple into
melt

Thermocouple
rests on
alloy when
solid
...
sinks when
molten

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Figure 5 Schematic showing experimental set-up for determining cooling curves. A small gap at the bottom
of the Pyrex tube assures that the thermocouple is reading the temperature of the alloy and not the glass
containment vessel. The gap is measured as shown at left. After melting, the thermocouple sinks into position, as shown on the right.

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Laboratory 3: Binary Alloy Phase Diagrams

Part I

To obtain cooling curves, perform the following sequence.

1. Record the identification number of your specimen that appears on the label tag of the Pyrex tube.
2. Insert a lava plug into the opening of the sample tube.
3. Slide a brass stop collar over the glass thermocouple sleeve and position the collar to allow the sleeve to maintain approximately inch clearance from the bottom of the Pyrex tube when the alloy melts.
4. Insert the thermocouple sleeve through the hole in the lave plug until it rests (gently) against the alloy charge,,
rotating it as needed so that it slides freely.
5. Insert a thermocouple into the sleeve, and connect the thermocouple to the data acquisition interface.
6. Turn ON the furnace power by rotating the rheostat all the way to the rubber stop located at 40 on the dial.
Monitor temperature rise, but do not begin recording yet. As the temperature nears 280C, gradually decrease the
furnace power to prevent overshooting the target temperature of 300C. Start data recording when the temperature reaches approximately 290C.
7. As the alloy charge melts, the thermocouple sleeve should sink into the liquid alloy until the brass stop collar
contacts the lava plug (Figure 6). If the thermocouple tube does not sink, it might be stuck in the lave plug. To
free it, gently tap the tube with the test tube clamp until the thermocouple slides downward. Do NOT jostle the
thermocouple too vigorously. If the thermocouple shifts out of position during data acquisition, experimental artifacts could be introduced. For example, if the thermocouple sleeve tilts toward the side of the test tube, where the
sample will be cooler than at the center, you may record a change in the cooling curve that could be mistaken for a
transition.
8. Let the temperature rise to approximately 305C, then turn OFF the furnace by rotating the rheostat control to
zero (0).
9. Stop recording data when the sample has cooled to 200C.

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Laboratory 3: Binary Alloy Phase Diagrams

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Figure 6 Photograph of furnace assembly after melting. The brass

stop collar is resting on the lava plug at the top of the Pyrex tube
indicating that the thermocouple has descended into the molten alloy
charge.

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Figure 7 Photograph of aluminum mold used in Part II
of this laboratory. A glass slide is inserted into the rectangular cutout on the left half before assembly, creating
a smooth solidification surface for subsequent optical
metallographic examination of the casting.

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Laboratory 3: Binary Alloy Phase Diagrams

Part II

To obtain samples for examination under the microscope, perform the following sequence.
1. Preheat an Al mold (Fig. 7) by turning on the mold heater switch and setting the mold temperature controller with
the arrow up () button to 280C.
2. Insert a thermocouple into the small well in the side of the mold and monitor the mold temperature in the lower
display of the controller. The controller will heat the mold automatically to the target temperature.
3. While the mold is preheating, re-melt the alloy sample as in Part I. The liquid should be at a higher temperature
this time (360C) so that it can infiltrate the mold completely before solidifying.
4. When the sample is fully molten at 360C, and while the tube is still in the furnace, carefully remove the thermocouple, the brass stop collar, the glass thermocouple sleeve and the lava plug. Now remove the Pyrex tube
containing the molten alloy and QUICKLY pour the liquid into the preheated mold without splashing. It should
be obvious that the molten charge is a serious burn hazard, so proceed with caution.
5. Turn OFF the power to the furnace by rotating the rheostat control to zero (0).
6. Adjust the arrow down () button to change the mold temperature set point to 0C. This will initiate solidification.
7. When the sample has cooled to 200C, loosen the compression screws on the back of the mold heater, withdraw
the thermocouple from the side of the heater, and slowly press the mold ejector lever to lift the mold out of the
heater box. Releasing the ejector lever should allow the mold to rest on the mold support at an angle so it can be
grasped with tongs.
8. Using tongs (while wearing gloves) lift the mold out of the heater and carry it carefully to the nearest water-filled
quenching sink.
9. Plunge the mold into the sink (it may sizzle as it touches the water so submerge it quickly) agitate it under water
for a few seconds, and leave it under water for a few minutes to cool. Keep track of your mold; there will be others using the same sink.
10. When the mold is completely cool, the casting can be released from the mold. The side of the casting that contacted the smooth glass slide is the observation side for optical microscopy, consequently it should not be touched
during handling.
11. Immerse the casting in the prepared etching reagent for about 1 second. Remove it quickly and immediately rinse
it with running water. Wash with alcohol and dry under a hot air blast.
12. Mount the specimen on a glass slide with a piece of plasticene so that the smooth surface can be conveniently observed under both microscopes. Note that under the metallurgical microscope the Sb-rich solid solution appears
as the bright phase; the Pb-rich phase is relatively dark with a brown color if the filter is removed from the micro-

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Laboratory 3: Binary Alloy Phase Diagrams

scope illuminator. However, the contrast is reversed when the specimen is viewed under the stereo microscope.
Make a sketch or capture a photograph of a representative microstructure field from your specimen. Your sketch
should have sufficient detail to allow you and any other observer to identify the alloy composition. It is therefore
important to be precise about relative volume fractions of phases and relative contrast.

Lab Report
Your report should include all thermocouple calibrations, cooling curves, a labeled copy of the Pb-Sb phase diagram
showing the location of your alloy composition, microstructural sketches, photographs, and answers to the following
questions.
Question 1

By direct comparison of your cooling curves and the phase diagram, what can you conclude about the composition of
your alloy?
How confident are you? Explain your answer in detail, noting all sources of experimental error and what you did to
minimize them.
What might you do to improve precision? Accuracy?
Question 2

Describe the successive changes in microstructure that took place during solidification of your alloy. Write a detailed
caption for your sketch of the microstructure from your specimen.
Label the microconstituents seen in your sketch and give your opinion of both the composition and the temperature at
which each constituent solidified.
Comment specifically on how you identified the Pb-rich constituent, the Sb-rich constituent, and the eutectic constituent. Cite all relevant references to support your answers.

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