MATE 215 - Lab 4 Phase Diagrams
MATE 215 - Lab 4 Phase Diagrams
MATE 215 - Lab 4 Phase Diagrams
Laboratory 4
Eutectic
Phase Diagrams
Goal
To use phase diagrams to predict stable phases, determine melting and freezing
temperatures, and identify suitable operating temperatures for alloys in applications.
Background
Importance of Phase Diagrams in Engineering
Each type of engineer uses graphical tools to communicate information or to perform
calculations. For example, electronic engineers use timing patterns to help analyze
the digital output of a circuit board; agricultural engineers use a contour map to
assist in designing an irrigation system. Materials engineers – especially
metallurgists and ceramists – use phase diagrams to determine which phases are
stable at certain combinations of composition and temperature. One of the more
important aspects of phase diagrams is that it will let you know at what
temperatures an alloy is solid and what temperatures it becomes either partially or
completely liquid. These things would be useful to know if your component was
designed to operate at high temperature (like many aircraft engine turbine blades).
Additionally, we can perform calculations with phase diagrams to determine the
amount of the various phases present.
Imagine a chocolate chip cookie, like the one shown at right. The
cookie consists of the “cookie base” and the chocolate chips. This
is a statement of the two solid phases present in our chocolate chip
cookie. The big reason they are separate phases is that you can
easily tell the difference between them. This is obvious, but it’s
important. Consider the chocolate chips: they have a homogeneous
composition, a given structure, and a real boundary separating
them from the cookie base. These are the three attributes of a
phase in materials engineering: composition, structure, and
boundary. Now consider the cookie base. This is an example of
a solid phase that is made up of more than one component:
flour, sugar, eggs, butter, etc. You cannot see these individual
components in the cookie because they form a solution – a solid
solution. The cookie base is single phase and multi-component.
In materials engineering, the analog to the multiphase chocolate
chip cookie is the multiphase microstructure as seen through the
optical microscope. An example of this for a cast iron is shown
at right – the light regions are one phase, and the dark regions
another phase.
In this laboratory, you will be dealing with various mixtures of phases in the lead-tin
(Pb-Sn) system. One of the phases is liquid – familiar to you. The other two phases
are solids, and – likely not as familiar to you. One of the objectives of this
experiment is to increase your knowledge of multiple solid phases.
Like hot tea and sugar, a liquid solution, solids can dissolve certain amounts of other
elements and create a solid solution. For example, lead can dissolve a certain
amount of tin creating a lead-tin solid solution. Imagine the tin atoms substituting
for some of the lead atoms in the crystal structure of lead, which happens to be FCC
(face centered cubic). A solid solution is usually given a Greek letter on the phase
diagram (such as or ). So, when you see (or ) on a phase diagram, that refers
to a mixture of two different elements in solid solution and not the pure element.
This bears repeating: is not a pure element.
Where you want to go deals with what will happen when you heat or cool your alloy
composition.
Consider Figure 1, which is the Pb-Sn phase diagram. Pb and Sn are the two
components of the system. The components are the pure elements. The phases
shown are solid , solid , and liquid. The phase diagram is therefore a map of what
phases can exist at various combinations of composition (%Pb-%Sn) and
temperature.
Interpreting phase diagrams is much like reading a map. For example, imagine that
you have an alloy with an overall composition of 40 wt.% Sn (60 wt.% Pb). The red
vertical line in Figure 1 represents this overall composition. The temperature you
want to consider is 300C. These coordinates (red dot in Figure 1) indicate that we
are in the single phase liquid region of the phase diagram. So, if we had some small
chunks of lead and tin handy, weighed out 40 wt.% Sn and 60 wt.% Pb, put our
chunks in a high-temperature stainless steel container, and heated it to 300C, the
mixture would turn to liquid. That liquid would contain a homogeneous mixture of Pb
and Sn atoms. Now, notice something interesting about our alloy – if we slowly
cooled it from 300C, it would remain liquid until about 240C (horizontal dashed line
in Figure 1). Below 240C, the liquid would cross into a two-phase region containing
solid and liquid – more about this in a bit. What this means is that the mixture of
Pb and Sn can exist as a liquid (mixture of liquid and solid) at temperatures well
below the melting temperature of pure Pb (327C). This is one of the fascinating
things about mixtures of elements. We will return to our 40 wt.% Sn example, but
first there are a few more things about phase diagrams to mention.
240°C
+ L
+ L
+
Figure 1. The Pb-Sn phase diagram. The red vertical line represents a particular alloy composition of
40 wt.% Sn – 60 wt.% Pb.
Hopefully, the and phase fields of the diagram are a bit familiar to you now.
These are our solid solutions at the two ends of the phase diagram. Because they
are at the ends, they are called terminal solid solutions. Notice that the maximum
L
Temperature
L→S
S
327C
Time
Figure 2. Cooling curve for pure lead. At the melting point, there is a thermal arrest when liquid lead
changes to solid lead at 327C.
Since this is a pure element, it freezes at a specific temperature on cooling from the
liquid. When the solidification happens, the temperature is constant producing a
thermal arrest. The temperature remains constant until all of the liquid has
transformed to solid. Thermal arrest occurs whenever there is one more phase than
there are components in the system. In order for these phases to be in equilibrium,
the temperature must remain constant. In our pure lead example, the system
contains one component (Pb), and during freezing there are two phases in
equilibrium (L, S). Take note that we did not use here because we are dealing with
pure lead and not a solid solution of lead and tin.
Cooling II - Alloy
An alloy is a mixture of two or more metallic elements. Cooling is much more
interesting when considering what happens to an alloy compared to a pure element.
Now we really need the phase diagram to tell us what is going on as we cool from
the liquid. Let’s return to our 40 wt.% Sn example once again (Figure 1). We have
heated it to liquid at 300C and are now going to plot out a cooling curve as it cools
to the solid state (Figure 3).
L
240C
Temperature L + Phases
183C
+
L→+
Reaction
Time
Figure 3. Schematic cooling curve for an alloy containing 40 wt.% Sn-60 wt.% Pb.
We already know about #1. The second one is called proeutectic , primary , or
(alpha prime). The third in our list can be two different things. It can be simply in
a mixture of and , if the overall alloy composition is less than 18.3 wt.% Sn. Or it
can refer to both proeutectic and formed below the eutectic temperature from
the eutectic reaction. This is a little confusing, but it will become clearer when we
discuss what the microstructures look like at various regions of the cooling curve.
Keep in mind that each of these is – single phase solid solution of mostly Pb and
some Sn – they just appear at different regions of the phase diagram.
phase diagrams: at any point in the diagram, we can sketch and label the
microstructure of the alloy. This is important because the microstructure – the
distribution and morphology of the phases – can control the properties of the alloy.
Figure 4. The microstructures formed during solidification of a 40 wt.% Sn alloy. Note that the
eutectic structure occurs as closely spaced layers of and .
Proeutectic
and in layers
formed by the
eutectic reaction
Figure 5. The microstructure of a Pb-Sn alloy slowly cooled from the liquid. Note the eutectic mixture
of and consisting of closely spaced layers of each phase.
The same kind of redistribution occurs when alloys freeze from the liquid. Instead of
people jumping into different cars, atoms will join different phases. Keep a few ideas
in mind.
1. We only have two components to work with, like Pb and Sn.
In two-phase regions, we need a tie line to determine the compositions of the phases
present. A tie line is a horizontal line at a specific temperature that goes between
the boundaries of the two-phase region. Consider the same overall composition of
40 wt.% Sn once again, but this time at 200C (Figure 6). There is a tie line drawn
in connecting the (left-hand side) and L (right-hand side) boundaries of the + L
two-phase field at 200C. The composition of each phase can be determined from
the endpoints of the tie line. The composition of is 18 wt.% Sn, and the
composition of the liquid is 57 wt.% Sn. What has occurred is a redistribution of Pb
and Sn atoms that were in a single-phase, homogeneous liquid at 300C to another
liquid phase and a solid phase at lower temperature. It’s much like the situation
where two of your road-trip group have just gotten into the alien car. The overall
composition of the + L mixture is still the same at 40 wt.% Sn, just like your two-
car caravan road-trip still has 60% women and 40% men.
Overall composition
Tie Line
+ L
+ L
+
Tie line
Overall Composition
18 wt.% Sn 57 wt.% Sn
Figure 6. The Pb-Sn phase diagram with a tie line at 200ºC for an overall composition of 40 wt.% Sn.
18 wt.% Sn 57 wt.% Sn
40 wt.% Sn
To determine the amount of in the two-phase mixture, we need to take the side of
the lever opposite from (think of what is balancing for the lever). The fraction
of is given by:
57 − 40
f = = 0.436 = 43.6% (1)
57 − 18
You can see that we simply use the wt.% Sn composition values from the tie line for
the calculation. The meaning of this number is that the two-phase mixture of + L
is 0.436 or 43.6% . The remainder (1-0.436 = 0.564) is L. So, if you had 250
grams of alloy that you melted to begin with, and then slowly cooled it to 200ºC,
0.436 x 250 g = 109 grams would be .
Key Terms
Phase
Liquid solution
Solid solution
Solubility
Component
Alloy composition
Terminal solid solution
Eutectic composition, temperature, reaction
Cooling curve
Thermocouple
Thermal arrest
Alloy
Proeutectic (primary) alpha
Eutectic microstructure
Tie Line
Lever rule
Always Be Safe
1. Be careful not to touch any hot surfaces of the furnace. At the temperature
range that we are working, surfaces will not appear to be hot.
2. Wear gloves when handling the furnace cap.
3. Do not heat any sample above 360°C.
4. Do not breathe any vapors coming from the melted samples. Use the exhaust
system while melting and cooling.
Lab Snapshot
You will generate cooling curves for two different alloy compositions (one known and
one unknown) in Pb-Sn system. For each composition, you will heat the sample into
its liquid state, transfer it to a cooling chamber, and use a thermocouple to monitor
the temperature as it cools to solid. Your cooling curves will be used to determine
the temperatures for the phase changes that occurred on cooling and to determine
the overall composition of the unknown alloy.
Directions
Heating and Cooling Alloys
1. Pb-Sn Phase Diagram. Locate the small copy of the Pb-Sn phase diagram.
Double-stick tape this into your lab notebook. You will be using it for
calculations; mark it up as you work through various parts of the experiment.
2. Known Alloy Composition. Choose a known alloy composition from the samples
at your lab station.
3. Alloy Composition and Phase Diagram. On your phase diagram, draw a vertical
line at the overall alloy composition you have just chosen. Make a listing of the
temperatures and reactions where phase changes will occur for your alloy
composition on cooling from the liquid. These temperatures will help you set
up your heating and cooling experiment.
4. Cooling Curve Set-Up. Using nearly a whole page in your lab notebook, set up
the axes to measure a cooling curve for your alloy (as in Figure 2 or 3). It’s
best to turn your book sideways for the plot. You will be taking data every 30
seconds for about 15-20 minutes; have 1 grid square correspond to 1 minute.
5. Alloy Samples. Examine your sample for a moment. There is an outer tube,
sealed at the bottom and open at the top, that contains the alloy. There is also
a small stainless steel tube inside the larger tube. This small tube will act as
the sheath for the thermocouple during heating and cooling.
6. Thermocouple. A thermocouple is simply a high-temperature thermometer. It
has a digital read-out and a long, thin metal probe with a plastic handle. Turn
on the digital read-out, and make sure it reads room temperature in degrees C.
The temperature is measured at the tip of the metal probe.
7. Alloy Sample into the Furnace. The furnace may be hot from previous lab
sections; take care and wear gloves if this is the case. Remove the metal cap
from the furnace. Place your alloy sample into the furnace chamber. Slide the
thermocouple’s metal probe through the hole in the cap. Place the furnace cap-
thermocouple combination onto the top of the furnace carefully threading the
thermocouple probe into the stainless steel small tube of your sample. Make
sure that the thermocouple is truly in the stainless steel tube before
proceeding.
8. Sample Heating. Turn on the furnace using the toggle switch. Do not adjust
the furnace controls. The furnace itself has a digital temperature read-out, but
this is the temperature near the heating elements, and not your sample. Watch
the thermocouple temperature during heating. You do not need to record any
data during the heating portion of the experiment. Turn on the exhaust hood
(knob is around the back of the unit).
9. Maximum Temperature. Your goal is to make your sample completely liquid.
You already know from your prediction with the phase diagram for your overall
alloy composition at what temperature this will occur. You want to go 20-30C
above this temperature. When you reach this temperature, check to see that
the alloy is liquid by gently moving the plastic handle of the thermocouple. You
should be able to move the stainless steel sheath around easily.
10. Furnace Off. Shut off the furnace.
11. Transfer Alloy Sample to Cooling Chamber. The transfer of your sample to the
cooling chamber requires two team members to complete. One team member
completely removes the thermocouple from the cap and sample. This same
team member removes the metal cap from the furnace using the gloves
provided, placing it onto the steel table, and then reinserts the thermocouple
probe into the stainless steel sheath while the sample is still in the furnace.
Another team member uses the hook to transfer the sample and thermocouple
to the cooling chamber. The first team member then puts the metal cap back
onto the furnace. Once the sample is in the cooling chamber, do not touch the
thermocouple or the sample.
12. Cooling Data and Curve. Using the stopwatch provided, begin taking time and
temperature data and plotting it as you go on your cooling curve axes. A
strategy: one person monitors the time, another person writes down the
temperatures, and the third person plots the data. It’s important to plot as you
go (not waiting until after the cooling has completed). Your alloy needs to be
completely solid for a few minutes to get the last part of the cooling curve that
means well below the eutectic temperature. This step should involve all three
team members, and it takes about 20 minutes to complete.
13. Return Alloy Sample to Rack. When your cooling is complete, remove the
thermocouple from your sample. Using the hook, place your sample back in its
original position in the rack of samples.
Questions
1. Explain how each of the three characteristics of solid solutions listed on p. 2 is
shown graphically on a typical phase diagram. Notes: (1) these characteristics are shown
all in the solid phase, that is, below the eutectic temperature. (2) Be sure that the response to this
question is clearly identified in THREE parts: 1, 2, and 3.
2. Explain why a change in slope (for example what is shown at 240C in Fig. 3),
not a thermal arrest, occurs in a cooling curve.
3. (a) Explain why a thermal arrest occurs in a cooling curve. (b) What specific
reaction is occurring during thermal arrest?
4. Determine the overall alloy composition of your unknown alloy sample using your
cooling curve and the Pb-Sn phase diagram in your lab notebook. The
composition will not be one of the ones already at your lab station. Include an
explanation of how you determined the composition.
Use the Pb-Sn phase diagram in your lab notebook, NOT a phase diagram in this lab write up, to solve the
following problem.
This is an important problem for this lab and for your understanding of phase diagrams. Remember
that compositions are always read off the x-axis of phase diagrams (%Sn, %Pb) and usually do not
involve mathematical calculations.
6. Two Pb-Sn alloys are in the running to be used in a structural application that will
see a maximum temperature of 185C. Alloy 1 contains 10 wt.% Sn; alloy 2 has
20 wt.% Sn. Using the phase diagram, determine which alloy to use and why.
Notebook Check
• Cooling curves for known alloy and unknown alloy (completely labeled
including temperatures, phases, reactions, and microstructures for each)
• Pb-Sn phase diagram showing evidence of your calculations
• Tie line and lever rule calculations – this should include the tie line that you
used for your calculations
• Answers to questions
Clean Up
• Each of the alloy samples should be in its original location.
• The digital thermocouple readout and exhaust hood should be turned OFF.
• The furnace cap should be on the furnace.
• Generally look around your lab area to make sure it is clean and well
organized for the next lab team.
• Push the stools underneath the lab table.