ASEN 2001

Introduction to Statics, Structures, and Materials

Fall 2004

Experimental Lab E3 - Phase diagram

Assigned: September 27, 2004 Due date: October 14, 2004 --------------------------------------------------------------------------------------------------------------------Objectives
After this E3 you should be able to: Describe how cooling curves of soluble, partially soluble-insoluble alloy systems are used to generate the phase diagram. Describe liquidus, solidus, and solvus lines on a phase diagram Use the phase diagram to determine the composition and relative amount of phases. Predict the microstructure and name microconstituents from the phase diagram Comprehend temperature limits in the engineering applications of alloys.

Background
A phase diagram is a collection of solubility limit curves for equilibrium states. On one side the single phase is not saturated. Beyond the curve the solubility limit is exceeded and a phase transformation happens. It describes the limits of existence of individual thermodynamic phases of a material. The phase diagram: 1. Tells us what phases are in equilibrium for a selected composition and temperature. 2. Allows us to determine the chemical composition of each phase. 3. Allows us to calculate the quantity of each phase that is present in an alloy. A phase has several characteristics: 1. one phase has the same structure throughout, 2. a phase has similar properties throughout, 3. there is an interface between different phases, a phase boundary. A binary phase diagram is a mixture of two components of various degrees of solubility. Copper-nickel alloys exhibit complete solid solubility, titanium and aluminum have limited solid solubility. A binary phase diagram, exemplified with a common eutectic Pb-Sn alloy shows four distinctive regions: 1) the liquid phase above the liquidus line, 2) the solid below the solidus line, 3) a solid-liquid slurry in-between, 4) the solid may be composed of , , or a combination of both which may be in form of a lamellar or fibrous structure called eutectic.

Phases and solubility limits

Technical alloys are often mixtures of phases, e.g. steel has iron phase and carbide phase, where carbide, Fe3C, is an intermetallic phase. A mixture is a material with at least two phases, each has its own atomic arrangement. Each phase in the mixture is usually a solution by itself. A solubility limit exists when both elements are too different in characteristics. FCC lead (Pb) can dissolve some (BCT) tin (Sn) in its structure, keeping the FCC

Jean Koster

ASEN 2001

Introduction to Statics, Structures, and Materials

Fall 2004

lattice. This solid solution phase is often called -phase. It is bound by a solvus line. BCT-tin can dissolve less Pb in its BCT structure. This phase is often called -phase. Resulting properties of mixtures are different from the properties of the individual phases due to the interaction of phases. Property modification is achieved by changing the shape and/or the distribution of phases.

Isomorphous alloy systems

Binary phase diagrams are constructed from several solid-liquid cooling curves. Cooling curves for pure elements show horizontal thermal arrest at their freezing point. Binary solutions exhibit sloped changes in their cooling curves after the first solid nuclei form in the liquid particle (two phase) system. A second change in cooling slope occurs when all liquid has solidified. The limit line bounded on one side by liquid L is called liquidus line. The limit line bounded on one side by solid is called solidus line. In between solidus and liquidus is a two-phase region with particulates in the liquid melt (solid + L-liquid). Particulates float in the melt and grow to form grains. When almost all melt is solidified the mixture is called a semi-solid. At any specific concentration an alloy has a specific freezing range (1280o-1240oC for Cu-40Ni). When the test volume reached the solidus line all material is solid. Under equilibrium condition the concentration of the solid now is equal to the concentration of the original superheated melt.

Lever rule calculation

Lever rule equations are derived from weight balances. Assume unit volume. Weight fractions for solid (XS) and liquid (XL) are constant: XS + XL = 1

Definitions: Concentrations C0 for total volume, CL for liquid phase and CS for solid phase. Solid Balance: (1) C0 = XL CL + XS CS XL = 1 - XS C0 = (1-XS ) CL + XS CS C0 = CL - XSCL + XSCS C0 - CL = XS (CS - CL )

Jean Koster

ASEN 2001

Introduction to Statics, Structures, and Materials

Fall 2004

XS =
Liquid Balance:

C0 C L as weight fraction of solid CS C L

XS = 1 - XL (1) C0 = XL CL + (1 - XL ) CS C0 - CS = XL (CL - CS ) as both (C0 - CS) and (CL - CS ) are negative we write:

XL =

CS C 0 as weight fraction of liquid CS C L

Graphical solution: Phase fraction percent =

opposite arm of lever x 100% total length of tie line

The Eutectic Phase Diagram

In eutectic binary alloys the pure elements have a higher melting point than dilute solutions of both. Above liquidus line the melt is a (homogeneous) solution of both elements. At one specific composition and temperature a triple point exists. This point is at the intersection of two solubility curves and is called the eutectic transformation. The solubility limit of e.g. tin in the FCC-lead is at the solvus line; and the solubility limit of lead in BCTtin is at the -solvus line. The highest possible solubility of either lead in tin () or tin in lead () is found at the temperature of 183oC. At higher and lower temperature the solubility is reduced; for the -phase (Pb in Sn) both elements become almost immiscible at low temperature.

Jean Koster

ASEN 2001

Introduction to Statics, Structures, and Materials

Fall 2004

The eutectic Pb-Sn alloy has a liquid and overall solid composition of 38.1 Pb - 61.9 Sn. The eutectic melt of that composition changes from a single liquid into two solids as it is cooled through the eutectic temperature: liquid (61.9 Sn)

183o C (19.2 Sn) + (97.5 Sn ) cooling

L1 S1 + S 2 cooling / heating

Heating reverses the reaction. The generalized transformation equation is:

where L1 is the liquid solution and S1 and S2 represent the phases and .

Hypoeutectic and Hypereutectic alloys

A Pb-Sn alloy with the original composition C0 of 19% to 61.9% is called a hypo-eutectic alloy. A Pb-Sn alloy with a composition C0 of 61.9% to 97.5% Sn is called a hyper-eutectic. During the solidification process the liquid melt nucleates first a homogeneous phase: the -phase in the hypoeutectic, and a -phase for the hyper-eutectic composition. In the final phase of the solidification process a residual amount of liquid solidifies in the eutectic composition and structure (e.g. lamellar or fibrous). Eutectic microconstituents surround the homogeneous solid phase. The homogeneous -phase (or -phase) that formed first is called primary or pro-eutectic microconstituent .

More details can be found in your textbook.

Jean Koster

ASEN 2001

Introduction to Statics, Structures, and Materials

Fall 2004

Experiments: Measure and analyze the cooling curves of 6 alloys and plot the phase diagram.
Safety: Eye-protection is required for the team-member handling the iron, solder, and thermocouple. Use gloves to handle the solders. Safety lecture will be given by Walt Lund and Trudy Schwartz. Health issue: As you work with lead components you must wash your fingers after the lab.
1. Given are a soldering iron, a soldering plate, and pieces of solid wires, which are commonly known as solders. Use your thermocouple that you manufactured in the Thermolab of ASEN 2002. Use the soldering iron in a safe manner. The soldering iron can/should be used to carefully stir the melt. 2. Six experiments: Requirement is that you make (1) one sample from each of the three provided solders (two PbSn-alloys of known composition and one pure Tin solder), and (2) three samples of any chosen mixture from these 3 solders. The molten solder must form a small droplet as close as possible to spherical shape. Use a small quantity of solder, but sufficiently large to allow for temperature measurements inside the melt, without that the thermocouple touches the supporting plate. The solder drop should be about 0.5-1 in. diameter to get good readings. 3. Cooling curves. The experiments consist of melting solder to above liquidus line followed by measurements of the temperature as it solidifies. You must first determine the required starting melt temperature which guarantees that the entire volume is in the liquid phase. That temperature can be taken from the phase diagram for known compositions (add 20K to be safe). The phase diagram gives you guidance for choosing the starting temperature when not knowing the composition (what temperature is that?). The soldering iron must be removed from the melt drop before useful measurements start. The thermocouple must be wetted by the melt and placed in the middle of the drop (an oxide layer may develop on the surface); avoid touching the plate with your thermocouple (heat losses = false measurements)! Elaborate on the requirement for thermal conductivity of the support plate, and the position of the thermocouple within the melt. Three (3) soldering wires of known composition are given to you. Cut pieces of about 5-6 inches for safe handling during melting. Label each piece with its composition. For the 3 mixtures of unknown composition you mix your choice of materials. You must stir the melt first to get a homogenous melt, either with the thermocouple or with the soldering iron. The solder iron needs to heat the melt continuously (slow stirring and continuous contact is recommended) and the thermocouple (TC) has to be introduced inside the droplet. Wetting of the thermocouple may be limited due to dirt on the iron and an oxide layer may form on the drop that prevents the TC to penetrate inside the drop. It is critical to get the TC wetted by the melt. A good way to do that is to heat the TC at the iron and slide it into the melt. The melt drop must have high temperature above the liquidus temperature. The iron must be removed before the actual cooling curve

Jean Koster

ASEN 2001

Introduction to Statics, Structures, and Materials

Fall 2004

data acquisition is started. Do not disturb the melt when your cooling curve is measured! During measurements keep the thermocouple still (no stirring/wiggling) in the middle of the drop; do not touch the plate. The team needs to assign tasks to each team member. One person heats the melt, one person does data acquisition, others need to be supportive. The person who controls the data acquisition and the person who controls the melt have to communicate well to give the signal to start data acquisition. As the person with the soldering iron can not observe the data acquisition, the person at the console has to lead the experiment. From computerized data acquisition plot the temperature as a function of cooling time, called the cooling curves. Evaluate the cooling curves and describe your experimental findings. Measure the liquidus and solidus temperatures from the cooling curves. How large is the freezing range? For unknown initial compositions determine the composition from the phase diagram. How does that value compare to your predictions? Assess what temperature range is required to communicate the underlying physics to the reader; unnecessary data may be deleted from plots. This experiment allows you also to calibrate your thermocouple as we have two invariant reactions at different temperature level. Calibration of thermocouples is always a requirement. Choose two solders that exhibit the required thermodynamic characteristic that allows you to get a calibration for all your measured temperatures. You must use this calibration for your Matlab plots. Mix solder from different samples (leftovers from previous experiments) to make your required 3 own alloy compositions. The composition may be calculated from the mass of the alloying samples; ITLL has a scale with 10 mg resolution. Stir the liquid solder with the thermocouple or soldering iron to get a well-mixed melt. Measure the cooling curve. Determine the composition of your mystery mix from the phase diagram based on the melting and solidification characteristics, i.e. determine liquidus and solidus for each solder mix. Make sure the melt is well above liquidus of the given composition before starting the experiment: what is the safest start-temperature to perform a melting experiment with a PbSn alloy of unknown composition? Describe your visual observations. Observe the consistency of the melt itself and the surface as it freezes. Discuss those observations. Plot all your measurements of transformation temperatures into the PbSn phase diagram. You can download the PbSn phase diagram from the web. Matlab assignment: Plot cooling curves in Matlab. You must show programming efforts (see Deliverables); using canned functions is not acceptable. Think about format of best visual presentation of results. a) Process: a. Take external Labview output files and read into Matlab b. Plot cooling curves in Matlab on a single graph c. Check using Excel results b) Deliverables: a. Single Matlab plot of all cooling curves b. Code (well commented) 6

Jean Koster

ASEN 2001

Introduction to Statics, Structures, and Materials

Fall 2004

c)

c. References (from where skills learned) Notes: a. The TAs will NOT help in any way; a written reference must be provided on where the student learned how to do it. b. The code must be commented in precise technical language. c. Students MUST use Matlab to read in an external file using codes such as read, xlsread, or load. The data must not be cut-and-pasted into code.

4. 5.

Minimum references are textbook and the lab-handout. You are encouraged to introduce other references. Conclusion: Describe your conclusion of the experimental results, what you learned about metallic alloys that is important to the aerospace system engineer.

NOTE: You can contaminate the melt with solder from the previous experiment that is attached either to the iron, plate, or the thermocouple: have a clean iron and clean thermocouple. Do not melt any plastic insulation from the thermocouple wires! Do not introduce dirt particles from the board into the melt. Clean the iron with the sponge; keep the sponge wet and do not burn the sponge. Lab management: Clean the solder iron and the ceramic plates before returning it to the TAs!

Evaluated outcomes: O1: Professional context and expectations O4: Written, graphic communication perspective O5: Knowledge of key scientific /engineering issues O6: Ability to define and conduct experiments O7: Ability to learn independently, find information O8: Ability to work in teams Reportstyle: According to the guidelines posted on the web. Style: compare JOM (Journal of Materials), or Advanced Materials & Processes, which you find in the Engineering Library.

Submit: One (1) individual report per each team member. Data must be shared. Each team member submits also one team evaluation form.

Note:
Figures are taken from textbook: D.R.Askeland, The Science and Engineering of Materials, PWS

Jean Koster

ASEN 2001

Introduction to Statics, Structures, and Materials

Fall 2004

Team Member Evaluation Form:

Return on due-date to the TAs.

Experimental Lab #2 - Phase diagram Lab Section: Your Name: AM PM Group Number: __________

Evaluate contributions of each team member (not yourself) on a 1(poor) to 5 (excellent) basis. Criteria can be along the Evaluation Outcomes from page 8. Team Members: _________________________________ _________________________________ _________________________________ _________________________________ _________________________________ _________________________________ _________________________________ Additional Comments on team work: Score: __________ Score: __________ Score: __________ Score: __________ Score: __________ Score: __________ Score: __________

Jean Koster