Engineering 45 Properties of Materials

Laboratory

Copyright 2001 Professor Ronald Gronsky the Arthur C. and Phyllis G. Oppenheimer Chair in Advanced Materials Analysis Department of Materials Science & Engineering University of California Berkeley, California 94720-1760

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Lab 2

Phase Diagrams

Objectives
To understand how phase diagrams are constructed from cooling curves To compare the as-solidified microstructures of different alloys in the lead-antimony system

Overview
This lab is designed to help obtain a better understanding of how phase diagrams are experimentally determined. Students will construct a simple phase diagram using the cooling curves provided for a series of lead - antimony alloys. The cooling curve of an alloy with unknown composition will be obtained by each student. The composition of the alloy will be determined from this information and from observing the microstructure.

Equipment
Computer data acquisition system Chromel + alumel thermocouple Pyrex test tube, 15 x 125 mm, containing Pb-Sb alloy (5%, 11.8%, or 15% Sb) Pyrex glass tubing, 4 mm diameter, 5" long, one end sealed Bi-grip test tube clamp Lava plug Coil furnace Mold heater Aluminum spacer Thermocouple tube stop Aluminum mold Glass slide in mold Tongs Gloves Etching reagent Glycerol 16 parts Acetic acid 1 part Nitric acid 1 part Microscope, 100x, 500x Stereomicroscope, 7x, 30x Microscope slide and plasticene Graph paper (20 to the inch), to be furnished by student

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Background
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 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 regions of temperature and composition over which a given phase will exist. For points on the curves, the two (or at the eutectic temperature, three) phases that are separated by the curve coexist and are said to be in equilibrium. Pure elements have well-defined melting points whereas alloys (materials containing more than one element) generally 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, when 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 below.

400 T (C) 300 Pure Pb 328 252 200 time

Fig. 3-1 Schematic cooling curve for pure lead. The thermal arrest occurs at the melting temperature, lasting as long as the two phases co-exist in equilibrium.

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. A series of cooling curves for alloys in the Pb-Sb system is given below. 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

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construct part of the Pb-Sb phase diagram, keeping in mind that the exact phase diagram cannot be determined solely from such a small number of curves. Look closely at the curves for the 7.5% Sb and 15% Sb alloys. They are nearly the same; both have a change in slope near 280C and halt at 252C. 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 determine 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.

400 T (C) 300 Pb-2.5%Sb 328 252 200 time 400 T (C) 300 Pb-5.0%Sb 328 252 200 time 400 T (C) 300 Pb-7.5%Sb 328 252 200 time 400 T (C) 300 Pb-10.0%Sb 328 252 200 time

Fig. 3-2 Schematic cooling curve 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. 3-4.

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400 T (C) 300 Pb-12.5%Sb 328 252 200 time 400 T (C) 300 Pb-15.0%Sb 328 252 200 time 400 T (C) 300 Pb-17.5%Sb 328 252 200 time 400 T (C) 300 Pb-20.0%Sb 328 252 200 time

Fig. 3-3 Schematic cooling curve 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. 3-4.

Techniques
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 of the hot junction. The potential difference is measured with a voltmeter, and converted to degrees using conversion tables.

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Unfortunately, the conversion tables usually assume a cold junction reference temperature of 0C. This necessitates 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, platinum+platinum/rhodium.

Temperature Stripchart Program To further ease the collection of data and to expedite digital data processing, a number of E45 stand-alone data acquisition programs have been developed and written in LabVIEW , a programming package by National Instruments for instrumentation and control. The first such program is the temperature stripchart. In this program, there are 3 displays and 2 controls. All 3 displays show the same information (degrees Celsius vs. time) in different formats. The Normal Resolution Display shows 25 minutes of data, and the High Resolution Display shows 100 seconds of data. A Temperature Display shows the last temperature value in digital format for highest accuracy. The 2 controls are the Run Button and the Start/Stop Recording button. The Run Button is the right-facing arrow in the upper left hand corner of the screen. Clicking this button starts the program and begins plotting the data on the displays, but the program is not recording any data to disk at this point. When you first click the Run Button, you will be asked to name the file1 that is to retain your acquired data. The suggested name includes the lab number, your section number and your name(s) or initials, up to 31 characters. To begin recording data to disk, click the Start Recording button in the lower right hand corner of the screen. The Start/Stop Recording Button activates the "record status" light when clicked, changing from a flashing red light to a steady red light. Recording begins immediately, but any data displayed on the screen prior to the start of recording is not captured. To stop recording, click the same (Stop Recording) button. Both data display and data recording will stop. NOTE: Please place your data file in the E45 folder of the hard disk so it will not be misplaced. After you have acquired your data, you may use the scroll bars at the bottom of both the Normal Resolution Display and the High Resolution Display to review the data that has passed off the display area. When finished, you can click the Close box located in the upper lefthand corner of the windows, or select "Close" from the File menu. If you want to start another acquisition, you will have to close/quit the program and restart.

In the dialog box that requests the file name, there is a button labeled "use llb" that is a function library. If you click this button, a new dialog box will appear. Unfortunately, some of the buttons in the new dialog box crash the program due to an uncorrected bug. If you accidentally press the use llb button, press the CANCEL button to get back to the original display.

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Procedures
Remote Preparation Compare the Pb-Sb phase diagram2 below with the above set of cooling curves. 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. The following will be done for you by the lab technician and GSIs. In a fireclay crucible, a 1500 gm charge of lead and antimony (amounts of both constituents are varied to yield different alloy compositions) is heated until the entire charge is molten. The heating is done as rapidly as possible to reduce the loss of lead by oxidation. The crucible is removed from the furnace, the melt stirred well and, as soon as a dull film forms on the surface, poured into test tubes for the experimental portion of this lab.

700 630.7 600

L

500 T (C) 400 327.5 300

Pb

251.2 11.2 95.5

Sb

3.5 200 100 Pb 0.44

10

20

30

40

50 wt % Sb

60

70

80

90

Sb

Metals Handbook, 8th Edition, Volume 8, American Society for Metals, Metals Park, Ohio, (1973), p. 329.

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Part I Each party will be supplied with a test tube containing a lead-antimony alloy as shown in Figure 3-5. To obtain a cooling curve: Record the identification number of the specimen. Place the lava plug in the test tube Insert the thermocouple into the thermocouple tube and place the tube stop on the tube to locate the bottom of the tube 1/4" from the bottom of the test tube when the sample melts. This is to prevent reading erroneously low temperatures near the ends of the sample. Place the test tube into the coil furnace. Connect the thermocouple to the data acquisition interface. Start the data acquisition program and start recording data. Turn the rheostat to the rubber stop to begin heating the sample. Heat the specimen to 300C. As the temperature nears 280C, begin to decrease the power to the furnace in order to not overshoot the target temperature of 300C. When the alloy melts, the thermocouple tube should drop and become supported by the clip. If the thermocouple tube does not drop by 280C, tap the tube with the test tube clamp as the tube might be stuck in the lava plug. Make sure the thermocouple remains in the same position during the data acquisition for experimental consistency. If the thermocouple is displaced toward the side of the test tube, where the sample will be cooler than at the center, you will detect a difference in the slope of the cooling curve, which could be mistaken for a transition. Turn the furnace off by turning the rheostat to zero. Stop recording data when the sample has cooled to 200C.

Part II The following procedure should be executed to obtain a specimen for examination under the microscope: Preheat an Al mold to 280C. The mold temperature is measured by a thermocouple in the small well at the side of the mold. Turn on the mold heater switch and press the up-arrow button until the desired temperature is indicated in the lower display of the controller. The controller will heat the mold to the desired temperature automatically. Melt the alloy while the mold is preheating as was done in part I. Heat the sample to 360C. When the alloy is fully molten turn the rheostat to zero, remove the thermocouple, thermocouple tube and the lava plug. Quickly pour the molten charge into the hot mold, making sure not to splash any, as it could cause serious burns. Using the down-arrow button, change the set point temperature to 18C. When the sample has cooled to 200C, loosen the compression screws on the back of the mold heater and slowly press the mold ejector lever to lift the mold out of the heater. Release the lever and the mold should rest on the mold support at an angle. Put on the gloves and using the tongs, lift the mold out of the heater and bring the sample to the sink. Carry your sample with the tongs. Please inform your fellow students and the TAs that you will be passing them with a hot mold. Plunge the mold into the sink and agitate the mold under water for a few seconds. Do not be intimidated by the sizzling sound which occurs when the mold touches the water and plunge the mold underwater quickly.

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As there may be many molds in the sink, make note of its position and inform the TA when asked. When the mold is cool, the TA will separate it and remove the casting. Take care not to touch the side of the casting that was against the smooth glass surface. The TA will immerse the casting in the prepared etching reagent for about 1 second. The sample will then be immediately rinse with running water. Wash with alcohol and dry under hot air blast.

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 when using the metallurgical microscope the Sb-rich solid solution appears as the bright phase; the Pb-rich phase is relatively dark and shows a brown color if the filter is removed from the microscope illuminator. The contrast is reversed when the specimen is viewed under the stereomicroscope. Make a sketch of a representative microstructure field from your specimen. Your sketch should show the microstructural features which help to identify the sample composition. The quality of your sketch should allow the TA to also be able to identify the sample composition.

Lab Report
Please include all thermocouple calibrations, cooling curves, labeled copy of the Pb-Sn phase diagram showing location of your alloy composition, microstructural sketches, 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.