MatE 310 Laboratory Manual

Fall 2011 Edition

Dr. Loren A. Jacobson, Instructor

The labs provided in this book will be the basis for MatE 310, Fall 2011.
Details on specific labs will be provided in class. It is recommended that
students carefully read the labs prior to class and complete any suggested
preparatory work before attending class such as looking up ASTM
standards, calculating molecular weights of compounds, and reviewing
MatE 202/235 lessons.

I am grateful to Prof. Deidre Hirschfeld for having developed this laboratory
course, and for her assistance in preparing this updated manual.
The following persons assisted with the development of these labs:
MatE 310 Students Fall 2009, G. Bahun, P. Dickens, Prof. J. McCoy, and Dr.
B. Roy.

Table of Contents
1 Introduction to Processing and Microstructure................................................................................3

2 Laboratory Safety...............................................................................................................................4

3 Laboratory Notebook Basics.............................................................................................................5

4 Plotting..............................................................................................................................................16

5 Summary and Conclusions..............................................................................................................18
5.1 PAPER #1 ......................................................................................................................................20

6 Ceramics ...........................................................................................................................................25
6.1 CERAMICS LAB #1 – CERAMIC SYNTHESIS AND SINTERING MULLITE (3AL2O3 ·2SIO2)...........................25
6.2 CASTING OF CERAMICS......................................................................................................................39

7 Metals................................................................................................................................................43
7.1 PROCESSING AND MICROSTRUCTURE OF METALS ................................................................................43
7.2 CASTING OF METALS.........................................................................................................................43
7.3 COLD WORK, RECOVERY, RECRYSTALLIZATION, AND GRAIN GROWTH......................................................47
7.4 HARDENABILITY OF STEEL USING THE JOMINY BAR................................................................................52
7.5 WELDING OF STEEL..........................................................................................................................54

8 Polymers............................................................................................................................................61
8.1 EXTRUSION AND HOT PRESSING OF POLYMERS......................................................................................61
8.2 POLYMER PHASE DIAGRAMS AND IDENTIFICATION..................................................................................63

9 Composites.........................................................................................................................................75
9.1 POLYMER MATRIX COMPOSITES ........................................................................................................75
9.2 METAL MATRIX COMPOSITES.............................................................................................................76

10 Lab Reports.....................................................................................................................................77


1 Introduction to Processing and Microstructure
Materials Engineering and Science is based on the interrelationship between Processing,
Properties, and Structure of Materials. All items used in daily life including bed, bath, kitchen, vehicles,
office/work/lab, and entertainment equipment are made out of materials. It is our discipline that
provides the know-how to produce these items in a cost effective manner that meets the performance
requirements. The discipline of Materials Engineering and Science is often described by the Structure-
Processing-Properties diagram shown in Figure 1. The structure of materials is examined on all scales:
atomic, cluster or nanometer, micro, macro, and device/component. By manipulating structure at the
appropriate scale through processing techniques, the performance of a material for a particular
application is obtained. Materials selection and performance from synthesis/extraction to
recycling/disposal is a result of the synergism between structure-processing-properties. All courses
within the Materials Engineering curriculum address aspects of this interrelationship.



Properties Processing
Figure 1. Material performance is a result of the Structure-Processing-Properties interrelationship: the
fundamental basis of Materials Engineering and Science.

The Materials Engineering curriculum has a three course sequence that provides basic
knowledge of structure-properties-processing: MatE 310, 311 and 410. MatE 310 examines the
structure-processing interaction. Different techniques will be used to synthesize and form ceramics,
process metals, form polymers, and make composites. The processed materials will be examined using
optical microscopy primarily, but also scanning electron microscopy, x-ray diffraction, and other
techniques. Samples made in this class will be used in MatE 311 Thermal and Mechanical Properties. In
MatE 311 students will see how the structure and processing of materials are related to thermal and
mechanical properties. The third course in the series, MatE 410 Characterization will provide a more
complete understanding of electron microscopy, x-ray diffraction, and other analytical techniques that
are utilized to evaluate materials.
In MatE 310, it is expected that students discuss how processing and structure are related in


2 Laboratory Safety
For this class, students are required to wear long pants, closed toe
shoes (no sandals or Teva type shoes with openings, flip flops, open shoes,
or bare feet), and safety glasses with side shields during laboratory
sessions. Other personal protection equipment will be provided. Specific
safety issues related to each lab is included in the lab descriptions and will
be discussed prior to beginning each lab. Students are required to provide
their own safety glasses with side shields.
In this lab, students will be working with concentrated acids, high
temperature furnaces, hot plates, liquid metals, saws, grinders, and
electrical power.
The main rule is that if any action or event appears to be unsafe, stop
and seek assistance from the instructor and/or TA before proceeding. It is
better to question rather than have an accident.
All students are required to have passed the departmental safety quiz
and be familiar with all Department and University Safety Procedures and
Students are encouraged to read and apply information supplied in
the Metallographic Lab Safety Section of the Buehler Summet Booklet. This
will be provided in electronic form to all students in MATE 310.


(9) list of laboratory partners. and questions about results. (8) Comments that include conclusions. This will establish who invented it and when. understand what experiments you have done. and gain insight into your project. etc. Someone should be able to use your notebook to reproduce your experiments. sources of materials. It is recommended that plots or trends in data be sketched as the experiment is being conducted to assist with interpretation and as a check on the results. the names/location of digital files containing raw data used to generate plots. For this course. Lab Notebook #1 5 . It can help you remember what happened. and problems that arose. This includes data collected by others that will be used in the final lab report. it is essential that students document the following as all these components are important in writing lab reports: (1) what the experiment was. never erasing or removing anything instead cross out errors in a manner such that the incorrect information can still be read. One student even made a table of contents at the front of the lab books so that others could find pages referring to different parts of the experiments. 20% Data Analysis including plots. (6) data collected. Rules for maintaining a laboratory notebook include signing and dating every page (sometimes the supervisor must also sign and date). and more. pictures.3 Laboratory Notebook Basics A Laboratory Notebook is essential to a practicing engineer or scientist. (5) observations. with whom you spoke. calculations. or other information can be attached to the notebook to supplement the written information. This will allow decisions to be made about issues such as if equipment was working properly and if the proper procedure was followed. For example. micrographs. notations on physical changes in the materials during processing. deviations from laboratory manual descriptions. A notebook must be kept for several reasons. This information will help those who are either continuing your work or confirming your work. 20% Observations and Comments. and conclusions drawn. (1) Patent Issues: Signed and dated pages will become legal documentation that your invention was created at a particular time and place. A good laboratory notebook simplifies the task of communicating results. copies or originals of any communication with suppliers or collaborators were attached to pages. (3) what materials were used. meetings. and (10) legibility and neatness. Both students kept track of all materials purchased including lot number and date of manufacture. ALL data must be recorded in the notebook including units. information gathered from other sources such as conversations or technical journal articles. (2) what equipment was used. This means that you make notes in your notebook on a DAILY BASIS and not once a week or once every few weeks. 20% Data Collection. and anything else that will help in writing a laboratory report. (3) how much of each material was used. (3) Documentation of your efforts: This is proof of what work you actually did which is critical for your performance reviews. It does take additional time to keep a good lab notebook but the benefits are well worth it in time saved later. comments and thoughts concerning the experiments. Example #1 has a lot of raw data with good plotting procedures and included comments. mistakes and corrections made. (4) brief description of the experiment conducted. It is good to make note of ideas. Two examples of good laboratory notebooks are provided. concerns. then you should print them out and include in your notebook and/or provide the name of the file and its location so the data may be retrieved. what you did. (7) appropriate plots and calculations. providing complete information including units. thoughts concerning your experiments in your notebook. writing reports and making presentations. and micrographs.. and other information that you record daily may determine the outcome of a lawsuit. photos. questions. If the data are recorded digitally. Comments on the data and experiments will help produce good laboratory reports. (2) Legal Issues: Notes on conversations. Computer generated plots and raw data. experiments.e. Laboratory Notebook Grading: 20% Neatness and Legible. 20% Experimental Description. Example #2 shows how to properly show mistakes and track procedures. contact information. It is important that you maintain your records over time so that you have a history of keeping track of events as this will give your notes more credibility. measurements. Neither is perfect but they demonstrate the level of detail required. i.

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7 .Plot of data attached to previous page using double sided tape.

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Note that the previous pages were reduced in size to save space. 9 . They are actually from a larger notebook.Figure Attached to previous page with double sided tape over top of sketched figure.

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Laboratory Notebook #2 13 .

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2. According to E. Tic marks should be at numbers suitable for the application (2. Tufte has developed these principles: “1. 4. Almost always involves several dimensions 5. R.0.0.scribd.html You can also use the plotting capability of R – an open source statistical package. Kalidegraph is available in the Dept.37. 2. and efficiency 3. Show the data 2. Computer 3. Get the viewer to focus on the substance of the graph and not on how the graph was developed 3. Use appropriate whole numbers for tic marks along axes and suitable range to convey the information. Tufte in The Visual Display of Quantitative Information.” For graphical excellence. Graphics Press. 1983.. Distance (m). Load (ft- lbs). All of you were taught how to plot using MATLAB and/or Excel in ES 110/111.87. 3. Encourage comparisons of data 5. You can also use spreadsheets by following one of many tutorials available on the web such as: EXCEL: http://www. 16 . More Suggestions for Plots 1. 2. It is required that students create plots of data which are meaningful and easy to interpret.4 Plotting An important skill required of all engineers and scientists is the ability to make plots that communicate information.37. the basic features of a proper graph should: “1. Serve a clear purpose 6. Be integrated with the statistical and verbal description of the graph in the text.5. precision. 3. Descriptive name and UNITS for each axis label are required. A well designed presentation of data that provides substance. Cheshire. Requires telling the truth about the data” Applying these concepts will insure that graphs and plots will communicate the information clearly. Gives the viewer the largest number of ideas in the shortest time with the least ink. function-Plotting-a-graph-Adding-Error-Bars OPEN OFFICE: http://www. statistics. CT.5) and not unusual numbers such as 2. Avoid distortion 4. and design 2. You can use any plotting package to create graphs. Communicates complex ideas with clarity.tutorialsforopenoffice.

The plot must include a legend identifying unique symbols/lines. Journal of Quality Technology. 147-152. polished. All plots. If you do fit a line. 17 .2 Lines should not connect the data points on a graph unless it is appropriate. sketches. All figures and tables must be referred to by number and described in the text. more details are required such as alloy and information about heat treatment. then prepared for metallography.” It should be noted that figure captions should not include detailed information that belongs in the text. This issue will be discussed in more detail in Senior Design or statistics classes. graphs. An improved caption would be: “Figure 1 Grain size of A153 increases with annealing temperature.” 8. 2. Only utilize trend lines if it is appropriate for interpretation. Trend lines should not be automatically drawn through data points that appear linear or to fit a particular polynomial function. an inappropriate caption would be: Figure 1 Grain Size of A153 increases with annealing temperature. "Leverage and regression through the origin. 37. Unfortunately. A caption which states something like: “Figure 1 Plot of grain size as a function of temperature” is not informative. you should do a proper statistical analysis as any set of data can be fit with a polynomial such that the R 2 is very close to 1.3. If there are multiple data sets on one plot. 56. Fitting lines implies that there is a mathematical relationship between the points. 9. It is improper from a statistical perspective to fit lines and provide a coefficient of correlation (R2) for lines going through the origin. If a legend is not included then there must be suitable identifiers on the plot. and others type of graphics are referred to as Figures and numbered sequentially within a report. the line fit becomes meaningless when using a many termed polynomial and is not applicable to additional real data that may be collected. charts. 4. 5. The figure captions must be descriptive such that the figure can convey information without reading a lot of text.1. 6. Casella (1983). For example. diagrams. the symbols and/or lines identifying the different points must be clearly delineated. in this case. Figures have numbered captions. They were then quenched in water using steel tongs. 1 G." American Statistician. Hahn (1977).J. drawings. Samples were annealed for one hour in a Lindberg Model XYZ furnace in air atmosphere. Try to keep the plots as simple as possible to clearly illustrate the concept presented. 7. Samples were annealed for 1 h at each temperature. 2 G. It is strongly recommended to use symbols and lines that allow the plot to be reproduced in black and white. Tables have numbered headings. The samples were cut from bars supplied by LMNOP Corp.

often including specific information. tensile strength. and what those results mean. if an experiment was conducted to determine the effects of Cu.7 185 245 Fe 0-0. Summaries provide a brief description of important results of data. details of any sort) helps with interpretation. etc. However. and how these observations related to modulus and strength are not included. For example. Table 1 Effect of Alloys on the Strength of Metal X Alloy Addition Amount Alloy Elastic Yield Strength Ultimate (% by weight) Modulus (MPa) Tensile (GPa) Strength (MPa) Metal X 0 16.15-0. are the grain sizes different in each micrograph.15-0. often making a table of experimental conditions with observations for each response (measurements.25 17. One technique that helps to clarify what the results of an experiment are is to put literally ALL the results out on a table and make comparisons. All data collected must be evaluated in terms of the experimental parameters.4 116 134 To summarize the presented data.25 17. chemistries.25 16. For example.6 155 178 Al 0-0. It is noted that the data provided in Table 1 are the averages of several tests with 95% confidence intervals of 2.9 180 230 Al 0. whether or not the alloy elements were interstitials/substitutional. is the Young's modulus. The data collected are listed in Table 1.1 17. analytical results. This includes micrographs. do the grains have a particular shape or aspect ratio.% elongation.5 Summary and Conclusions It requires practice analyzing data to learn how to summarize data and draw conclusions. For simplicity. the following statements can be made: 18 .1 16.9 115 129 Cu 0-0. trends. anything that was done over the course of the study period.5 120 130 Cu 0. quantities. or yield strength appropriate? To help formalize the results.1 15. observations. if these observations were available. the question WHY? must be answered.8 113 128 Fe 0. Al. Students have difficulty summarizing data collected from their experiments. Then look for differences and similarities in great detail even if the property was not the main focus of the experiment. and Fe additions on the strength of Metal X were determined. then the minor as well as major differences and similarities noted. the details about on microstructure. they would be included in the summary and conclusions. Conclusions are a listing of what was learned and are more broad in scope.0 GPa for Elastic Moduli and 5 MPa for the strengths. and finally.15-0.

Cu. 3. The paper deals with zinc diffusion in alpha brass. With Al additions of 0.25% did not improve the modulus.15-0. one example is provided for practice.Metal X has an elastic modulus of approximately 17GPa.1% have a YS of 180 GPa and UTS of 230 GPa. YS. Cu additions of 0. and ultimate tensile strength (UTS) of 129 MPa. or Fe do not affect the elastic modulus. experimental procedure.25% increase the YS to 155 MPa and the UTS to 178 MPa. or UTS The strength values for the Fe additions ranged from 113-116 GPa for YS and 128-134 GPa for UTS. double spaced. easy-to-read font with suitable margins. 19 . once all of the homeworks have been turned in.15 - 0. You are to write up the conclusions you would draw from this work. Points will be deducted for typos. Al additions significantly increased the YS and nearly doubled the UTS of Metal X HOMEWORK ASSIGNMENT To gain practice at analyzing data and drawing conclusions. 2. Al additions of up to 0. Fe alloy additions did not affect the YS and UTS of Metal X. Cu. Alloy additions of Al. The conclusions that are drawn from this study are: 1. Fe additions up to 0.25% the maximum YS and UTS are achieved of 185 and 245 GPa respectively. and has introduction. Copper additions of 0. 4. Al additions increase both the YS and UTS. and Fe did not affect the elastic modulus of Metal X.25% of Al. The alloy additions up to 0. and discussion sections. grammatical errors and mis-spelled words. Your homework should be in the form of a typed narrative report (not an outline or bulleted list). yield strength (YS)of 115 MPa. Cu additions of 0- 0.1% do not have a significant effect on the strength as compared to the base alloy.15% or greater increased the YS and UTS. There will be a classroom period devoted to the discussion of this paper. results.

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Tetra Ethyl Ortho Silicate [TEOS] (Si(OC2H5)4) or Tetra Methyl Ortho Silicate [TMOS] (Si(OC2H3)4) or other compounds. It is strongly recommended that students utilize these references in preparing their labs. Starting powders have a significant effect on processing techniques as well as final properties.S.. mullite pellets will be formed by using: Commercial powder (Mulcoa). Silica (SiO2). and sintering will be observed. density. measure density. Usually ceramic powders are first sized. 1978. examine ceramic microstructures. they will learn to dry press. The student will also learn about working with furnaces and acids in a safe manner. density. the microstructure and microhardness of the pellets will be examined. The student will also know about milling. The density of the pellets will be determined in both the green and sintered state. Powders formed by sol gel and combustion synthesis will have very small particle sizes as compared to the commercial or solid state reactants. and measure hardness of the sintered body. and Combustion synthesis of aluminum nitrate with fumed silica. The size of the powders used to make the pellets will be determined. microstructure. Reed. e. chemical solution. and/or Kaolinite (Al2Si2O5(OH)4). Wiley. Solid state reaction from Alumina (Al2O3). the press and sinter process. Finally. Kyanite (Al2SiO5). 2nd Edition.g. Once the ceramic powders are prepared. After firing. strong ceramic. The relationships between powder processing method. and combustion synthesis techniques. and other thermo-mechanical properties such as hardness. The classic textbook for ceramics is Kingery. then a polymeric binder is added to provide sufficient strength (green strength) to the as pressed body (green body) allowing handling prior to firing. Wiley.6 Ceramics 6. 1995. In this lab. Bowen and Uhlman. They will learn how to measure particle size and techniques used to characterize the resulting powders. Principles of Ceramics Processing. Experiment 25 . oxidizing atmospheres. and the preparation of ceramic micrographs. Introduction to Ceramics. or TMOS. Mullite is the focus of this lab because of its importance as a cost effective. Sol gel synthesis using Aluminum Nitrate (Al(NO3)3). and then sintered. use binders. INTRODUCTION There are many ways to process ceramics for use as engineering materials. the ceramic must be characterized. This is expected to have a significant effect on the sintering and final properties of the formed ceramic body. It is currently being used in a wide variety of applications as both a monolithic and matrix for composites in high temperature. they will be mixed with a binder using mortar & pestle. This lab will acquaint the student with several synthesis techniques. 2nd Edition. sinter. particle size and distribution.1 Ceramics Lab #1 – Ceramic Synthesis and Sintering Mullite (3Al2O3 ·2SiO2) GOALS : Students will know how to synthesize ceramics using solid state reaction. A classic reference for the processing of ceramics is: J. TEOS. pressed into pellets.

pp.. For particles greater than about 40 microns. Wiley. NIST. usually water. 2001 26 . many images are required to insure adequate statistics. This applies not only to ceramics but also to metal and polymer powders. To adequately quantify particle size distribution using microscopy techniques. the angle broadens. For this technique. Powder particles are described based on their shape. After shaking. Laser scattering techniques are based on evaluating the light pattern formed by dispersed particles passing trough a collimated light beam4 By analyzing the resulting pattern. large spheres scatter primarily in a forward direction and as the size gets smaller. 3 Sedimentation techniques rely on the application of the Stokes Equation which assumes spherical particles and laminar flow. dry sieving is used. cubic. base. Lum. size. and absorption. a small amount of an acid. selecting a different binder. powder is placed onto a stack of sieves having successively finer meshes that are vibrated. Powder Characterization Before utilizing a powder. To keep the particles suspended in the liquid. H. The morphology is readily apparent as acicular (needle-like particles) with high aspect ratios (length to diameter ratio) are obviously different from spherical. NIST Recommended Practice Guide: Particle Size Characterization. 1995. For finer particle sizes down to approximately 2 microns. the powder left within each sieve is weighed to provide a size distribution. Coordinate any experimental changes you would like to examine with the instructor.SP 960-1. Most often techniques for opaque powders utilize diffraction methods which occur at the surface of the individual particles. Diffraction can be considered to occur due the differences in the path length of the light waves interating with individual particles. The laser light can be scattered by four different mechanisms: diffraction. refraction. Students are required to follow all safety guidelines and use appropriate personal protective equipment. or block-like particles. information about size and particle distribution of the powder can be obtained. Automated systems use centrifuging to speed settling times and lasers to monitor the number of particles at a given height. Particle shape is quickly determined using microscopy techniques. varying pressing parameters. wet sieving is accomplished using a suction to pull the liquid and the small suspended particles through the meshes. reflection. 2nd Edition. knowledge of its characteristics will have an impact on how the powder is processed to produce a component. and distribution of sizes.. The basic lab procedure is described but modifications to the process may be made such as milling time or type.S. Most instruments utilize some 3 J. Another common technique for classifying size distribution is sieving. Reed. There are many techniques3 available for characterization of powders and the more important will be briefly described. S. J.92-117 4 Jillvenkatesa. The size of the falling particles is related to the time required for settling to a specific height. Dapkunas. Simplistically. Commercial units utilize a dilute suspension and monitor the fraction of particles that have settled to a specific height or the fraction of particles at a specific depth. These differences cause interference to create characteristic diffraction waves that are scattered in different directions. L. using a different sintering temperature or time. or other experiments. This will allow groups to compare the effects of various processing parameters. A. The direction of scatter is a result of the size and shape. Principles of Ceramics Processing. or surfactant is added.

each lab group will be provided with Alumina. Particle size distribution plots are then constructed. The chemical analysis of the powders will be provided.2 Solid State Reaction Each lab group will be given approximately 8 g of commercial mullite powder (Mulcoa). however. solvents. Calcination should be carried out at 800-1000°C for 1-4 h depending on batch size. place powder in top sieve with largest mesh. mix thoroughly by milling (commercial) or using a mortar & pestle (laboratory). then calcined and ground by milling or mortar & pestle. Table 12 (located at end of section 4. Both approaches are based on detailed mathematical solutions to the scattering of incident light first formulated by Mie (and also Lorenz) for cases when the particle size is about the same as or slightly smaller than the wavelength of the incident light. PSA (Particle size analysis): A Beckman-Coulter LS 13320 particle size analyzer which uses a laser light scattering technique will be used to measure the size distribution of the commercial powder at EMRTC. Binders are added to provide good green strength for handling.combination of Fraunhofer diffractions for forward scattered light when particle size is much larger than the wavelength of incident light and Rayleigh calculations for particles smaller than the wavelength. calcine to drive off moisture. is to determine the batch composition of raw materials. After milling the powders will be dried and ground again using a mortar & pestle. Processing of Solid State Reaction Samples 1. these additives limit the maximum temperature at which the component can be utilized. press. then sinter. Silica. Each lab group will be assigned a different set of raw materials from which to make mullite. To use the sieve sizer. Weigh out appropriate amounts of raw materials to make mullite (3Al2O3·2SiO2 ). For additional details. weigh the components. as was done in MATE 235. and gases. 27 . each sieve below should have a finer mesh. The Mie theory has been extended to describedifferent shaped particles and aspect ratios as well as the refractive index of the material being analyzed.1)summarizes the different techniques of evaluating particle size distribution. it is recommended that the NIST Special Publication 960-1 on Particle Size Characterization be consulted. The stack is closed then placed in the vibrator and shaken for approximately 15 minutes allowing the powder to distribute. For many ceramic materials. Powder characterization – Sieve Sizing: The commercial powder will be sized using a sieve sizer and the physical characteristics of the powder noted. blend with binder. Each lab group will have a different supply of raw materials. and/or Kaolin to make 6 g of mullite (3Al2O3 ·2SiO2). 2. Kyanite. The powders are to be ground and mixed in a plastic jar with alumina grinding media and deionized (DI) water and milled for 8 hours or blended using mortar & pestle using a small amount of either alcohol or acetone as a fluidizer. sintering aids such as low melting point glasses are added to enhance densification. The typical procedure for solid state reaction processing. Physical characteristics of the powder should be noted and samples saved for optical/electron microscopic evaluation after calcining. The powder in each sieve is carefully removed then weighed. In addition.

The first reference to synthesis of ceramics using sol gel techniques was in 1846 by Ebelmen5 Almost a hundred years passed before the research by Blodgett in 19356. 1007(1935) 7 R. 3-4 g of powder are placed in the die lubricated with cooking spray and pressed at 15. 3.7 followed by thin silica film coatings by Geffcken and Berger during World War II5. Scherer. 1990 6 K. Brinker and G. In addition. Sol Gel Science . 7. Powder characterization – Milled powder is next sized using sieves and/or the Coulter particle size analyzer. . Fundamental Principles of Sol-Gel Technology.000 psi. or solvent extraction. . lead to lower sintering temperature and time which can be a significant cost advantage. methylcellulose (Methocel) is dissolved in a small amount of water. There should be about equal volumes of grinding media and powder with enough deionized/distilled water to cover balls and powder. Firing – A heating scheduled must be determined. 4. very fine grain. acetone. Chemical Solution Techniques or Sol Gel Synthesis The formation of pure. Chem Soc. Blogett. 1989 28 . After the powders are dry. Milling – The calcined powder will be placed in a plastic jar with alumina grinding media and milled for 8 hours. The production of very fine grained powders. The basic process involves the formation of a stable dispersion 5 C. Am. It should be noted that chemical solution techniques are often generically called sol-gel synthesis. Alternatively. or alcohol then blended with the powder. spinning. New York. the powders may be blended using mortar and pestle using a small amount of alcohol or acetone. often nanometers in diameter. Academic Press. Alternatively. See Sintering section for details. Binders will be provided in lab. these techniques have been the subject of much research and are widely used in a variety of industries from coating mirrors to electronics. Solution methods were largely forgotten until the late 1950's when automotive glass mirrors were coated with (TiO2-SiO2-TiO2) in large volume. or spraying and the formation of hollow spheres and even ultra low density xerogels. If Polyvinly butyl (PVB) is used first dissolve it in a small amount of acetone before adding to powder. These general chemical solution techniques for producing inorganic materials have been given the generic name of sol gel synthesis. Physical characteristics of powder should be noted and samples saved for optical/electron microscopic evaluation. 5. Jones. London. The students must examine the appropriate phase diagram and decide what sintering schedule to use during the second lab session. A second pellet of similar size should be made with the remainder of the milled powder. solvent evaporation. In the late '60's. 6. Lab groups will be assigned different milling and calcining parameters for comparison with the class. Dry Pressing – Blend using mortar and pestle approximately 6 g of milled powder with 2 wt% binder. The same should be done with the powders made by other techniques. highly reactive ceramics utilizing chemical solution techniques are well known and can categorized as precipitation. some material should be saved for x-ray diffraction analysis. the technology had begun to mature with the development of a variety of coating methods by dipping. Because the reactions occur on an atomic level often at low temperatures in very short times. Institute of Metals. for 2-3 minutes per instructions. 57. Green Density – Each group must approximate the green density of their pellets (measure dimensions and weigh) and note physical characteristics.

The control of the process is dependent on complex chemistry that begins with formation of the sol. powders synthesized by this method sinter to full density at low temperatures. a sol which is then transformed to a 3D polymeric network or colloid (gel) by additives or aging. silica can be sintered at temperatures as low as 1000°C. In the most general form. This hydrolyzed form is then reduced to an oxide by removal of the alcohol and water through controlled drying. if hydrolysis is too rapid. i. Other ions present in the solution may alter the growth rate and morphology by adsorbing on particular surfaces. The classic reference for sol gel processing is the text by Brinker and Scherer. R is an alkyl group. Also. the precipitation reaction begins with hydrolysis which generates a hydroxide or hydrated oxide which will precipitate in the form of a gel or coagulated into particles.e. If ions are similar in size and have similar chemical properties. The precipitation of the ceramic occurs by nucleation and growth processes resulting in particles that are very fine grained. mixing rate. Other factors that may control the form of the ceramic are the temperature. The general procedure for sol gel synthesis beging with a metalorganic compound.. oxalates. Si(OC2H5)4 where R=C2H5 . Precipitation techniques3 often utilize classic wet chemistry to cause an inorganic salt that is in solution to form an insoluble precipitate by chemical means or changes in temperature or pressure. and other salts may be used as precursors. then precipitation will result rather than gelation. small pore structure and with acid. Academic Press. Sol-Gel Science: The Physics and Chemistry of Sol-Gel Processing. A knowledge of the physical chemistry of colloids is essential for a complete understanding the process which is beyond the scope of this laboratory. then drying and firing the gel to form a ceramic composition. and the method used to precipitate the colloid or form a gel. The molecular form of the gel depends on the pH of the solution determining whether long polymeric chains or colloidal agglomerates are formed. usually nanometers in diameter. 1990. the powders produced are 29 . There are a number of different hydrolysis reactions that may occur: Si(OR)4 + H2O  Si(OH)(OR)3 + C2H5OH or Si(OR)4 + 2H2O  Si(OH)2(OR)2 + 2C2H5OH or Si(OR)4 + 3H2O  Si(OH)3(OR)1 + 3C2H5OH or Si(OR)4 + 4H2O  Si(OH)4 + 4C2H5OH Then by removal of water and alcohol the result is silica Si(OH)3(OR)3  SiO2 + H2O + C2H5OH To elucidate the effect of pH. nitrates. The gel can be dried under vacuum to form xerogels or other framework structures (aerogels and zeolites) or may be used in the gel form for processes such as gel-casting. San Diego. citrates. coprecipitation of a solid solution may result. Because of the small particle size. and concentration. silica catalyzed with acid yields a high surface area. By controlling the process parameters a variety of particle morphologies may be achieved.of fine solids in a liquid. It should be noted that in addition to hydroxides and alkoxides.7 The first step is hydrolysis followed by condensation whereby water is introduced using either a acid or base catalyst. As an example. often an alkoxide of the form M(OR)n where M is the metal ion. CA. the type of solvent. consider the formation of silica from TEOS. For example. Again the conditions are critical. and n is the valence of the metal. a denser gel with large pores and low surface area as shown in Figure 1.

and xray diffraction performed before pressing into pellets. The dried gel must next be ground then given to the Lab Assistant for particle size analysis. 30 . Use a plastic pipette to very slowly (drop by drop continually stirring and pausing after every few drops) add HF per instructions of the TA. mix stoichiometric amounts of Aluminum Nitrate (Al(NO3)3) and TEOS or TMOS to yield ~6 g of mullite. The gel should be dried overnight in a drying oven. If the solution has not yet gelled. NOTE: PLEASE FOLLOW OF ALL SAFETY RULES DEALING WITH HF! Note the volume of precursor liquids and gel formed as well as the physical properties during the process. Si(OR) OH. heat the stirring solution to 100-150°C while adding HF. After calcining. A small amount of the dried gel should be examined using microscopy. The liquids are to be continually stirred in a beaker using a stirring hot plate then titrated with HF until a gel forms. again note physical properties. Effect of Processing on Gel Properties adapted from Jones7 For this experiment. The aluminum nitrate is extremely hygroscopic thus must be weighed immediately before use and cannot be allowed to sit around! The amounts will be added to 30 ml ethyl alcohol and 6 ml DI(deionized) water. A maximum of approximately 15 ml 50% HF is required. The solution should gel within 10-15 minutes. Because of the extremely small grain size.amorphous. If it does not appear to be gelling. examined using microscopy. particle size determined. Follow directions for Solid State Reaction Method to characterize powders and press pellets starting from Step 3. xray diffraction. the samples will have to be ground again. the powder will sinter at lower temperatures for very short times. calcining is required to crystallize the ceramic and also to remove any organic species remaining.Catalyst H+ Catalyst HYDROLYSIS High Rate High Rate POLYCONDENSATION Of Condensation of Hydrolysis Rapid Slow DRYING Gelation Gelation Low Density Gel High Density Gel Dried Gel Large Pores Small Pores Low Surface Area High Surface Area Figure 1. and calcining. stop and get assistance from the instructor.

70. i. When producing steel. This welding process is cost effective and easy to do even in remote areas. The commercial application of combustion synthesis has been slow9. a chemist. even at temperatures colder than room temperature and produce oxide powder. In this case. Over the years many other materials were formed by combustion synthesis or similar processes such as borides. refractory. and nitrides.Combustion Synthesis Combustion Synthesis is a process for producing ceramics. And the beautiful colors produced by fireworks are the result of exothermic reactions as different combinations of metals oxidize. 240-243(1991) 9 J. catch fire. Near net shape components (parts produced that require little or no machining before implementation) have been produced using Self-propagating High temperature Synthesis (SHS). A sparkler is used to ignite the charge in the crucible causing an exothermic reaction that lasts for about 30 seconds and generates temperatures over 2200˚C after which molten steel flows into the gap and partially melts the rail ends then solidifies forming a continuous piece of rail. carbides. zirconium and hafnium metal sheet was sliced into filaments which were encapsulated in glass with metal electrodes connected to the camera. the rail ends are first cleaned and a sand mold placed around the gap between the rails to contain the weld metal. Progress in Materials Science. Shape memory alloys for medical applications and heat-resistant. 243-273(1995) 31 . The SHS technique utilizes reactant powders that are pressed into an appropriate shape then ignited to produce the finished 8 V. To weld rails as they are being installed.Feng. “Combustion Synthesis of Advanced Materials:Part I Reaction Parameters. Dr.. This process is still used primarily for welding large structural sections and railroad rails. As the camera shutter was opened. One example of a sustained exothermic reaction are the sparklers that kids of all ages play with during July 4th celebrations. found that he could produce a variety of metals and alloys by mixing the metal oxides with aluminum metal then igniting them and using the resulting exothermic reaction of aluminum and oxygen to both reduce the metal oxides and provide the heat necessary to melt the metals. iron oxide. Hans Goldschmidt. Ceramic Bulletin. ceramic- composites. 39. Primary industrial production has been in the formation of carbides for polishing and honing. and intermetallic compounds that is economical and simple as compared to conventional processing. and wear-resistant materials are also produced by this process.Moore and H. The rail ends are preheated then a crucible containing the exothermic charge is placed above the gap.J. is the Goldschmidt8 or Thermite process for welding. aluminum metal. Hlavacek. Another significant application of combustion synthesis.e. Conventional processes for producing high purity ceramics and intermetallics require days or weeks to clean and process raw materials to usable forms followed by reactions to combine the materials to achieve the proper chemistry. and other alloying elements are mixed to form a charge that when ignited will produce liquid steel. This very same concept was used to make the flash bulbs that photographers used in the 1950's through the 1970's. He noticed that zirconium metal could be ignited. One of the first descriptions of combustion synthesis was reported by Berzelius8 in 1825.J. a spark was discharged in the bulb igniting the metals causing a bright light sufficient for good photos. The process of combustion synthesis involves an exothermic reaction of reactant materials that produces a pure product. In the late 1880's.

the combustion reaction may proceed quickly producing high temperatures throughout the body affecting performance of the component. “Combustion Synthesis and Properties of Fine Particle Fluorescent Aluminous Oxides. The temperature of the reactants will also affect the product. hot plates. or fumed silica plus carbohyrdazide (CH6N4O ) or glycine ( C2H5NO2) as a fuel. Ignition methods also have a major effect.2] 6-12 (1990).A.. Komarneni. J. If the powders are large. The combustion reaction may start from a small point or a large area. and shape all have a significant effect on the combustion reaction and products.” J. L. and G. Am. Kingsley. 13 [22] 179-189 (1990). Ravindranathan.25 CO2 (g) +22. Patil. N. Kingsley. Mater. Pederson. D. and K. McKittrick. Small Particle Size Luminescent Oxides Using an Optimized Combustion Process. Shea. In the late 1980's. A. liquid. Manickam. 13 P. D. the desired product may not be formed or the reaction may be slow. Lopez. 369-371 (1993). 12. Lett.E..12] 427-432 (1988). 6 [11. C. 10 [1. Obviously. Roy. 15 L. Powder size. G. Sci. Patil. 79 [3] 63-67 (March 2000) 11 J. J. the wet chemical process of combustion synthesis was developed to allow for good mixing of components yielding a high purity product. Pederson. Maupin. This method exploits an exothermic redox reaction by which an aqueous precursor solution of metal nitrates (oxidizers) and carbonaceous fuels (reducing agents) react at low temperatures to instantaneously produce homogeneous. and R. and O. Kiminami.13and metal nitrate-glycine14.” Am. “Microwave Synthesis of Alumina Powders.” Bull. how the combustion reaction is ignited. lasers. Sci. or gas. density. Exarhos. J. and K. K.part. Bull. they may react very quickly or form a different compound than if they are near room temperature. M.. If the powders are small.” Mat. R. 17 L. and D.12. Metal nitrate-carbohydrazide combustion synthesis has also been used successfully to produce oxide ceramics16 and high emission intensity phosphors for flat panel displays17. and how it proceeds through the part to completion. C. Chick. 32 . 87. Soc.C. Thomas. E. “Synthesis of Lithium Aluminate.” J. 4 [5] 603-615 (1994). E. Bates. ovens. Lett. “Glycine- Nitrate Combustion Synthesis of Oxide Ceramic Powders. Stat. 79 [12] 3257-3265 (1996). This process requires control of how the powders are manufactured. “Glycine-nitrate Synthesis of a Ceramic-Metal Composite.G. Patil. Clark. Folz.15 precursors were among the earlier examples of the process. C. L. multicomponent oxide powders and ceramic-metal composites.. Combustion synthesis using metal nitrate-urea11 . the combustion reaction will be affected by whether the reactants are solid. “Synthesis of Red-Emitting. or microwaves10. G. Mater. The reaction can be started by torches. For this laaboratory. If some of the powders are near their melting point. R. Morelli. TMOS. how powders are mixed and shaped.5 N2 (g) or glycine + fumed silica 6 Al(NO3)3 (oxidizer) + 10 C2H5NO2 (fuel) + 2SiO2(fumed)  2SiO23Al2O3 (s) + 34 H2O (g) + 20 CO2 (g) + 14 N2 (g) 10 R.25 CH6N4O (fuel) + 2SiO2 (fumed) 2SiO23Al2O3 (s) + 33. “A Novel Combustion Process for theSynthesis of Fine Particle alpha- Alumina and Related Oxide Materials. Ceram. J. Mullite. Sol. sparks.R.H. Maupin. 435-442 (1990).75 H2O (g) + 11.” Mater.A. Chem. Suresh. 12 J. fuses. Ceram. A. 16 J. and Coloured Zirconia by a Combustion Process. 14 L. Lett. The chemical reaction for this process can be one of the following: 6Al(NO3)3 (oxidizer) + 11. J. J. and L. combustion synthesis is used to produce a nanoscale mullite using aluminum nitrate and silica as either TEOS. “Combustion Synthesis of Fine-Particle Rare Earth Orthoaluminates and Yttrium Aluminum Garnet. Chick. Kingsley and K. crystalline. D. L.” Nanostructured Materials..” J. S.

Note the change in temperature of the new compound. Sintering The sintering of ceramics usually occurs at temperatures of ½ to 2/3 the melting point which causes atomic diffusion for solid state sintering or difusion with viscous flow for liquid phase sintering or chemical reactions to bond powder particles together. The TA will use xray diffraction to determine if mullite powder. The adiabatic flame temperature of the reaction is over 1900˚C. While mixing the hygroscopic species will absorb water creating a clear viscous liquid. Before sintering begins. dehydrates. The heating rate must be slow enough to allow the organics and moisture to burn off without leaving any residues. Follow directions for the Solid State Reaction Method to characterize powders and press pellets starting from Step 3. sintering must be carefully controlled. furnace atmosphere. The nature of the gases produced depends on the type of fuel and the oxidizer/fuel ratio. fluffy foam powders that occupy the entire volume of the reaction container. During sintering the grain size and shape changes. A large volume of brown gases. All of these processes depend on the heating rate. sulfates or other species must be removed by a pre-sintering step to avoid the formation of cracks and pores or distortion of the ceramic body. and structure of the ceramic. use stoichiometric amounts by weight. Some powder should be saved for microscopic examination of morphology and particle size. cover the beaker with a screen then place in a furnace or on a hot plate set a 300˚C or higher. After the beaker cools. The mixture then ignites vigorously after several minutes depending on water content. including traces of ammonia. There is a proper procedure for calculating the fuel to oxidizer ratio which takes into account all the components but for simplicity. any moisture. A flame is produced in areas of the decomposed reactants and proceeds around the container until all of the precursor materials are consumed. organic additives such as binders and carbonates. The amounts of each compound should be based on stoichiometry for the appropriate reaction. The as-synthesized products are typically voluminous. Flame duration depends on fuel content. Why does this happen? After the liquid become uniform and gels. pore shape changes. may be generated in the combustion reaction if the fuel to oxidizer ratio is not 1 and the reaction is incomplete. The compounds should be combined and mixed with a spatula in a beaker (250 or 500 ml) . It is preferred to use a furnace as more uniform heating of the precursors is achieved than using a hot plate but one does not get to see the reaction.or carbohydrazide + TEOS 6 Al(NO3)3 (oxidizer) + 5 CH6N4O (fuel) + 2 Si(OC2H5)4  2SiO23Al2O3 (s) + 45 H2O (g) + 21 CO2 (g) + 19 N2 (g) The aluminum nitrate is extremely hygroscopic and will adsorb moisture from the atmosphere thus one should not waste time in weighing it out and should react it immediately after weighing. The solution of oxidizer and fuel boils. To achieve the desired properties. The main driving force for sintering or densification is the reduction in surface energy and lowering of the surface free energy by eliminating soild-vapor interfaces. There must be sufficient open 33 . and decomposes. the reaction products should be ground with mortar and pestle prior to adding binder and sintering. NOTE: Assume at least 9 H2Os are attached to the aluminum nitrate when calculating the amount required for the reaction. the amount of water contained in the aluminum nitrate could be determined by heating to a temperature sufficient to remove all the moisture. If time were available. and pore size decreases.

and grains will begin to grow. shape. the water may not be removed until temperatures as high as 700˚C. and packing of the particles plus the presence of additives has a major effect on this stage. These stages are illustrated in Figure 2. the pellets can be characterized by (1) density. The largest pores which are about the size of the grains will shrink very slowly. The first stage (initial or necking) is when there is neck growth between two touching particles. The smaller pores shrink or disappear completely and may contain furnace atmosphere. In the case of liquid phase sintering. There is often adsorbed moisture and attached water to oxides that must also be driven off if the powder was not properly calcined prior to sintering.porosity in the body to allow the burned gases to leave. Depending on the size of the body. and (4) xray diffraction. The density is determined using ASTM C-20 which is based on Archimedes's principle. (3) microhardness using Vicker's indentation. Characterization After sintering. the average pore size will decrease significantly.5-1 h. The second or intermediate stage has pores shrinking and grains growing. The main mechanism is surface diffusion and evaporation- condensation by sublimation and vapor transport to surfaces having a lower vapor pressures. If there are hydrated species. a small amount of low melting temperature phase. This state is usually avoided as there is a reduction in mechanical strength and other properties. often a glass. The surfaces of the particles become smooth and any interconnected regions become rounded. Most polymeric binders burn off by 500˚C thus a slow heating rate ( <5˚C per minute) should be used to this temperature then held for an appropriate time (minimum 0. slower heating rates may be used omitting the holds at intermediate temperatures. The last step is to ramp to the sintering temperature at a faster rate and hold for a suitable time to allow densification to occur. hold for 0. The transport mechanisms will include grain boundary and lattice diffusion in addition to surface diffusion mechanism. A typical sintering schedule would go from room temperature to 300˚C at 3- 5˚C/minute then hold for 0. is blended with the ceramic particles then heated to a temperature at which the second phase flows binding the ceramic particles together. There is no shrinkage of the body during the initial stage. The solid state sintering of ceramic bodies has three stages.5 h) to allow all organics and moisture to burn off. This allows for relatively low temperature processing but the effect on properties must be considered. also. (2) microstructure using both optical and scanning electron microscopy.5-1h . The size. The overall size of the body will begin to decrease in volume as surfaces are minimized. Thus the sintering cannot be done in a one step heating process but must be tailored to the binder used and knowledge of the ceramic. It is 34 . There is an additional stage when the ceramic is over sintered and exaggerated grain growth occurs and the large pores remain large and the pores within the large grains do not shrink much. The sintering temperature for mullite in this lab may be determined by examining the phase diagram provided in Figure 3. then ramp to the sintering temperature at 5˚C per minute and hold for the specified time 2-8 h then ramp down at 5-10˚C per minute to room temperature. Grains will grow and maximum densification will be achieved. The size of the pellets and location in the furnace must also be considered in determining the sintering time. The final stage of sintering results in closed porosity and high densities. Pores intersecting grain boundaries will shrink. the holding times will vary appropriate to the size. continue ramping at the same rate to 600˚C.

grain growth. pores disappear18 Figure 3.recommended to use a modification of the standard test omitting the 24 h soak in boiling water. 183. The microstructure is evaluated by ceramography which is basically the same procedure used for metallography in MATE 202 and microhardness measurements which was also done in MATE 202.gif 19 I. and (d) Final Stage – densification. 69(1974) 35 . Pore Shrinkage and Grain Growth. (b) Initial Stage – Necking. (c) Intermediate Stage – Shrinkage. Alumina – Silica Phase Diagram19 18 http://www. a b c d Figure 2 Stages of Sintering (a) Packed Particles. Askay and Pask.azom.

Ceramography is accomplished by attaching the pellets to a bolt or other piece of metal using a thermoset plastic (Crystal Bond) to attach them prior to polishing using standard procedures for metals: begin with large grit to smaller sizes. USE EXTREME CAUTION WHEN USING HF and follow all safety procedures! If the pellet does not have sufficient strength to withstand polishing. Xray diffraction will show what ceramics are present and if mullite did indeed form in the final pellet. Polish to 0. either thermal etching or acid etching can be used.03 m or smallest size provided until a mirror finish is achieved. Characterize the microstructure noting the grain size. It is beyond the scope of this course but the crack lengths around an indent has been used to estimate the fracture toughness of ceramics. What procedure yields the most or purest mullite? Why? What is the microstructure and how does it relate to the beginning powder? Why? Was there a difference in grain size and/or structure? Explain. EVALUATION AND CONCLUSIONS After completion of this lab. grain morphology. These are a beginning but there are other conclusions that may be drawn depending on the experiments conducted. The Vickers' Microhardness can be determined and any cracks that form from the diamond points can be examined for how they grow: through the grains or around grains. 36 . What procedure yielded the densest mullite? Was there any relationship between green density and fired density? Why? What stage of sintering was achieved for each powder and why? What procedure yielded the hardest mullite? Why? To help you interpret the data collected in this lab. An example is provided in Table 2 to help you get started. then the fracture surfaces of the pellet can be observed using scanning electron microscopy. there will be sufficient data available for you to draw conclusions about the production of mullite from a variety of raw materials and their relationship to the resulting microstructure and properties. it is recommended that a master table of all results be created. To assist with the lab report. Physical properties of the pellets should be noted and comparisons made between the different starting materials. some questions that should be discussed are listed. Additional columns or rows may be added as appropriate. the samples can be etched using HF acid by either spreading the HF (50%) on the surface using a cotton swab or setting the sample surface side down in a shallow pan containing the acid for several minutes. rotating the sample to avoid “comet” formation. Clean pellet and hands thoroughly between each grit size.The density of the sintered pellets should be compared to the estimated green density and the theoretical density of mullite. Alternatively. To observe the grain structure. Thermal etching is accomplished by heating the sample rapidly to about 100C below the sintering temperature and holding for 10 -45 minutes to allow diffusion from the grain boundaries. and presence of grain boundary phases.

37 .

38 .

Critical to the process of slip casting is the properties of the slurry which will be examined in detail in MATE 311. The liquid is preferably water for health and safety reasons as well as cost but may also be an organic solvent like toluene or alcohol. liquid. adjusting pH. improve consistency. a slurry or slip (fine clay solids suspended in a liquid usually water) is poured into a porous mold often made of Plaster of Paris (gypsum: hydrated calcium sulphate) which then absorbs liquid from the slurry by capillary suction. The rheology of slips can be modified by changing solids loading. Theoretical aspects may be discussed in MATE 301 and additional reference material may be found in Reed. Surfactants alter the surface charge on the particles thus cause the particles to be hydrophobic or hydrophilic which also affects how they interact with the other additives and the liquid.6. Coagulants control how the particles agglomerate whether into clumps. It is evident that all the additives interact with each 39 . and binders to improve the green strength. A variety of additives are used to stabilize the slip. This causes the solid particles to be deposited on the mold walls forming a cast. casting.2 Casting of Ceramics GOALS: Student will become familiar with forming ceramics by both slip and tape casting. and additives. citrates) to reduce settling. and using additives.g. Slips are made of ceramic powders. Typical surfactants include a variety of stearates.. removal from the mold. They will make a plaster mold then cast a ceramic and examine the resulting microstructure. sodium silicate. and how cracks interact with phases in the ceramics. allow it to have a reasonable storage life. Deflocculants produce particle charging hence the interaction with the liquid by altering the pH of the liquid with acids/bases or with other additions (e. Typical aqueous additives which usually total no more than a 1-3% by weight include deflocculants which alter the surface charge on the particles. If a slip is allowed to sit even overnight. Principles of Ceramics Processing3 and in the technical literature. Briefly. methyl cellulose. hardness. or open frameworks. After further drying. drying in the mold. surfactants that produce a lyophobic surface that can alter coagulation. not only may the ceramic particles settle to the bottom of the container but ions may dissolve from the ceramic or additives altering the overall chemistry and properties of the slip. Slips are also subject to aging. then measuring the resulting viscosity and settling height. sulfates and chlorides. trimming and finishing the cast. Typical coagulants include ions added as oxides or amines. which affect final properties of the body. phenols. The students will make a tape cast a ceramic to which particles/fibers have been added making a ceramic matrix composite. polyacrylates. The main steps in the casting process are preparation of the slurry. and firing the body to sinter the ceramics. PVB. coagulants that control how particles agglomerate. INTRODUCTION Slip casting3 is one of the most cost effective processes of forming ceramic objects having complex shapes. and provide good green strength. acrylics). The solids loading and rheology will determine the casting rate and density. changes with time and temperature. Students will examine the microstructure. stacked like cards. the cast must exhibit sufficient green strength to be removed from the mold then fired to form a finished product. Binders are usually polymers that provide good mechanical strength to the body before firing and are the same as used for pressing pellets (PVA.

chemical reaction with the liquid.  is the viscosity of the liquid moved. If a kaolin slip is fully coagulated. the effect on slip and hence cast properties can be dramatic.g. To insure good casts. air bubbles may be trapped in the cast. e. kaolin. 3-5% by weight of ceramic is added to water or other liquid along with additives then mixed thoroughly and allowed to settle. These charged surfaces attract ions or additives in the liquid altering the surface chemistry. slips can be readily developed for new materials by characterizing the surface charge using settling experiments or zeta potential measurements (measure of surface charge on particles). Plaster molds1 for slip casting normally have 40-50% porosity with micron sized open pores for drawing out the liquid by capillary suction. are 40 . slips for common ceramics are well developed and with experience. plasticizers. (2) the deposited ceramic. flexible green sheets. J is the volume cast/volume liquid removed.5 L is the cast thickness. Because ceramic powders1 typically have high surface area and low solubility in liquids. however. Tape casting3 is similar to slip casting but contains up to 50% additives by volume to produce thin. pressure may be applied to the cast or vacuum drawn through the mold. P is the apparent mold suction. Rc is the inverse of the permeability of the cast. their behavior in liquids is controlled by surface chemistry. the slip is usually de- aerated before casting.other making the development of a good slip a complicated process. The settling behavior is monitored as a function of time noting how much settles and how much stays suspended in the liquid (cloudy). the alkali ions are desorped and go into solution leaving negative charges on the plate faces and positive charges on the edges. Typically the thickness of the cast forms by filtration of the liquid through (1) the mold. The particle surface can become charged by desorption of ions from the surface. In addition to the additives for slips. however. For this lab. Casting thickness as a function of casting time can be approximated by : L= (2JPt/ Rc)0. then the mold will become the rate limiting factor. If kaolin is mixed in water. Kaolinite. Drying is critical as well because if it is too fast the drying shrinkage will cause the cast to crack and/or warp. The cast must have sufficient strength to withstand drying stresses and forces associated with removal from the mold. become charged by desorption of alkali ions. This behavior is readily characterized using settling experiments which is used for determining the effects of additives on slips. To speed up casting. Clays . such as PEG – polyethylene glycol or PPG polypropylene glycol. The viscosity of the slip can be decreased by heating but temperature may dramatically affect surface charges. and t is the time. has potassium or other alkali ions adsorbed on the surface for charge neutrality. Casting times can vary depending on the thickness of the component being manufactured. If the aggregates are stacked these cations are adsorbed on the interfaces between crystallites which are plate-like in kaolin weakly bonding the plates together. a discussion of kaolin surface charge is helpful. it is assumed that the liquid transport through the cast is rate limiting. For this equation. This charge controls the slip properties as discussed previously. J becomes higher with higher solids loading in the slip. the mineral. there will be a dense stack of plates with the smaller particles remaining suspended in the liquid. if it is fully deflocculated. the plates will settle quickly and form a “house of cards” or porous cast. otherwise. Because kaolin had different charges on the faces and edges. and/or by adsorption of ions or additives from the liquid. Conditions yielding minimum settling height are usually desired for casting. If a mold is reused several times and/or not fully dry before casting.

funnel. Tapes can also be stacked then fired to make electronic packages. Drying is often done in a controlled manner as capillary forces transport the liquid out of the tape through the thickness. There has been a trend in the last 20 years to use aqueous slurries for health and environmental reasons. For detailed information on tape casting. almost 2-D shape the tapes are often stacked and topped with plates to achieve uniform heating. Slip Casting Each lab group will be given plaster of paris and forms (paper cups) for making at least finger 3 molds (test tubes) plus one other mold of a simple shape such as a crucible. Once the target time is reached the slip should be poured out of the mold. The green tapes are removed from the substrate then cut to size. The next day remove the plaster casts from the forms and place them in a drying oven for 24 h. ~ 50 v% solvent. non-aqueous liquids were used extensively. Schematic of a tape casting machine1 EXPERIMENT 1. 35 v% organics. Three molds should be used to determine the cast thickness as a 41 .forming a film on a substrate which is either plastic or glass.added to give the tape flexibility. After the molds are fully dry. Plaster forms are made by mixing plaster to water in a ratio of 7:10 by weight then allowing them to dry over night. American Ceramic Society. the classic reference is by Mistler and Twiname. Do not heat molds above 50°C to maintain strength. Westerville. Because of the flat. Tapes are formed by having the slurry flow beneath a knife edge called a doctor blade. It is common for the dried tapes to be about half the doctor blade height. Dried tapes are about 60 v% ceramic. or other object. A typical tape caster is shown in Figure 1. The tapes can be screen printed with ceramic inks. Figure 1. and 20 v% additives. OH. and 15 v% porosity. Mix thoroughly by putting 1 or 2 alumina balls in plastic jar with the slip in the wrist shaker for 5 minutes then measure pH. The pH of the slip should be adjusted to between 8 and 8. When tape casting was first developed in the 1950's. then carefully drying the tape. When the slips are fully mixed. Mix the slurry using the wrist shaker then remove the alumina balls. Slurries are usually about 30v % ceramic powder. 2000. Tape drying and subsequent firing must be strictly controlled to insure a defect free product. slips can be made using Kaolin with ~15 wt% solids in deionized water and about 2% by weight of solids binder (Methocel or PVA).5 using acid (HCl or HNO3) or base (NaOH or NH4OH). Sintering of the dried tapes or electronic packages requires a long time to fully burn out the organics and then sinter to full density. fill the mold with slurry and keep filling for a specified time. Tape Casting: Theory and Practice.

are there any defects such as crow's foot cracks. Examine the as cast green body. Determine the microhardness for various phases. platelets. longitudinal cracks or other defects? After drying at low temperatures. 42 . Tape cast samples must be fired more slowly with extra hold time and lower heating rates until the binders and plasticizers are burned out. Examine microstructure of resulting tape in different directions with respect to casting process. Further dry the green cast overnight in drying oven then fire the next day. Once the relationship between cast thickness and time is established.function of time to help determine an optimum casting time for the slip. Stack several cast plates and weigh them down during firing to prevent curvature due to drying stresses. the casts with or without molds can be placed in a drying oven for 8 h or more. After drying. If additional drying is needed. Note if there was any cracking or defects and wall thickness if a hollow body was made. Tape cast the slurry by slowly drawing the doctor blade set for 0. 2. Allow to dry overnight in air covered with a damp paper towel. Examine microstructure. Tape Casting Form a tape casting slurry by mixing 50w% kaolin with in deionized water with approximately 3w% PVA binder and 6w% PEG relative to the slurry. microhardness for various phases. The next day. Adjust pH to appx. It is recommended that an alumina plate be placed on top of the green tape. Remove from mold when dry. note any defects in the body. orange peel (rough surface). 8. Fill mold with slip then pour off excess slurry leaving a suitable wall thickness. and how cracks emanating from Vicker's indents interact with phases.5 mm thickness across a mylar film. Ball mill thoroughly. have the defects changed? After firing. It is suggested that one of cast finger molds also be fired for microstructural analysis. When dry to touch. add whiskers. Allow the green body to dry overnight or longer. or other composite filler to the slurry. another cast should be made with the 4th mold. If desired. Note how the tape forms.5. place in a drying oven to completely dry before firing. the cast should be removed from the molds and thickness measured. After firing. and how cracks emanating from Vicker's indents interact with phases. Suggested firing is to heat slowly to 300 C hold for about an hour then heat to 600 C hold for an hour then heat to 1500 C hold for at least 8 hours to get significant growth of mullite then cool to room temperature.

7 Metals 7. the grains will be elongated parallel to the rod axis in the direction of the extrusion. or other metallic component along with sections mounted for metallographic examination.2 Casting of Metals Goal: Students will gain an understanding of the effects of casting parameters on the microstructure of solidified metals. screw. Hot working vs. The macrostructure along with the microstructure should provide evidence of how the component was made. nail. and rolling affect the microstructure. Students will have an understanding of how common fastners and other metal components are manufactured. chill zone. This is illustrated in Figure 43 .1 Processing and Microstructure of Metals GOAL: Students will observe how processing methods such as forging. very thin region of deformation along edges. columnar structure. Upsetting. Subsequent processing and properties are influenced by this initial step thus knowledge of how metals solidify is very important to a materials engineer. For example. EVALUATION AND CONCLUSIONS Describe how you think the particular component was manufactured based on the evidence indicated in the microstructure. cold working will affect the overall microstructure. if a metal rod is extruded. extrusion. 7. upsetting. Introduction Casting is the first step in the production of many metal components. Utilizing knowledge of MATE 202 and MATE 235 plus other resources. and types of shrinkage porosity. There will likely be a thin region around the circumfrence of the rod with smaller distorted grains due to the friction forces along the die wall. Students will know how cooling rate is related to secondary dendrite arm spacing. The nucleation and growth of solids within a liquid metal is primarily dependent on the undercooling of the liquid assuming that the latent heat and entropy of fusion do not vary much with temperature. Describe how the processing affects the microstructure. and other processes will leave evidence in the grain structure by how the grain shape and size is distorted. Students will be able to identify dendrites. rolling. Students will become familiar with the effects of composition. equiaxed grains. EXPERIMENT Manufacturing methods affect the microstructure and properties of components. each lab group will be provided with a bolt. Machining is a cutting operation and may leave burrs (thin strips of metal) or have a very. forging. The samples will require final polishing and etching with an appropriate acid to bring out the macrostructure and/or microstructure.

2d). When the liquid is cooled below the melting point many nuclei form at the mold wall. Cast Microstructure of (a) pure metal. 4th Ed. that at temperatures near the Tmp . small perturbations form in the solid surface which can then grow forming dendrites as illustrated in Figure 3. Usually. The secondary dendrite arm spacing (SDAS) is directly related to solidification rate as illustrated in Figure 4 and also. G =TSf where T (= T-Tmp ) is the undercooling. (b) solid-solution alloy. Figure 1. Only with large undercooling can homogeneous nucleation occur whereby solid nuclei of critical size can form readily without an impurity particle or solid surface. there is sufficient time for the atoms to move to preferred orientation sites forming a columnar structure (Fig. If there is localized undercooling (liquid temperature is less than the solid). Schmid. and (c)metal with a nucleating agent added 21. The transition from equiaxed chill zone to columnar structure is a direct result of the temperature gradient in the cast. 2003. Phule.). Upper Saddle River. The science and engineering of materials (4th ed. Prentice Hall. Recall from thermodyanamics. NJ. mechanical properties of castings will be studied in MatE 311.1. protuberances will not form and the interface between solid and liquid will be planar. Askland and P. With sufficient undercooling. Manufacturing Processes for Engineering Materials. Subsequent development of microstructure depends on heat transfer and presence of alloying elements. If the liquid temperature is higher than that of the solid. USA (2003) 21 S. Kalpakjian and S. solid crystals form along the mold wall as many nuclei quickly reach stability forming a chill zone. If the liquid is warmer. 44 . atoms can cluster to form nuclei but they must reach a stable critical size before growth can occur. Undercooling is the driving force for solidification as the solid phase has the lower G20 (a) (b) (c) (d) Figure 2. Thomson. and (d) temperature gradient associated with columnar and equiaxed growth20 20 D..

PWS Publishing. Illustration of SDAS22. and proper placement of runners to allow the flow of liquid metal. the classic text on solidification is B. and physical metallurgy texts such as the classic one by Reed-Hill and Abbaschian. OH 45 . Clothing worn during this lab must not be synthetic and shoes must be leather! 22 ASM Handbook. discrete. Shrinkage has a significant impact on final dimensions of cast components and on how the casting molds are designed to minimize shrinkage porosity defects. Dendrites form from protuberances which grow rapidly if the liquid is undercooled. and the relationship between SDAS and cooling rate for selected metals.20 Figure 4. or large voids depending on how the casting mold was designed. Metallography and Microstructure (1985). Vol. Wiley. Pores can be interdendritic. Care must be taken in handling liquid metal and etchants. typical dendritic microstructure in an Al alloy22. Be sure to follow all safety procedures which will be reviewed in class. MA. Unlike water. 1964. ASM International. Physical Metallurgy Principles. Techniques to reduce shrinkage voids include hot topping. most metals shrink upon solidification causing the formation of a well in the ingot. New York.20 The shape of the solidified ingot is related to how the metal shrinks as it densifies in going from liquid to solid. Principles of Solidification .Figure 3. The liquid temperature raises back to Tmp as the the latent heat of fusion is removed. placement of chills. 9. 1994. For more detailed information. Boston. which expands on solidification making ice with peaks. Materials Park. A dendrite is also shown. Chalmers. Further details on solidification are provided in introductory Materials Engineering texts such as those by Askeland & Phule 20 or Callister or other text used for MatE 202 and MatE 235. Shrinkage pores are formed when there is not sufficient liquid flowing into the solidifying cast.

Samples produced in this lab are to be saved for MatE 311 for correlation of SDAS with mechanical properties. The cast ingots will be sectioned longitudinally and all sharp edges ground. The lab report should focus on how heat transfer and composition affect the resulting microstructure. then polished using usual metallographic techniques. 356. and pure Al will be cast in both a standard graphite mold and a mold with a water cooled base also called a chill mold that will promote directional solidification. When using Keller's etch extra care must be taken and only enough etch for immediate use the lab should be made. and ingot shape. It is very important to (1) use polishing cloths that have not been contaminated with steel or ceramics. porosity. (2) rinse the sectioned ingots thoroughly with soap and water between each grit size. The chill molds will have side walls that are either graphite or ceramic. A good lab report should include a discussion of why/how the microstructure is oriented should be included. 46 . macrostructure. If required. The etch remaining after lab must be disposed of properly. Etching requires a minimum of 2 minutes possibly up to 6 minutes to delineate the microstructure.Laboratory An Aluminum casting alloy. The differences in the microstructures of the ingots will be compared. Secondary dendrite arm spacing will be measured using the line intercept method from micrographs. Each lab group will select their casting temperature/mold temperature with approval of the TA/instructor. plus other observations. Keller's etch may be used to delineate the microstructure. a correlation of SDAS with location of dendrites within an ingot and with casting parameters for different ingots. Each lab group will use different liquid metal casting temperatures and/or molds will be at different intial temperatures to show the effect of these parameters on cooling rates. and (3) wash hands thorougly between each grit size.

3 Cold Work. this increment in internal energy is associated with an increase in the dislocation density as well as the density of point defects. Grain size and ductility will similarly decrease as schematically shown in Figure 1. Figure 1 Schematic of change in strength. This usually means holding the cold worked metal at a 47 . (http://info. recovery. and electrical resistivity with the amount of cold working. the grains become markedly elongated in the direction of working and heavily distorted. strength. there is a marked increase in hardness. the dislocation density increases from the values of 106-107 lines/cm2 typical of the annealed state.html) Microstructurally. While the increased hardness and strength which results from the working operation can be important. Background A small percentage of the energy expended in plastically deforming a material remains stored in the metal as an increase in internal energy.1012 lines/cm2 after heavy Thus. and ductility with increase in cold work on a metal. This distortion is evident from a bending of annealing twins and from an unevenness in etching caused by local strain inhomogeneities. changes are produced in both its physical and mechanical properties. and grain growth on microstructure and mechanical properties of metals. and Grain Growth Goal: Effect of cold work. recrystallization. At a microstructural level. such as vacancies. Principally.farmingdale. Recovery.7. to 108-109 after a few percent deformation and up to 1011. it is often necessary to return the metal to its initial condition by annealing. Recrystallization. and interstitials. Identification and understanding of twinning in metals. grain hardness. For most metals.

The lowest temperature at which stress-free grains appear in the structure of a previously plastically deformed metal is termed the recrystallization temperature. Grain growth depends on the fact that the grain boundary energy of the material is reduced due to the decrease in grain boundary area (i. 3. internal stress and strength (or hardness) of a plastically deformed material is illustrated. The recrystallization temperature is usually 1/3-1/2 the absolute melting point of the material. Boundaries between annealed grains migrate and larger grains grow by an increase in the average grain size (or a decrease in the ASTM grain size number. This depends upon the grain size. the severity of plastic deformation. A distinctive feature of the recovery process is that it does not involve any change in the grain structure of the cold- worked metal. in Figure 2.jpg) 48 .. Small changes in hardness. Strength and hardness decrease considerably and ductility increases.e.temperature above about 1/3 of the absolute melting point for a period of time.farmingdale. schematically. if the temperature is raised) nucleation and growth of strain-free grains in the deformed matrix will take place. the only changes taking place are the dislocation arrangements within the existing grains. number of grains) for a given volume of material. tilt and/or twist low-angle boundaries). which are sometimes observed during recovery. 2. Grain Growth: If a recrystallized material is further annealed at the same temperature or at a higher temperature grain growth usually occurs. As these grains grow. Strength Hardness Ductility Grain Size Figure 2 Schematic of the effect of Annealing Temperature on Hardness. can be attributed to the decrease in the dislocation and point defect density and to the growth of the subgrains. the dislocations in the matrix are annihilated at the boundaries of the newly-formed grains. The effect of recovery. The annealing treatment is divided into three distinct regions: 1.e. Recovery: This usually occurs at low temperatures and involves motion and annihilation of point deflects as well as annihilation and rearrangement of dislocations resulting in the formation of subgrains and subgrain boundaries ( Recrystallization: If increased thermal activation is available (i. Strength. and the presence of solute atoms or second phase particles. n). Ductility and Grain size (http://info. and grain growth on grain size.

Hardness value may be calculated from the load applied divided by the surface area of the indentation. Procedures Specimen Preparation 70-30 brass stock (70% copper. However. The wedges are then annealed in an inert atmosphere at 850°C. At least three hardness measurements should be made on a smooth surface of each specimen to achieve some statistical significance. A 1/16" steel ball indenter with 100 kg load corresponds to Rockwell B scales. 30% zinc) is cut into pieces 0. You should run a hardness test on the test standard for the particular scale being used before and after each set of measurements. They are then rolled crosswise to give the following specimen. 49 . Each piece is machined to a wedge shape as shown below.5" x 0.Measurement of Hardness (ASTM E18-07) Throughout this experiment. hardness measurements will be made using a Rockwell hardness tester. the instrument you will use is calibrated to read hardness values directly.25" x 2" long.

samples may be held with rolled duct tape. recrystallization. 4. They might be slightly tarnished. If the initial strip thickness is 0. and grain growth stages if possible. On the cold-rolled sample. do not reduce thickness by more than 30%. percent reduction in thickness.125” or thinner . Plot a curve of hardness vs. It is recommended that the samples be polished-etched then polished a second time using the final one or two alumina polishes followed by etching to yield better microstructural definition. Plot curves of hardness at several equivalent places across the specimen vs. and annealed at different aging temperatures. 50 . Share the microstructures with everyone in the lab to determine the effects of annealing and identify the recovery. perform the following: 1. microstructure. 3. Each student should to take responsibility of 1-2 samples. annealing temperature Microstructural Investigation 1. Determine the ASTM grain size number for the four highest annealing temperatures' samples. Cut the specimen into four pieces about 1/2 in. and 700 oC then quench in in cold water. Examine the microstructure of the final rolled piece for comparison to the as recieved and the heat treated samples. Cut a 1/2” long piece from the strip and keep it for measuring the initial thickness. 5. 4. as there will be a gradient in amount of reduction across the specimen. and separate measurements by about 0. Cold mount samples in epoxy then polish and etch samples: as-received. long 2.125 inch. This can be done after the final rolling step. Review of Terms Understanding the following terms will aid in understanding this experiment. Be careful in handling these polished samples as they are very susceptible to scratching. 3. 600. A heat treatment used to eliminate part or all of the effects of cold working. and hardness 2. cold worked. 3. 500. Measure the hardness across each specimen after the above heat treatment using the Rockwell B scale. For the rest of the strip-reduce the thickness up to 50% by many small rolling steps. Start close to the end with the highest reduction. 2. Heat the four pieces for 30 minutes at the following temperatures: 300. perform the following: 1. As an alternative to cold mounting. Grain size determination is described in ASTM E112-96. Tighten the rolls only a small amount at each step or a safety pin will break. Annealing. which requires that they be re- polished with the smallest polishing grit size then etched again. Examine these samples with the optical microscope noting grain size and shape.On the fully-annealed strip.

or other microstructural features in a particular direction of plane in material as a result of its processing. the matrix is more difficult to define. and grain growth of the alloy should be indentified by the microstructure and hardness then related to the processing procedure. Interfacial energy. Typically the first solid material to form during cooling of an alloy. Matrix. Recrystallization temperature. causing the metal to be strengthened as its shape is changed. the number of dislocations increases. annealing temperature. ASTM grain size number (n) vs. Preferred orientation. A medium-temperature annealing heat treatment designed to eliminate all of the effects of the strain hardening produced during cold working. 4. At this temperature atomic mobility becomes high enough to allow recrystallization. Some of the plots that may be incorporated in the lab report 1. Etches for Brass. The energy associated with the boundary between two phases. and other factors. This temperature is usually one-third to one half the melting temperature (in absolute degrees K or R). inclusions. which you find relevant as well. Hardness vs. The recrystallization temperature is not a constant for a material but depends on the amount of cold work. 96 ml ethyl alcohol. 25 ml DI water. 25 ml NH4OH. Sketch or photograph of the microstructures at each of the different temperatures of annealing. the annealing time. temperature for the three highest annealing temperatures. then removed.. should be answered in the lab write up follow: How does final grain size varies/changes compared to initial grain size? What happened to the microstructure during cold working? How does hardness change during cold work and why? What is the effect of different stages of annealing on grain size/shape and hardness and why? You should discuss other topics. 10 ml 3% H2O2. However. in random order. The recovery. the matrix is continuous and a second phase precipitates from it. 2. An alignment of grains. recrystallization. Recovery. percent reduction in thickness. Hardness vs. During cold working. The temperature above which the effects of strain hardening are eliminated during annealing. Nucleation and growth of a new stress-free microstructure occurs. 51 . in some complex alloys.Cold working. Plastic deformation. 3. Deformation of a metal below the recrystallization temperature. Recrystallization. Some questions. A low-temperature annealing heat treatment designed to eliminate residual stresses introduced during deformation without reducing the strength of the cold worked material. Recrystallization must be accomplished above the recrystallization temperature.. Usually. Analysis and Conclusions The lab report should discuss the relationship between microstructure and processing. Permanent deformation of the material when a load is applied.

understand hardenability and the effects of quenching on microstructure and properties. 4340. W-1 Tool steel. Materials Required: Jominy End quench bars: O-1 Tool steel. Part 1: Jominy End Quench (ASTM A255-02) The Jominy end quench is a test used in industry to compare the relative hardenability of different steels.References 1. Elements of Materials Science and Engineering. Equipment Required: Programmable box furnace capable of 1000C operation. The Principles of Engineering Materials 3. Barrett. 1045. Rockwell C hardness tester Mounting grinding and polishing equipment Optical microscope with imaging software Procedure: This lab will consist of two exercises: the Jominy end quench test and metallography of individually quenched samples. quenching. 1095. then placing it in a fixture where a stream of water is allowed to impinge on one end of the sample. Engineering Materials and Their Applications. and hardness. Hardenability is defined as “the relative ability of a ferrous alloy to form martensite when quenched from a temperature above the upper critical temperature. Vol. In this lab. due both to its excellent properties and its low cost. SAE 1018. plus. 2. variation of the microstructure with cooling rate. Nix and Tetelman. Van Vlack. Flinn and Trojan.4 Hardenability of Steel using the Jominy Bar GOAL: Students will know the effect of heat treatment on microstructure development in steel. Concepts covered will be hardenability.” The test involves heating a steel bar (typically 1-inch diameter by 4-inches long) above the upper critical temperature. Once the sample is cool. the effects of different heat treatments on the microstructure and mechanical properties of different steels. The hardness profiles of different steels can be compared to get a relative measure of hardenability. Introduction: Steel is one of the most important materials in our modern society. 4130. Chapter 6 2. Chapter 3 7. and/or 8620. The cost-effective properties of many steels are in large part due to its ability to undergo phase and microstructural changes by heat treatment. a hardness profile is taken. Heat Treating and Cleaning of Metals 4. ASM Handbook. measuring hardness versus distance from the quenched end. 52 .

1018. hardness testing. grind. 1045. each sample then quench the sample in Jominy apparatus. and 8620. Prior to the lab. along with the hardness. After the samples have fully cooled. which should be answered in a lab report are as follows: How does the variation of the hardness along the length of the bars compare with the corresponding microstructure? How do hardness and microstructure are change with the compositions? Under what conditions is each microstructure formed? Which steels are more hardenable and why? There are other questions that can be discussed but these will help begin the analysis. wet grind a flat along the length of the sample and take a hardness profile using the Rockwell C indenter along the length of the sample. Jominy tests will be conducted on a variety of steels that may include: tool steels: O-1 or W-1. in random order. 53 . What is the cause of the formation of various microstructures? What are some issues involved in quenching. it is required to find the composition and corresponding data on heat treatment procedures for each alloy per ASTM. First austenize. The various microstructures observed should be categorized for applications. 4130. Record the distance from the quenched end for each hardness test point. 1095. and polish samples in preparation for imaging with an optical microscope. Part 2: Microstructures of quenched steels Following the Jominy hardness testing mount. 4340. and microstructural analysis of the real components? Evaluation and Conclusions: Some questions.

Manufacturing Processes for Engineering Materials. prior heat treatment. however with proper procedures and heat teratments the properties can be improved. 23 The strength of a weld is often stronger than the original metal. Schmid.and flux cored welding. It is not unusual for the heat affected zone to be the lowest strength region and subject to more severe corrosion because of grain growth. prior state of the metal (cold work). For example. Arc welding was first developed in the mid-1800's and is widely used in industry for both joining and maintenance. submerged arc. slag inclusions from the fluzes or improper shielding. The mechanical properties of welded joints depend on heat transfer. incomplete fusion where the weld bead does not fully coalesce with the base metal. These can all be avoided with proper selection of filler materials and welding parameters. and welding process parameters. know the safety procedures and hazards associated with welding. gas tungsten arc.. If a filler metal is used then the weld metal will be a mixture of the base and filler metals. will have knowledge of the basic types of welding (SMAW and GMAW). The properties of the heat affected zone depend critically on the metal chemistry. After the heat is applied and the weld pool formed. it cools following a solidification path similar to that in casting forming a small equiaxed region then a dendritic columnar region which grows parallel to the heat flow direction. 54 . composition.7. and cracking due to thermal stresses or embrittlement. NJ. depends on many factors: alloying 23 S. Prentice Hall. The weldability. The cast weld structure usually has course grains with relatively low hardness. Fillers are not required for all types of welding. A schematic of these regions is shown in Figure 1. Some of the common weld defects are porosity due to gasses that are trapped during solidification or generated by contaminants. There are many different types of welding: shielded metal arc.5 Welding of Steel GOAL: Students will understand the basic principles of welding. capacity of a metal to be welded satisfactorily to meet application requirements. The focus of this laboratory will be the welding of metals using arc welding which may or may not have consumable electrodes. a brief review of the metallurgy of welds is required. heat affected zone. 4th Ed. the base metal may undergo recrystallization and grain growth if there was sufficient cold work prior to joining. and weld quality. toughness and ductility. and base metal. 2003. gas metal arc. the joint may be preheated to reduce cooling rates. Before reviewing the techniques of welding. strength. thermal properties of the metal and filler. INTRODUCTION The joining of two materials by fusion welding is accomplished by melting together and coalescing of two materials (metals and thermoplastics) using heat as supplied by electrical or other high energy means. Kalpakjian and S. The weld metal is fully melted allowing the coalescence of the two pieces the temperature decreases going through a heat affected zone where the mircostructure of the base metal is affected then out to the original base metal which has the lowest temperature. and will understand the development of microstructure and properties of welds in steel. Upper Saddle River. A typical welded joint has three zones the fusion zone. In the heat affected zone. will learn the procedure for stick welding.

and many more. If thicker sections are to be welded then 55 . A schematic is shown in Figure 2. processing history. and high alloy steels are weldable with proper shielding to avoid oxidation. Nb. Stainless steels and Ni alloys are weldable. Figure 1. most steels are weldable except those that are galvanized or contain high carbon content. WELDING TECHNIQUES Shielded metal arc (SMAW) and gas metal arc welding (GMAW) are the focus of this SMAW19 is also called stick welding because the electrodes are stick- shaped. For sheet metal welding. Aluminum is weldable with high rates of heat input except alloys containing zinc or copper. Lastly. The electrodes are usually long thin sticks of metal coated with a flux. Mg. Cast iron may be welded. Also. The current used ranges from 50-300A with power generally less than 10kW and can be either AC or DC. Zr. the type of welding used and process parameters vary considerably. the flux coating. The heat generated melts a portion of the electrode.elements. In general. and contaminants. and the base metal which solidifies. One end of the electrode is connected to the power source and the other terminal is connected to the base metal as shown in Figure 3. AC is used for welding thick has extensive information.The following is a brief listing of the weldability of some metals19. Ti. Schematic of the fusion weld zones and temperature distribution from the weld into the base metal19 For specifications on welding for both procedures and testing. Reverse polarity where the electrode is positive is used for thicker pieces requiring deep weld penetration. the American Welding Society (http://www. The process consists of an electric arc struck between an electrode and the working piece which is moved along the piece quickly as a distance sufficient to maintain the arc. the preparation of the surfaces is very important and has a major effect on the success of the joint: presence of oxide films. The flux coating acts as a deoxidizer and provides a shielding gas. SMAW19 is the most popular form of welding used for both joining and maintenance as well as being low cost and versatile. Straight polarity DC is used where the workpiece is positive and electrode is negative for continuous heat input. SMAW is portable and low cost suitable for thicknesses from 3-19 mm. adsorbed gasses.

The arc must be an ideal length. and gas mixture and appropriate for specific welding positions. This process was formerly known as MIG welding for metal inert 56 . With SMAW the person is primarily in control whereas with GMAW. Figure 4 shows a schematic of the GMAW process. The electrode is a consumable wire fed automatically through the nozzle. Electrode Coating Solid Slag Shielding Gas Arc Figure 2 Schematic of shielded metal arc welding process24.19 the weld pool is protected by an external source of inert gas such as Ar. electrode size. the travel speed and current must also be properly set.multiple passes are required which requires the removal of the slag before the next pass is made. metals. The electrode metal is deposited in the mold by one of three methods: (a) spray transfer whereby small droplets are rapidly projected into the weld (b) globular transfer occurs with CO2 shielding where large globs of metal are transferred to the pool. and thicknesses. In order to properly make a weld using SMAW techniques. CO2 or others with deoxidiers incorporated into the electrode metal. control of the process is critical and a challenge to learn. He.lincolnelectric. To provide some insight as to how parameters affect the 24 http://www. Each of these deposition mechanisms is controlled by suitable selection of power. and ( c) short circuiting whre the metal is transferred as droplets as the electrode tip touches the weld pool. the equipment provides more control. Figure 3 Schematic of the basic equipment for SMAW or stick welding20 In gas metal arc welding.

(a) Schematic of GMAW process24 (b) Schematic of GMAW equipment23 Figure 4 Schematics of GMAW process and equipment.jpg 57 .weld.umd. Figure 5 shows good and poor welds. Figure 5 Effect of process parameters on welds.25 25 http://iaa. It should be noted that the weld should be no wider than twice the stick

you will set up the welder and metal pieces to produce a 4-6” butt weld joining two 3/8” mild steel plates. shoes. The travel speed is the speed at which the electrode moves along the base material while welding Too fast of a travel speed results in a ropey or convex weld . The electrode should be held approximately perpendicular to the top of the plates (work angle) then angled 20-30 deg along the direction of travel between the electrode and the plane (travel or lead angle) as illustrated in Figure 5 . Figure 5 Schematic of Work and Travel Angles for SMAW24 58 . They are highlighted here but will be reviewed in lab by the instructor. After striking the arc. At the end of the weld. Remove the slag using a wire brush and/or hammer before making additional passes. The SMAW process can withstand wind and exhaust near the arc from ventilation equipment. the operator breaks the arc which creates a ‘crater.Choose correct filter shades for your visor.’ Use a short pause or slight back step at the end of the weld to fill the crater. and covering to protect yourself. Wear leather or appropriately rated aprons. WELDING PROCEDURE24 You will first practice welding a bead on a steel plate under the supervision of the TA/Instructor.EXPERIMENT SAFETY When welding there are serious safety considerations that must be taken24. Arc Rays can injure eyes and skin . Use enough ventilation. Fumes and Gases can be dangerous. gloves. When you have gained adequate proficiency. Large craters can cause weld cracking. The first step is to strike an arc by either scratch starting: scratch the electrode on the base metal like a match or tap starting: tap the rod against the base metal. If the arc length becomes too long. maintain about 1/8” between the electrode and workpiece If the arc length becomes too short. Do not touch the electrode or metal parts of the electrode holder with skin or wet clothing. to keep fumes and gases from your breathing zone and the general area. Molten Metal – Wear clothing that is not synthetic to avoid burns should liquid metal splash. Electric Shock can kill – to receive a shock your body must touch the electrode and work or ground at the same time. undercut.Too slow of a travel speed results in a wide weld with an excessive metal deposit. Keep your head out of the fumes at all times. The proper procedure for restarting a weld is shown in Figure 6. spatter. or both. the electrode will get stuck to the workpiece or ‘short out’. and porosity can occur. Wear long sleeves and pants keeping your body covered to avoid a serious sun burn. exhaust at the arc. Keep dry insulation between your body and the metal being welded or ground.

1” Wide Bend Bar B A Weld C Figure 7 Schematic of samples cut from welded plates: A.1” bend bar. then etch with either nital or nitric acid to reveal the microstructure. and will supervise students as they weld. It is recommended that a series of micrographs be taken from the center of the weld to the parent metal showing the change in microstructure.Micrography along center of weld. Move Electrode to Crown of Crater 3. slice a 1” wide strip perpendicular to the weld for a bend bar test.24 CHARACTERIZATION After welding the plate and removing the slag. steel. Polish the sample after rounding sharp edges. 1. Strike Arc Here 2.The instructor/TA will provide detailed information on the electrodes. 59 . For microstructural analysis. This piece will be machined and used for an AWS bending test. cut two cross-sections: one perpendicular to the weld that extends about 5 cm into the parent metal and a second along the center of the weld about 2 cm long (Figure 7). The width of the samples should be about 5-8 cm to make polishing and microstructure analysis easy. Resume Forward Travel Figure 6. and C. suggested settings for welding. The proper way to restart a weld. B – Micrography from weld center to parent metal.

does the hardness correlate with the phases present. Be sure that the hardness indents are spaced sufficiently apart ~0. EVALUATION AND ANALYSIS The lab report should discuss the relationship between the heat transfer and microstructure. Determine the hardness of the join from the center of the weld through the heat affected zone to the base metal. compare the microstructres of the weld. Some considerations that should be made when reviewing the results: is there evidence of dendrites in the weld pool. 60 . was the microstructure affected by multiple weld passes. heat affected zone. Correlate the hardness with the phases present (microstructure) and the heat input during welding. and base metal.25”.

Cooling at the hopper end prevents softening/melting of the polymer beads. As the tube exits from the die it is cooled to below Tg or Tm to stabilize the shape and avoid deformation due to gravity and to stabilize the shape.8 Polymers 8. It has to be designed specifically for the polymer being extruded to properly mix. by forcing it through a die creating objects with constant cross section. They will be able to identify the main process parameters. tubes. the die has a circular mandrel fixed in the center of a larger circular orifice. The extruder capacity. is determined by the barrel The dimensions of the screw groove: depth and width. Vents are located along the barrel to allow gases and trapped air and gases to escape without losing the pressure being applied to the melt. Barrels may be heated or even cooled to optimize extrusion. the amount of polymer that can be processed per hour. with length:diameter ratios of 20-30:1. or polymer. Figure 1 shows a schematic of an extruder. for example twin screw extruders have two screws rotating in opposite directions at different speeds to enhance mixing of fillers. The support of the mandrel needs to be well back in the die in order to allow rehealing of the melt to avoid a weak weld along the axis . Polymers usually exhibit orientation of the polymer chains or crystallites due to 26 http://gertrude-old. About 60% of all polymers are processed by extrusion including rods. Screw design is very important to the extrusion process23. sheets. be it metal. the extruder operates at temperatures and pressures suitable to force high viscosity.1 Extrusion and Hot Pressing of Polymers GOAL: Students will learn about the extrusion and hot pressing of polymers. The temperature along the barrel increases progressively primarily due to friction between the screw and the melting polymer. Barrel diameters about a meter long for processing of thermoplastics. or polymer blends. but is more expensive. INTRODUCTION Extrusion is the shaping of a material. For the extrusion of polymers. which would plug the entrance to the barrel. For the extrusion of tubes or pipes23. pipes. high molecular weight polymers through dies. melt and compress the polymer. There are variations on extruder design. The polymer extruder23. The twin screw design usually operates at lower temperatures. Amorphous polymers continuously soften continuously through the glass transition and beyond. Typically extruders for elastomers have lower length:diameter ratios. similar to what many children do when making polymer clay Pressures on the melt can be up to 100 MPa. determine the compression ratio and usually decreases along the barrel length.26 consists of a hopper which feeds polymer granules into a long tubular barrel containing a rotating screw which creates the pressure necessary to force the polymer through the die. and profile shapes. reinforcing agents. Different screws are needed for different molecular weight polymers as well as different degrees of crystallinity. while semicrystalline polymers exhibit a sharp transition at the melting point. ceramic. filiments.21 The first reported extrusion21 was the application of rubber sheathing to metal wires in 1880. Wires were coated by pulling them through the die at the same rate as the emerging polymer.htm 61 .

. Continue feeding the polymer until the mass is created. barrel. Turn off the heaters. This process should take 15. Examine the sheet for any defects such as air bubbles or thin sections. mechanical. It will consist of several layers. Gradually apply pressure allowing the mass to melt and fill the die. Move the die plate back and forth to create an extruded mass about ¾” thick by 2” wide by 4”long at the center. Heating insures rapid and complete filling of the die. the polymer swells due to the relase of applied pressure. for non-symmetric shapes. breaker plate. Discard the first few inches extruded. Typical extrusion defects23. Cut dog bone samples using the dog bone die by placing it over the area to be cut in the hot press (at room temperture) and gradually applying up to 7000 lbs. the overall bulk material can have different properties e. and crystalinity. Extruding changes the microstructure of polymers. As the polymer comes out. raise the press. Is there evidence that the polymer chains are entangled? Is there a difference in the optical microstructure of the recycled and new polymer? 62 . Follow the same procedure to cut additonal samples. Carefully cut thin slices of polymer for optical examination using the transmission optical microscope with polarizer. solubility. Allow the mass to cool. and a variety of surface defects. Turn on the screw and set speed as instructed.g.26 are: incomplete melting. collect the strand on the hot press die. Some questions for discussion: For polyethylene and recycled bags. EVALUATION AND ANALYSIS The lab report will describe the process of extrusion and hot pressing. dog bone samples will be cut from the sheet. Stop feeding polymer and collect the remaining polymer on a metal plate. Raise press and remove die and sample. It should be noted that upon exit from the mold. degradation of the polymer due to high temperatures. the degree of entanglement. NJ) onto a plate then hot pressed into a thin sheet. depending on whether the chains are entangled and if entangled. The hot pressing of polymers is accomplished by filling a heated die with a polymer then applying sufficient pressure to form the materials. die) will alter the entanglement. The auger barrel will be preheated to 190oC while the exit die is set to o 195 C. this may cause distortions.20 minutes before the die is fully closed. The flat sheets formed can then be cut into appropriate shapes. high density polyethylene pellets and/or recycled plastic bags will be extruded using the Haake extruder (Saddle Brook. Allow the die to cool for about 1 hour then remove the polymer sheet. Save some for optical microscopy. why was the temperature for these processes set at around 190oC. a second sample will be made using a different screw speed Place the die with the mass and the top plate into the hot press that has been preheated to 195oC. and remove the die. The design of the extruder (auger or screw. EXPERIMENT For this lab. Finally. If time permits. inadequate mixing. Feed polymer into the hopper and press it into the screw gently with a dowel rod.extrusion which may yield undesirable anisotropic mechanical properties. Due to the chain structure of polymers.

For example. Modern Infrared Spectroscopy. 8.Figure 1. is composed of an electrical component and a magnetic component. when infrared radiation is incident on matter.. where h is Planck’s constant and c is the speed of light. This causes covalent bonds in the material to vibrate 28.1 FTIR For Identification of Polymers Infrared spectroscopy27 is the study of the interaction of infrared light (radiation) with matter.: Boca Raton (1996) 29 Stuart B. 28 Smith B. like other electromagnetic waves.. This correlation between wavenumbers at which a molecule absorbs infrared radiation 27 T. John Wiley & Sons.29. Fundamentals of Fourier Transform Infrared Spectroscopy. 2003. Schematic diagram of an extruder. hc Functional groups within molecules tend to absorb infrared radiation in the same wavenumber range regardless of the structure of the rest of the molecule .: West Sussex (1996) 63 .2. Backgound Information on FTIR as provided in thesis.2 Polymer Phase Diagrams and Identification GOALS: Students know how to identify polymers utilizing Hildebrand solubility parameters and FTIR(Fourier Transform Infrared Spectroscipy) Students will utilize optical microscopy to identify multiphase polymers and other structural features. Infrared radiation. New Mexico Tech MS Thesis. and carboxylic acids.23 8.C. Surface Modification of Polyimde Composites for Bond Coat Adhesion Improvement. Ltd. aldehydes. Ndalama. the C=O stretch of a carbonyl group occurs at ~1700 cm-1 in ketones. CRC Press Inc. A wavenumber. Students will know how to generate a polymer phase diagram using cloud-point measurements. W. is defined as the reciprocal of the wavelength of a light wave and is related to the energy of the wave as follows: E W . Molecular substances absorb the electrical component.

light transmitted by the beamsplitter strikes and reflects off the fixed mirror. At this point. and  is the reduced mass of the atoms involved in 2  the vibration. no matter how small or large the rest of the molecule may be. the third arm contains a moving mirror and the fourth arm is open. When the moving mirror is at an equal distance with the fixed mirror. such as the concentration of a molecule in a sample27. A molecule can only absorb radiation if the frequency of the incoming infrared radiation is equal to the frequency of the fundamental modes of vibration of the molecule. after which it strikes the detector. A. As a result. as follows: A c . which splits a beam of light into two beams and makes one of the light beams travel a different distance than the other 27.e. which is designed to transmit half of the infrared light that impinges on it and reflect the other half. Because bond stiffness and/or the reduced mass of atoms in functional groups is unique. infrared spectra can provide quantitative information. This means that the vibrational motion of a small part of the molecule is increased while the rest of the molecule is left unaffected28. The reflected light beams recombine at the beamsplitter and leave the interferometer to interact with the sample. has four arms. 1). which is used in many FTIR spectrometers. allows the identification of unknown molecules from the molecule’s infrared spectrum. the fundamental mode of vibration of each functional group falls in a specific range.and its structure. The basis of all quantitative analyses in FTIR is Beer’s law. In addition to the identification of chemical groups. At the intersection of the four arms is a beamsplitter. l At the heart of an FTIR spectrometer is an interferometer. it is said be at zero path displacement. where  is absorptivity and l is pathlength. IR Source Moving Mirror Beamsplitter IR Detector Light Sample Fixed Mirror Figure 1: Diagram of a Michelson interferometer27 64 . all light waves in the recombined beam are in phase i. The first arm holds a source of infrared light. c. A molecule can be looked upon as a system of masses joined by bonds with spring-like properties 28. Vibrational frequency for a particular degree of freedom for polyatomic molecules is given as: 1 k  . the intensity of light for every wave in the beam is high. the second arm holds a fixed mirror. and the light reflected by the beamsplitter strikes and reflects off the moving mirror. to absorbance. where k is the bond stiffness. which relates concentration. A Michelson interferometer (Fig..

. Each of the waves contains information about the wavenumber of a given infrared peak and amplitude information about the peak intensity at that wavenumber. the intensity of every infrared wave in the beam increases and decreases in a sinusoidal manner. which contains contributions of the instrument and the environment to the infrared spectrum. 247. Absorbance is related to transmittance as follows: A   log10 T There are several infrared sampling techniques that are commonly used with FTIR spectrometers which will be studied in detail in MATE 410. By increasing the number of scans. The distance that the moving mirror is moved from the zero path displacement position is termed the mirror displacement27. The major limitation with reflectance methods is that the depth to which the infrared beam penetrates into a sample is not accurately known. most of the contribution to the spectrum comes from the surface of the sample.30.1-5 mm. the Attenuated Total Reflectance (ATR) technique will be explained. The evanescent wave decays exponentially with distance from the crystal/atmosphere or crystal/sample interface. The single beam infrared spectrum is a plot of raw detector response versus wavenumber. The interferogram measured by the FTIR detector is a summation of all the sinusoidal waves in the infrared beam. By applying Fourier transformation. To generate a complete interferogram. which is called the optical path difference. A single beam spectrum obtained without a sample in the infrared beam is called a background spectrum. All reflectance techniques require special accessories that are placed into the spectrometer’s sample compartment 27. the light strikes the surface of the crystal at such an angle that the beam undergoes total internal reflection. (1997) 65 . The accessory contains mirrors. the interferograms are added together. the distance that the light striking and reflecting off the moving mirror travels is two times the mirror displacement. which improves the signal to noise ratio. which focus the infrared radiation on to the face of the crystal. thereby reducing random noise. The main component of the ATR accessory is a crystal of infrared transparent material having a high refractive index (Fig. suitable for surface analysis. 30 Gryczynski I.R. where the moving mirror is translated back and forth..” Analytical Biochemistry. Transmittance is defined as: I T . the evanescent wave penetrating the sample is attenuated by the sample’s absorbance. Because depths of penetration are typically 0. By moving the mirror at a constant velocity. Thus. A transmittance spectrum of a sample is produced when a sample single beam spectrum is ratioed against the background spectrum. 2).. when an infrared absorbent sample is brought into contact with the crystal. “Two-photon excitation by the evanescent wave from total internal reflection. and Io is the intensity Io measured with no sample in the beam. A plot of light intensity versus optical path difference is called an interferogram. based on the relationship between the wavelength of the light and the optical path difference. a scan is made. This is what makes FTIR with ATR sampling. where I is the intensity measured with a sample in the beam. The most common are Attenuated Total Reflectance and Transmission. The spectrum is a plot of transmittance (T) versus wavenumber (cm-1). 69-76. Gryczynski Z. For this lab. Therefore. A standing wave called an evanescent wave is generated around the point of internal reflection in the crystal from the summation of the incident and the internally reflected light waves 27. Lakowicz J. a single beam infrared spectrum is calculated from the summed sinusoidal waves in the interferogram27. Inside the crystal.

An example of FTIR usage is to monitor the changes in the surface of a polyimide with UV/Ozone etching26 The goal of this study was to determine the amount of etching required for maximum bond strength of a coating on a polyimide composite.087 (C-N imide) (Benzene rings) Figure 3: Molecular structure of PMR-15. The molecular structure of PMR-15 polyimide is shown in Figure 3. The effects of different surface treatments on PMR-15 make it much more reactive as indicated by the reduction in benzene markers as shown in Figure 5. (C=O imide) (Imide ring) O O O N CH 2 N N CH 2 N O O 2. An FTIR spectra of untreated PMR-I5 is shown in Figure 4 with the notable features such as benzene and imide rings identified with particular wave numbers. 100 98 Benzene ring %Transmittance C=O 96 Benzene ring Benzene ring Benzene ring Imide ring 94 Imide ring 92 C=O C-N 90 1500 1000 Wavenumbers (cm-1) 66 . Pressure Sample Evanescent wave To detector IR beam ATR crystal Figure 2: Schematic of an ATR accessory 28. showing chemical bonds relevant to the major peaks in FTIR spectrum26.

reflective microscopes used to examine metals and ceramics are used. the samples will be given to Dr.2 Optical Microscopy of Polymers Optical microscopy of polymers is accomplished primarily by using transmitted light.ibase. The crystallinity is observed due to differences in refractive index which is seen through the use of a variety of filters and changing the angle of the polarizer. optical microscopy will be used to characterize the microstructure of each polymer (Section 8. .26 100 T ran sm ittance (arbitrary units) As Received 95 90 RF Argon Plasma Etched 85 UV/Ozone Etched 80 75 RF Oxygen Plasma Etched 70 2000 1800 1600 1400 1200 1000 800 -1 W avenum ber (cm ) Figure 5. For example. These samples are put onto a microscope slide with a cover slip placed on top then examined using polarized light.nist. Note that the Benzene absorbances are significantly altered by treatments. Kalugin who will provide FTIR spectra for identification. one must know what functional groups or bond types are present. 8. Procedure and Analysis For this lab. Figure 4: FTIR spectrum of as-received PMR-15 composite. Samples are cut using a microtome to yield very thin sections of soft materials or with great care. The lab report will describe how each polymer was identified. polyethylene terephthalate (PETE) has the molecular structure and the corresponding FTIR pattern as shown in Figure 7. students will be given a variety of polymers without identification.2).jp/sdbs/cgi-bin/direct_frame_top. sometimes slices can be cut using a razor blade. In addition.2.html. polarized light will help identify differences in microstructure. FTIR Spectra of PMR-15 modified by different surface Thus when using FTIR as a tool to identify polymers or other materials.2. There are several good sources of spectra from multi-volume books of organic and some inorganic materials and on the internet at http://riodb01. Again. Some polymers are made of more than one type of 67 . For polymers that are not transparent or translucent.aist.cgi and http://webbook.

High molecular weight (MW) polymers typically do not readily dissolve. Sawyer. Figure 6. In the language of introductory chemistry. Meyers.go. Grubb. an extremely effective solvent must be used. Springer. 2008.ibase. A polymer of low molecular weight can disperse itself much more effectively. Structure and FTIR spectrum of PETE from http://riodb01.polymer. the solvent must be just “like” the 68 .2. Note those that have distinctly different phases and relate those to other characterization Additional information on the polymer microscopy can be found in texts such as: Polymer Microscopy. In order for a high MW to dissolve.cgi 8.3 Dissolution and Solubility of Polymers The dissolution of polymers depends upon physical properties as well as chemical structure. Recall from freshman chemistry that the entropy of mixing is used a as measure of the increase in disorder of the mixture as compared to the original materials before mixing. resulting in a much higher entropy of mixing than a high molecular weight polymer.aist.

However.. Each molecule of a solvent has a cohesive energy density. for a high MW polymer. In the case of a cross-linked polymer. Energy of vaporization of a solvent Dissolving an amorphous polymer in a solvent is described by the free energy of mixing1. The energy change when a solvent molecule is removed from the liquid is a measure of the energy of vaporization (Fig. such as polyacrylic acid and polyvinyl alcohol are soluble in water and other polar solvents. T = the temperature in Kelvin and m= the entropy change of mixing. It should be noted that the EVAP for the polymer cannot be directly measured because polymers typically have a low vapor pressure. Thus. V. EVAP Fig 1. the most effective solvent for a polymer is the one that best matches the EVAP/V .2 69 . and between solvent molecule and polymer monomer are assumed to be those of relatively featureless spheres. The square root of EVAP/V is known as the Hildebrand solubility parameter.1 where the change in Gibbs free energy. then that polymer will dissolve. Therefore. Eq 1. . Non-polar polymers. are soluble in nonpolar solvents. negative changes in free energy favor mixing.polymer because like dissolves like. between polymer monomer and polymer monomer. If the cohesive energy density is the same for both a polymer as for a solvent. a simple model of solution is proposed where the interactions between solvent and solvent. it will swell. In the Hildebrand approach.e. Sm is very small and the Hm term dominates. This “like” is quantified by the Hildebrand solubility parameter. stickiness. Sm is always positive because the disorder is increased by mixing and because -TS is negative. The polarity of a polymer is also important for the general principle of like dissolves like. the enthalpy change of mixing. Polar polymers. i. 1). The enthalpy term resulting from this theory is:1 Eq 1. The Hildebrand formulism does not account for strongly polar solvents and polymers. The large size of the polymer must be corrected-for by using the molar volume. it favors mixing. such as polymethyl methacrylate and polystyrene. but there are other generalized solubility parameters which do which are beyond the scope of this course. From thermodynamics. The most common way of determining this parameter by solvent matching. the like dissolves like criteria becomes the matching of EVAP/V for the polymer to that of the solvent.

The most obvious way for this to happen is for the solubility parameters of solvent and polymer to be equal (and for the Hm to be zero).4 RT S m     1 ln 1  2 ln  2  R  n  where 1 is the volume fraction of the solvent 2 is the volume fraction of the polymer.where V = volume of mixture. for each phase. and 12 is the Flory-Huggins c parameter. The  underbar indicates division by the number of solvent molecules plus the number of solvent sized repeat units in the polymer.3 Notice that the Hm from Eq.2 is always positive (favoring non-solvation). Working in the other direction. regions with the lowest free energy indicate stability and mixtures of the phases are characterized by tangent tie lines between phases. 1. the solubility parameter of a good solvent for a polymer can be used to find the solubility parameter of the polymer. the energy of vaporization of the component i. The solubility parameters for common solvents and polymers are provided on Tables 1. The cohesive energy density is defined as the energy of vaporization per cm3. It describes the attractive strength between molecules of the material. The Flory-Huggins solution theory is a model of the thermodynamics of polymer solutions which takes into account the difference in molecular sizes. Also. once the  parameter is known. 1. The Hildebrand solubility parameter is then defined as the square root of the cohesive energy density. When Gm/RT is plotted against .2. and the volume fraction of component i.1 and 1. An expression for the Gibbs free energy3 is: G m H m S m   RT RT R H m  121 2 Eq 1. the c parameter can be estimated from the Hildebrand Parameters of the polymer and solution: Eq 1. the phase diagram can be generated which shows the boundary of a miscibility gap between a complete solution and a phase separated solution.5 where Vm = the molar volume of the solvent. Within the Flory-Huggins theory.6 RT  70 . Vi = the molar volume of the component i. the  parameter can be used as a fitting function for the phase diagram using the form: A  Eq. the small Sm term must dominate over the (usually) much larger magnitude of Hm. Thus. Eq 1. The edges of these regions determined as a function of temperature become the boundaries of the two phase region on the phase diagram as shown in Figure 2. n is the number of repeat units of the polymer. In order to have the polymer dissolve in the solvent.

or photodetection. molecular weight. The basic technique for cloud-point measurement is to hold a specific composition at a specific temperature until it has reached equilibrium then observe if a phase separation has occurred as indicated by the formation of a non- transparent phase. Figure 2. Examples of polymer solution phase diagrams are provided in Fig. Schematic Diagram showing how DG for each component is used to generate a phase diagram that includes the effects of mixing. Cloud-point measurements are used to produce phase diagrams of polymer solutions. ultrasonics. pressure. and biological separations as a function of composition and temperature. Once A is known. and the thermodynamics of polymer solutions. There are many techniques used to detect when the solution become turbid or cloudy indicative of a phase separation which not only depends on temperature and composition. Hildebrand Parameters.“A” is then adjusted to best fit the phase diagram. For more information on the Flory-Huggins Theory. 3 which also shows the effect of molecular weight. the polymer solubility parameter can be found though Eqns. The experimental points were found using cloud-point measurements. The solid line was generated using a Flory- Huggins fit. Alternatively. thermal and chemical techniques may be used such as differential scanning calorimity (DSC) or changes in the solution by FTIR. but also. 1. read references 5-7. and other factors. The detection of the phase separation can be made by visual observation.5 and 1.6. 71 . wax formation in petroleum products.

Figure 3. Phase diagrams of Polystyrene-Cyclohexane solutions showing the effect of
molecular weight.4 Note that circles are cloud point measurements, triangles are
critical points, and lines were determined using Flory-Huggins calculations

Table 1.1 Hildebrand Parameters of Selected Solvents2
Substance δ (MPa1/2)

Acetone 20.2
Ammonia 33.3
Benzene 18.8
Cyclohexane 16.8
Ethanol 25.2
Hexane 21.1
Isopropanol 23.5
Methanol 17.4
Mineral Spirits 14.9
Methyl Ethyl Ketone (MEK) 14.1
Napthalene 20.3
Trichloroethylene 18.7
Toluene 18.2
Turpentine 16.6
Xylene 18.0


Table 1.2 Hildebrand Parameters for Selected Polymers2
Substance δ (MPa1/2)

Poly(methyl methacrylate) (PMMA) 17.0 – 20.7
Poly(vinyl acetate) 18.2 – 19.3
Polyethylene 16.3 – 17.9
Polystyrene 17.7 – 20.8
Polyethylene Terephthalate 19.5
Polyisoprene 16.3 – 17.8
Polyvinyl Siloxane (Silicone) 15.0 – 19.0
Polytetrafluoroethylene (PTFE) 12.7
Polypropylene 15.7 – 19.2

This lab involves a variety of organic solvents, be sure to wear appropriate personal
protective equipment: gloves, safety glasses, and long sleeved lab coat along with
standard lab clothing. Check to be sure that the gloves you are wearing are
appropriate for the solvents being used. Dispose of used solvents in appropriate
organic waste containers.
1. Several unknown polymer samples and vials filled with specific solvents
marked with the Hildebrand Parameter will be provided. The change in weight of the
polymer with time will indicate whether the samples have dissolved, swelled, or not
reacted with the solvent. Weigh each polymer sample to the nearest 0.1 mg. Place
one sample of each unknown polymer into each solvent vial. Note any immediate
change. Let the samples stand for one (1) hour in the vials, then remove, dry
completely with a paper towel to ensure an accurate reading, weigh, and record the
new weight and any qualitative changes.
After weighing, place samples back into their respective vials and let them soak
for 24-48 h as instructed, then weigh again after drying and note any qualitative
Samples that swell are indicative of cross-linked polymers. For these samples,
make a graph of the Hildebrand parameter vs. the percentage change in mass divided
by the intial mass of the sample. Use the data for the 24-48 h mass change.
For samples that dissolve, create a table of which solvents dissolved each
polymer or a graph that plots disolved/not disolved vs. Hildebrand Parameter (solvent).
Based on these data, draw conclusions about the identity of each polymer
sample. Compare to the FTIR and optical microscopy results from 8.2.1 and 8.2.2
2. Phase Diagram Generation
The entire class will work as a group to generate a phase diagram of
Polystyrene-cyclohexane. Each lab group will be given polystyrene and cyclohexane
along with glass vials and will conduct cloud-point measurements on specified
compositions. Using ice and water mixtures, the vials will be subject to a variety of
temperatures and the turbidity observed visually. Based on these data, a phase
diagram will be generated similar to those shown in Figure 3. Use the Hildebrand


Parameters from part 1 to calcualte the Flory-Huggins c parameter and compare it to
the phase diagram.

1. Brandrup, J., Immergut, E. (1989). Polymer Handbook, 3rd Edition, Wiley
2. Barton, A. (1991). CRC Handbook of Solubility Parameters and Other Cohesion
Parameters, 2nd Edition, CRC Press,
3. Flory, P. Journal of Chemical Physics. (1941) Vol 9, Issue 8, p. 660
4. Terao, K., Okumoto, M., Nakamura, Y., Norisuye, T., Teramoto, A.
Macromolecules 31, 6885 (1998).
5. Lipatov, Y. S., Nesterov, A. E. Thermodynamics of Polymer Blends, CRC Press
6. Koningsveld, R., Stockmayer, W. H., Nies, E. Polymer phase diagrams Oxford
University Press, (2001)
7. van Dijk, M. A., Wakker, A., Concepts of polymer thermodynamics (1997)CRC
Press, (1997).

Evaluation and Analysis
The lab report should include a description of how the various polymers were
identified, comparisons of the different techniques, descriptions of the microstructure
observed using optical microscopy related to possible processing methods, and a
phase diagram generated using cloud-point measurements. To help with this report,
some additional questions that should be considered include: In the tables, the
solubility parameters of the solvent are very precise while the solubility parameters of
the polymers have large uncertainties. Why? Compare the structure of polystyrene and
cyclohexane, would one expect them to be miscible or immiscible?


9 Composites
Composites provide the opportunity to specifically design a material unique
to a given application. Composites can have a polymer matrix reinforced with
particles, short fibers, or continuous fibers made of other polymers, metals, or
ceramics, a metal matrix reinforced with intermetallics or ceramics, or ceramic
matrix composites reinforced with high temperature metals, intermetallics, or
ceramics particles and fibers. Producing designer materials creates exciting
possibilities along with interesting technical challenges such as how to effectively
join two composite components or a composites to a monolithic material while
maintaining performance specifications.
Because ceramic matrix composites were addressed in section 5.2 Casting
of Ceramics, polymer matrix and metal matrix composites labs will be included

9.1 Polymer Matrix Composites
Reinforced plastics have become important materials engineered to meet
specific design requirements such as high strength-to-weight and stiffness-to-
weight ratios. Because of their structure, special methods are required to fabricate
them as was discussed in MATE 235. In this lab, fiberglass reinforced epoxy will
be laid up by hand to make a multiply composite and a graphite-epoxy composite
will be made using prepreg. Specifics will be provided by the TA or instructor.
When working with fiberglass and epoxy, be sure to wear gloves and other
appropriate protective equipment. The lay up and curing must be done in a well
ventilated area.
Fiberglass reinforced epoxy will be used to make a component plus a few
tensile testing bars. Design a small components such as a box, cylinder, boat, or
other simple shape no larger than a 20 cm cube that will be the mold positive that
will be covered with the composite. The mold will be made of foam, wood, or
other stiff material, smoothed, and coated with a wax or other release compound.
Cut pieces of fiber glass being careful to not to disturb the fiber orientation in the
pattern desired. Mix the 2 part epoxy then pour the epoxy on single ply of fiber
glass and squeegee the excess away from the center of the cloth. Make sure the
epoxy fully penetrates the fiber glass. Add additional 1-3 plies, using peel ply or
other cloths to make the edges uniform. Allow the component to cure until fully
dry. De mold and smooth any rough edges with sand paper.
For tensile coupons, lay out the fiberglass strips onto mylar or aluminum foil
the soak with epoxy, squeege, then add a second ply following the same
procedure. After the tensile coupon has cured, determine the tensile strength and
modulus. Compare results with other lab groups. Cut a portion of the composite off
and mount in epoxy, then polish and examine the microstructure. Note defects,
porosity, the degree of bonding between the epoxy and fiber glass, and the degree
to which the epoxy penetrated the fiberglass.
Squares of unidirectional graphite epoxy prepreg provided are to be laid up
with several plies per the instructions of the TA. The composite may be
unidirectional, quasi-isotropic or other combination of angles. The plies will then
be covered with scrim cloth and separating layer then hot pressed to densify and
cure the composite. Upon cooling to room temperature, note any warping of the
composite. Slices of composite are to be cut for tensile testing. In addition, a piece


polish then examine using an optical microscope to characterize the microstructure.550C for up to 1 h in an argon atmosphere.will be cut to mount.2 Metal Matrix Composites A metal matrix composite will be made using aluminum powder blended with 10% by weight alumina or other ceramic powder as instructed by the TA. After milling the blend will be uniaxially pressed in a lubricated die using the same method used for ceramics. 31 M. Rahiminan. et al. The lab report should discuss the effect of alumina on hardness. Journal of Materials Processing Technology 209 (2009) 5387–5393 76 . the samples will be polished. and microstructure of the composite. The pressed pellets will then be sintered at 500 . This lab will repeat some of the experiments originally conducted by Rahimian et al31. a pure metal pellet will also be pressed. grain growth. After sintering. and the microstructure examined. etched. 9. The powders will be blended in ethanol with several alumina balls for varying times using the wrist shaker or ball mill. Rockwell B hardness will be measured. For comparison.

References . I. results and conclusions 2. Results . materials. "Processing of Ternary Sulfide Ceramics. and Literature Review 3. Jones.Detailed account of technique. Discussion .List numerically using the following format with numbers placed in text appropriately: 1. Attached is a description of detailed requirements and suggestions for writing reports in Dr. Smart.10 Lab Reports The general format for lab reports unless otherwise instructed are: (1) Double Spaced. Font Size 10 or 12 pt. 2. Experimental Procedure . and equipment 4. May 1. Nowhere.Significance of Results. Am.List . Affiliation. Personal Communication. The lab report should have the following sections.. It is better to keep discussions simple and clear.1" on left and right (If bound in a folder use 1.5" left and 0. The reports should not be overly long nor too short. H's classes. Smith & S. Title.Clear Presentation of Data (May be combined with 5.Background Information.75". Abstract . 2009 A bibliography style list of references is not acceptable. in an easy-to-read font such as Times New Roman or Ariel (2) Margins: 0. M. Introduction . Only discuss the points appropriate. NM.5" right) (3) Figures which include both Drawings & Graphs should be computer generated and clear (4) All Figures and Tables must have captions and be referenced in the text (5) At least one peer reviewed technical journal article must be referenced in each report.. 66(1)18-22(1983). Discussion) 5. Theory. Conclusions . Date Your report should include the following sections as appropriate for the assignment: 1. Comparison with Theory or Hypothesis 6. The length of the lab report should be complete and to the point." J. Soc. Follow the style and format used in peer reviewed technical journal articles. ABC Corp. The article must be applicable to the lab content. Authors (for lab reports indicate lab partners).Ceram. J.Note that this is NOT the same as the Results or a Summary but rather what was learned from the Results 7. 77 .short summary of what was done.

For most college lab courses. Am. If you are writing a brief progress report. the student can write these sections easily based on lab handouts and information in introductory textbooks. To:. Each journal has a specific format for submission that is published annually in either the January or December issues or found on the publisher's web page. Some people read the Abstract first. From:. and subject as well as to whom the memo is being sent and sender." Many researchers find that writing the Experimental Procedure section first is easiest because one can write it as it is occurring. If it is a memo. Often. Every organization has its own unique style of memos. The Introduction and/or Theory sections can also be written before the work is complete because this provides background information to the reader. The author should follow the scientific process of presenting a thesis and then proving it with their results. you should keep a hard copy of important electronic memos or messages. Some people prefer to write the conclusions before the Discussion so that the Discussion can be written in support of the conclusions. Email is fast replacing the written memo but to protect yourself. Subject:. There are another group 78 . reports. The important information is contained in the next paragraphs. Materials/Ceramic Engineering Major for J. The body should have a brief introduction or provide necessary background information about a paragraph in length. & TECHNICAL ARTICLES for Students of Dr. each major task of the project will have its own paragraph unless there is nothing significant to report.g. Deidre Hirschfeld The writing of memos is a skill all engineers need to know. Soc. The author is trying to convince readers to reach the same conclusions based on data provided. It is a brief written communication on the status of a project or possibly important occurrence. then Results and Discussion. Format is usually: Date. Results Section is next and that is usually written followed by the Discussion. Lastly. e. Ceram. the Introduction and Experimental sections last. there may be cases when the results are not at all what was expected and a major revision of the Introduction and Theory sections may be required. A new author should be aware of the order in which technical articles are read. these two sections are combined if the author believes it makes understanding better. The parts of a memo are a heading and body. or lawsuit. BRIEF PROGRESS REPORTS. These sections can be written while samples are firing in the kiln or drying. etc. The typical reader for professional journals is assumed to be a senior level student with a degree in the appropriate field. Other readers just look at the Abstract and conclusions. In industry. Some popular trends are described and can be followed to help avoid the "write the paper at 2am on the day it is due time crunch. there will only be one or two paragraphs. Of course. next the Conclusions. and if necessary. but it is usually easier to revise writing than to start from the beginning . The way one begins writing a technical paper is very personal. so once on the job. you will have to adapt what you have learned in school. HOW TO WRITE MEMOS. The heading has the date. a memo can affect the fate of a project. This description details one method of writing a technical journal article and explains the parts of an article as it would appear in a scientific journal. the Abstract is written in terms of the most important conclusions and the Title finalized. The theme throughout the article should point directly to the conclusions. product. double spaced along the left margin. aligned vertically.

In technical publications. Also. poor experimental technique is an unacceptable excuse for anything. It is important that the author is not overwhelmed by the data and can 79 . either only main steps are given here or it is put in an appendix at the end of the paper. Tell the reader what to see on the graphs and tables. Only show useful data and not intermediate steps. This may be combined with the Theory Section. how does it impact the known world. include broad implications. OR for college labs. what was done.The Abstract is meant to be an executive summary. In formal journal articles. these cannot be used as a reason that a particular theory was not followed. background information. It gives enough information to the potential reader to let them know important details and conclusions. and reasons. EXPERIMENTAL PROCEDURE .Background information is presented here.Relate Results to theories and discuss specifics about what was discovered. are given.major conclusions and sometimes significant results are discussed. It should entice the potential reader to take time to read the whole article. procedure techniques can be used as one of the main points of the study! DISCUSSION . If data do not follow theory. Why was this work conducted. Do not just create tables and figures with no explanation. It may be combined with Introduction.. as the old saying goes: A picture is worth a thousand words. The author should just include enough information to let the reader know what was learned. facts.Tell what was done in sufficient detail to allow someone to duplicate the work. explain what is happening or present a new theory. In college labs.Tell the reader what important data were collected. A brief review of other related work is made here. If long derivations are necessary. ABSTRACT .e. Raw data are unnecessary especially if hundreds of tests were conducted. Do not describe safety precautions unless it is critical to the experiment. Optional but usually a good idea. Include statistical analyses with results: Are data from group A truly different from group B? Give only important details of the analysis. i. The goal is to help the reader draw the same conclusions as the author. who after reading the abstract will actually read the whole article in proper order.Describes in more detail important theories applied to the work. however. state or country. A graphical figure may make the point more clearly than a table.of readers. Abstracts are 100-150 words in length with 250 usually the maximum. what is its importance. with city. Figure 1. Table 5. Label (Number and Title) all figures and tables and refer to them specifically by number in the text. Set reader up for Conclusions by providing proof. major theories examined. IF extra or intermediate information will help reader then that information should be put in an Appendix. if poor lab procedure or other problems arise. Some describe an abstract as a mini-advertisement. An Abstract commonly follows this form: Sentences 1-2: WHY. INTRODUCTION . what can be done is that poor procedure can be used to omit data - which is described in either the Experimental or Results sections. THEORY . RESULTS . Sentences 3-6: HOW. manufacturers of chemicals and make/model of equipment. and serious scientists. Important information on Experimental Procedure and possibly major theories applied Sentences 7-10: WHAT . Describe WHY the data are as presented. AKA grad students. Results may be combined with Discussion.

Do not say things like "Treated aluminum oxide bars exhibited average MOR values of 200 MPa and untreated. Do not provide locations for figures. “as shown in Figure 1 below” (or above) because the reader can find the figure." REFERENCES .” 80 . The Discussion may be combined with Results if this makes the presentation more clear to the reader. It is inappropriate to tell reader to “See Figure 1” as that is unnecessary. When in industry. In College labs. Inanimate objects do not have emotions. it should be in the main body. diagrams. APPENDICES . Appendices are for extra material. drawings. Do not put important figures.Notation of sponsors. 5. Figures do not have to be embedded in the text. or draw conclusions. Technical Writing Suggestions for MatE 310 Technical writing should meet the requirements of the audience or customer. it is recommended that the following styles be employed: 1. CONCLUSIONS . 3. 2. All charts. All Figures must be discussed in the text body and referred to as has been done in this lab manual.. funding. and persons who assisted with the work in a special way.Here is where all the other information that may be important to only the most interested reader or key information that does not quite fit in the main article are placed. senses. or data in an appendix. All micrographs must have a scale bar included showing magnification. raw data may be put here. and others are mentioned. Just saying 50X for a particular microstructure is not appropriate because the size of the picture could have been changed which will affect magnification. Usually if there are few results. Try to make all figures black and white to reduce printing costs. e. For example. Figures copied from other sources must be referenced.g. Appendices are usually identified by sequential letters and are referenced in the text body. samples can not and do not “feel cold. References must be numbered sequentially in text and proper citations made for information that is not original. micrographs are referred to as Figures. diagrams. it is easy to combine them. 150 MPa" Instead. Follow guidelines provided in section 4 Plotting. photos. For MatE 310. Some information is considered common knowledge but it is very obvious to readers when words seem plagiarized from a text. Footnotes or Reference Section must be used for the citations. page numbers. This is where lab TAs. Bibliographies are not acceptable. Label Figures sequentially from start to end. ACKNOWLEDGEMENTS . If the information is important.Cite all your references. follow company standard format and styles which may be very different from what was required in any class at NMT.draw conclusions based on the "big picture" or overall knowledge base. state that "Treatment process (describe the key feature of treatment) increased the flexural strength of aluminum oxide. but can be placed at the end of a section. Use appropriate Journal format and include article title.Conclusions are not a restatement of Results but rather what was learned from the Results. even if it is an elementary textbook. 4.

Pick one and consistently use it. Avoid the use of personal pronouns throughout the report. 8. 7. Whether – Weather. 81 .6. technical jargon that is often used and mis-spelled should be added to the software dictionary. e. Watch Significant Figures! When copying data tables from spread sheets be sure to truncate the numbers to the appropriate number of digits. per-peer. Ration. Some technical publications permit their use and others do not.Be wary of automatic Spell Checker corrections. Common problem words are: To-Two-Too.Ratio. 9. Do not switch tenses from present to past to future. Use active instead of passive voice. do not use them. Do not refer to samples/experiments in terms of the students performing the test. Also. For this class. “ John and Susie's formulation contained 50% X by weight” 10.g. etc. Do not identify lab partners who did certain tasks within the main body as the report is a team project. Assistance is noted in the Acknowledgment section of the report. Software packages often make mistakes with words. Wear – Where. Use a consistent verb tense throughout the report.