Transcript Slide 1
Tim McClure
Analysis Shared Experimental Facility Project Technician Office: 13-4149 Phone: (617) 258-6470 Email: [email protected]
http://mit.edu/mtim/www MIT Center for Material Science and Engineering
77 Massachusetts Avenue, Cambridge, Massachusetts 02139
IAP 2008
Analysis Shared Experimental Facility (ASEF) ASEF Staff Office: 13-4149
Tim McClure X8-6470
Thermal Analysis Spectroscopy
13-4111 13-4139 - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - -
Libby Shaw X3-5045 [email protected]
AFM/Thin Film Surface Analysis 13-4147 13-4137 13-4111 13-4139 13-4147 13-4137 13-4149 IAP 2008
Optical Thermal Characterization Laboratory (OTC) OTC Lab 13-4111 & 13-4139 Optical
Instrumentation
Thermal Thin Film/ Metrology
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Optical Thermal Characterization Laboratory Optical UV/VIS/NIR FTIR Raman Thermal Analysis Microscope DSC DTA DMA TGA Optical Microscopy Microscope Metrology Profilometer Thermal Co evaporator Flexus Hot Stage Microscopy
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Optical Thermal Characterization Laboratory UV/VIS/NIR Microscope FTIR Optical Raman Optical Microscopy
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Microscope
Optical Spectroscopy
Spectroscopy
is the study of the interaction between radiation and matter
Optical Spectroscopy
involves interactions of matter with electromagnetic radiation
Spectrometry
is the measurement of these interactions
Spectrometer
is the instrument which performs these measurements IAP 2008
Optical Spectroscopy
Spectroscopy
is often used in physical and analytical chemistry for the identification of substances through the spectrum emitted from or absorbed by them IAP 2008
Electromagnetic Spectrum
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Optical Spectroscopic Analysis Methods in the OTC • UV/VIS/NIR • FTIR • Raman IAP 2008
Spectrometer Drawing
Source Sample Resulting Data IAP 2008 Detector
Optical Spectroscopic Sampling Reflection Transmission Specular Diffused IAP 2008
UV/VIS/NIR Spectrophotometers
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UV/VIS/NIR Applications Ultraviolet and visible light are energetic enough to promote outer electrons to higher energy levels UV/VIS/NIR Spectroscopy is routinely used in the quantitative determination of solutions of transition metal ions and highly conjugated organic compounds It is USUALLY applied to molecules and inorganic ions or complexes in solution IAP 2008
Transmission •Solids •Liquids •Pastes UV/VIS/NIR Samples Reflection •Solids •Pastes •Specular from 20° to 70° •Diffused hemisphere or cup IAP 2008
UV/VIS/NIR Data
UV Protection IAP 2008
Resolution Vs Detection Limits
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Fourier Transform Infrared Spectrometer (FTIR) • • Beam splitter, Detector, Source combinations allow measurement in the Mid, Near and Far IR ranges. Accessories – Emission Experiments – Horizontal Attenuated Total Reflectance – Variable Angle Reflectance – Optical Cryostat – Solid, Liquid, Gas Sampling Accessories IAP 2008
IR Spectroscopy Studies
• Identification of a Substance • Determination of Molecular structure • Determination of Purity • Reaction Kinetic Studies • Fundamental Studies of Molecules IAP 2008
Hooks Law
Hooke’s Law
For stretching of the bond A-B, The vibrational frequency v (cm-1) is given by the equation:
v = (1/2µc) (f/µ)1/2
c = Velocity of light f= Force constant of the bond
µ
= reduced mass of the system
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Vibrational Modes
Symetric Stretching Mode Symetric Bending Mode Antisymetric Stretching Mode IAP 2008
CO2 IR Spectra
Asymetrical Stretch Bending Mode Symetrical Stretch IAP 2008
FTIR Sampling Reflection Transmission Specular Diffused IAP 2008
Fourier Transform Infrared Samples
Solids, Liquids & Gases can be measured
• Powders • Thermalplastic polymers • Soluble polymers • Thin polymer films • Thick films and plaques • Irregularly shaped polymers • Dark colored polymers • Layered polymer films • Polymer film on reflective substrate • Adhesives • Rubber • Fibers IAP 2008
Choosing an FTIR Sampling Technique • Physical State of sample • Sample environment • Information required • Sample integrity • Sample Size • Time and cost per sample IAP 2008
Raman Spectrometer
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Studies
•Chemical Composition •Bonding Structure •Phase •Localization •Size •Induced Stress •Reaction Mechanisms Raman
Sample Types
•Semiconductors •Pharmaceuticals •Polymers •Minerals IAP 2008
Raman Advantages
•Not as sensitive to water •Little or no sample preparation •Spectra is robust to temperture changes •Largely unaggected by sample cell materials such as glass •High spatial resolution IAP 2008
Raman Applications •Art •Biology •Carbon •Corrosion •Electrochemistry •Fluorescence •Forensics •Microreactors •Pharmaceuticals •Polymers •Process •Semiconductor •Solid State IAP 2008
Joblonski Diagram IAP 2008
Raman Data Example
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0 .8
0 .6
0 .4
0 .2
FTIR & Raman Spectrum of Cyclohexane 1 .2
Cyc l o hexa ne FT I R 1 .0
1 40 Cyc l o hexa ne Ram an 1 20 1 00 8 0 6 0 4 0 2 0 -0 3 000 2 500 2 000 W ave num bers (c m -1 ) IAP 2008 1 500 1 000
Raman Excitation Frequency
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Raman Mapping Application Example Hard Coating (Al 50 Cr 50 N) 670 X 430 um Raman Image •Red - Hematite (Steel) •Green - Protective Coating •Yellow - Equal Contributions Optical with overlaid Raman image Ball-On-Disk Tribological Test IAP 2008
Raman Mapping Example Cocoon fiber produced by the Bombyx mori silkworm •Red - Acrylic matrix •Green - Fibroin thread •Blue - Sericin matrix •17 X 17 um image •1um steps •514.5nm, 0.5mw, 80sec •6.42 hours Image aquired by Marie-Eve Rousseau Ph. D candidate, University of Qubec IAP 2008
Optical Thermal Characterization Laboratory DSC DTA Thermal Analysis TGA DMA
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Thermal Analysis
International Confederation for Thermal Analysis (ICTA) Definition A group of techniques in which a physical property of a substance an/or its reaction products is measured as a function of temperature whilst the substance is subjected to a controlled temperature program IAP 2008
Thermal Analysis
LaChatel in 1887 (first) Temperature influences the state of a system (Sample, material, etc..) which can be observed in phase transitions, chemical decomposition as well as in thermal expansion Structural changes will change the mechanical performance •Inorganic Chemistry •Organic Chemistry •Polymer Chemistry •Technology IAP 2008
Physical Properties Measured by Thermal Analysis
Physical Property
Mass Temperature Enthalpy
Derived Technique
Thermogravimetry Evolved gas analysis Differential thermal analysis Differential scanning calorimetry IAP 2008
•Heat Capacity •Thermal emmisivity Thermal Analysis Applications •Purity •Create phase diagrams •Vulcanization of rubber •Vaporization of water •Solid-Solid and Solid-Liquid transformations
Polymers
•Glass Transistion •Estimation of Crystallinity •Blend analysis •Concentration determination •Estimation of solvent composition •Melting prperties of ski wax IAP 2008
Thermal Analysis Samples Typical 5-10mg •Volume •Thermal Conductivity •Atmosphere •Conditioning, (Thermal History) •Compatability Sample Pans •Material, Aluminum up to 650°C •Volume •Sealed or Vented IAP 2008
Thermal Analysis Methods
• Thermogravimetric Analysis, TGA • Differential Thermal Analysis, DTA • Differential Scanning Calorimetry, DSC • Simultaneous Thermal Analysis, STA IAP 2008
Thermo Gravimetric Analyzer (TGA) A technique in which the
mass
of a substance is measured as a function of temperature while the substance is subjected to a controlled temperature program Time/Temperature IAP 2008
TGA Data of Calcium Oxalate
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Differential Thermal Analyzer (DTA) IAP 2008
DTA Data of Gold
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Differential Scanning Calorimeter (DSC) IAP 2008
DSC Data of PET
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DSC Data of PET Glass Transition
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Thermo Gravimetric/Differential Thermal Analyzer (TG/DTA) IAP 2008
TG/DTA Data of Calcium Oxalate
50 to 800 °C @10°C/min, Nitrogen @150ml/min, Sample Weight 0.965mg, Platinum Pans, Data Interval 0.5sec
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Optical Thermal Characterization Laboratory Profilometer Thermal Co evaporator Thin Film/ Metrology Flexus Hot Stage Microscopy
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Profilometer 2um radius 60 ° Styli
Max Sample Size
10 X 10 X 1.25 in.
Max Stage Travel
6 in.
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Step Heights
100A to 327um
Profilometer Data Example IAP 2008
Profilometer Data Example IAP 2008
Temperature Controlled Microscope Stages IAP 2008
Sign up for my other IAP sessions to learn more about these analysis techniques Thermal Analysis Instrumentation at CMSE Spectroscopic Instrumentation at CMSE Thurs Jan 23, 10am-12:00pm, 13-2137
No limit but advance sign up required (see contact below) Signup by: 22-Jan-2008 Single session event
Thurs Jan 31, 10am-12:00pm, 13-2137
No limit but advance sign up required (see contact below) Signup by: 29-Jan-2008 Single session event The Center for Materials Science and Engineering's Analysis Shared Experimental Facility has an assortment of Thermal Analysis instrumentation available for the use of MIT researchers. These include Differential Scanning Calorimeter (DSC), ThermoGravimetric Analyzer (TGA) Differential Thermal Analyzer (DTA) and Dynamic Mechanical Analyzer (DMA). There will be presentations on the instrumentation and the various measurement techniques available.
The Center for Materials Science and Engineering's Analysis Shared Experimental Facility has an assortment of Thermal Analysis instrumentation available for the use of MIT researchers. These include Differential Scanning Calorimeter (DSC), ThermoGravimetric Analyzer (TGA) Differential Thermal Analyzer (DTA) and Dynamic Mechanical Analyzer (DMA). There will be presentations on the instrumentation and the various measurement techniques available.
Preregister via e-mail.
Contact: Tim McClure, 13-4149, x8-6470, [email protected]
IAP 2008