Tim%20McClure

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Tim McClure
Analysis Shared Experimental Facility Project
Technician Office 13-4149 Phone (617)
258-6470 Email mtim_at_mit.edu http//mit.edu/mtim/w
ww MIT Center for Material Science and
Engineering 77 Massachusetts Avenue, Cambridge,
Massachusetts 02139
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Introduction to the CMSE Shared Experimental
Facilities

• Anthony J. Garratt-Reed, SEF Staff
• Thu Jan 10, 02-0500pm, 13-2137, Refreshments
  provided
• No enrollment limit, no advance sign up , Single
  session event
• The Shared Experimental Facilities in the Center
  for Materials Science and Engineering provide a
  wide range of Materials Characterization
  instrumentation openly available to researchers.
  This includes electron microscopes, X-ray
  diffraction systems, surface analysis,
  spectroscopy techniques, thermal analysis and
  crystal growth furnaces. Come and find out more
  details about what we have, what it can do for
  you, and who runs it! Each staff member will give
  a short introduction to the instruments in their
  care. Most staff will be offering a more detailed
  presentation about their equipment later during
  IAP.
• Contact Anthony J. Garratt-Reed, 13-1027,
  x3-4622, tonygr_at_mit.edu
• Sponsor Center for Materials Science and
  Engineering
• Latest update 25-Oct-2007

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Analysis Shared Experimental Facility (ASEF)
ASEF Staff Office 13-4149 Tim
McClure mtim_at_mit.edu X8-6470 Thermal
Analysis 13-4111 Spectroscopy 13-4139 - - - - -
- - - - - - - - - - - - - - - - - - - - - - - - -
- - Libby Shaw elshaw_at_mit.edu X3-5045 AFM/Thin
Film 13-4147 Surface Analysis 13-4137
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Optical Thermal Characterization Laboratory (OTC)
OTC Lab 13-4111 13-4139
Optical
Thermal
Instrumentation
Thin Film/ Metrology
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Optical Thermal Characterization Laboratory
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ASEF OTC Instrumentation List

• Thermal Analysis
• Perkin Elmer Diamond Differential Scanning
  Calorimeter
• Perkin Elmer Pyris 1 Differential Scanning
  Calorimeter
• Perkin Elmer PSI Differential Scanning
  Calorimeter
• Perkin Elmer DTA7 Differential Thermal Analyzer
• Perkin Elmer TGA7 Thermogravimetric Analyzer
• Seiko DMS 110 Dynamic Mechanical Analyzer
• Seiko Dual TG/DTA 320 Thermogravimetric/Differenti
  al Thermal Analyzer
• Perkin Elmer 2Z Auto Balance
• Support
• Harrick Scientific PDC-32G Plasma Cleaner
• Linkum Scientific FTIR 600 Freezing/Hot stage
• Janis Supertran-VP System Liquid Helium Cryostat
• Oxford Instruments Liquid Helium Cryostat
• Lasers Argon Ion, Titanium Sapphire, Solid
  State 785nm

• Spectroscopic
• Cary 500i UV-VIS-NIR Dual-Beam Spectrophotometer
• Cary 5E UV-Vis-NIR Dual-Beam Spectrophotometer
• Kaiser Hololab 5000R Raman Spectrometer and
  Microprobe
• Nicolet Magna 860 Fourier Infrared Spectrometer
• SPEX FluoroLog Model FL212 Spectrofluorimeter
• Thin film/Metrology
• Tencor P-10 Surface Profilometer
• Tencor FLX 2320 Thin Film Measurement System
• Sharon Vacuum Thermal Co-Evaporator
• Mettler FP900 Thermo system Hot stage
• Microscopes
• Zeiss Axioplan Optical Microscope
• Zeiss Ultraphot Optical Microscope
• Reichert Zetopan Optical Microscope
• Spectra Tech Nic Plan Microscope

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Optical Thermal Characterization Laboratory
UV/VIS/NIR
Optical
FTIR
Raman
Microscope
Microscope
Optical Microscopy
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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
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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
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Electromagnetic Spectrum
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Units
The wavelength is the distance between repeating
units of a wave pattern
Wavelength Length of the wave in microns (µ) 1
micron 10-4 cm
Wave numbers Number of waves per centimeter
(cm-1) Reciprocal Centimeter
Wavenumber 104/Wavelength
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Optical Spectroscopic Analysis Methods in the OTC

• UV/VIS/NIR
• FTIR
• Raman

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Spectrometer Drawing
Source
Sample
Detector
Resulting Data
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Optical Spectroscopic Sampling
Reflection
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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
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UV/VIS/NIRSamples

• Reflection
• Solids
• Pastes
• Specular from 20 to 70
• Diffused hemisphere or cup

• Transmission
• Solids
• Liquids
• Pastes

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UV/VIS/NIR Data
Transmission Filters
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UV/VIS/NIR Data
UV Protection
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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

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IR Spectroscopy Studies

• Identification of a Substance
• Determination of Molecular structure
• Determination of Purity
• Reaction Kinetic Studies
• Fundamental Studies of Molecules

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Hooks Law

• Hookes 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
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CO2 IR Spectra
Asymetrical Stretch
Bending Mode
Symetrical Stretch
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Infra-Red Spectroscopy Theory

• Infra-Red radiation promotes transitions in a
  molecule between rotational and vibrational
  energy levels of the ground (lowest) electronic
  energy state.
• This is in contrast to the energetically more
  powerful ultra-violet radiation, which
  facilitates transitions between vibrational and
  rotational energy levels of different electronic
  levels.

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FTIR Sampling
Reflection
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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

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Choosing an FTIR Sampling Technique

• Physical State of sample
• Sample environment
• Information required
• Sample integrity
• Sample Size
• Time and cost per sample

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FTIR Mapping Data Example
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Raman Spectrometer
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Raman
Studies
Sample Types

• Chemical Composition
• Bonding Structure
• Phase
• Localization
• Size
• Induced Stress
• Reaction Mechanisms

• Semiconductors
• Pharmaceuticals
• Polymers
• Minerals

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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

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Raman Applications

• Art
• Biology
• Carbon
• Corrosion
• Electrochemistry
• Fluorescence
• Forensics

• Microreactors
• Pharmaceuticals
• Polymers
• Process
• Semiconductor
• Solid State

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Raman Effect

• Classical
• Perturbation of the molecules electric field
• Quantum mechanical
• scattering is an excitation to a virtual state
• lower in energy than a real electronic transition
  with nearly coincident de-excitation and a change
  in vibrational energy
• The scattering event occurs in 10(-14) seconds or
  less

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Joblonski Diagram
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Raman Data Example
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FTIR Raman Spectrum of Cyclohexane
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Raman Excitation Frequency
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Raman Mapping Application ExampleHard Coating
(Al50Cr50N)
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
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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
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Optical Thermal Characterization Laboratory
DSC
Thermal Analysis
DTA
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

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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

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Physical Properties Measured by Thermal Analysis

• Physical Property Derived Technique
• Mass Thermogravimetry
• Isobaric mass-change determination
• Evolved gas detection
• Evolved gas analysis
• Emanation thermal analysis
• Thermo particulate analysis
• Temperature Heating curve determination
• Differential thermal analysis
• Enthalpy Differential scanning calorimetry
• Dimensions Thermodilatometry
• Mechanical characteristics Thermo mechanical
  analysis
• Dynamic thermomechanometry
• Acoustic characteristics Thermosonimetry
• Thermoacoustimetry
• Optical characteristics Thermoptometry
• Electrical characteristics Thermoelectometry
• Magnetic characteristics Thermomagnetometry

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Physical Properties Measured by Thermal Analysis

• Physical Property Derived Technique
• Mass Thermogravimetry
• Evolved gas analysis
• Temperature Differential thermal analysis
• Enthalpy Differential scanning calorimetry

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Thermal AnalysisApplications

• Heat Capacity
• Thermal emmisivity
• Purity
• Create phase diagrams

• Polymers
• Glass Transistion
• Estimation of Crystallinity
• Blend analysis

• Vulcanization of rubber
• Vaporization of water
• Solid-Solid and Solid-Liquid transformations
• Concentration determination
• Estimation of solvent composition
• Melting prperties of ski wax

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Thermal AnalysisSamples

• Typical 5-10mg
• Volume
• Thermal Conductivity
• Atmosphere
• Conditioning, (Thermal History)
• Compatability

• Sample Pans
• Material, Aluminum up to 650C
• Volume
• Sealed or Vented

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Thermal Analysis Methods

• Thermogravimetric Analysis, TGA
• Differential Thermal Analysis, DTA
• Differential Scanning Calorimetry, DSC
• Simultaneous Thermal Analysis, STA

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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
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TGA Data of Calcium Oxalate
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Differential Thermal Analyzer (DTA)
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DTA Data of Gold
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Differential Scanning Calorimeter (DSC)
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DSC Data of Indium at Multiple Heating Rates
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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)
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TG/DTA Data of Calcium Oxalate
50 to 800C _at_10C/min, Nitrogen _at_150ml/min,
Sample Weight 0.965mg, Platinum Pans, Data
Interval 0.5sec
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Optical Thermal Characterization Laboratory
Profilometer
Thermal Co evaporator
Flexus
Thin Film/ Metrology
Hot Stage Microscopy
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Profilometer
Step Heights 100A to 327um
Max Sample Size 10 X 10 X 1.25 in.
Max Stage Travel 6 in.
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Profilometer Data Example
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Profilometer Data Example
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Curvature Measurement System
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Thermal Co-Evaporator
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Plasma Cleaner
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Temperature ControlledMicroscope Stages
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Sign up for my other IAP sessions to learn more
about these analysis techniques
Thermal Analysis Instrumentation at CMSE Thurs
Jan 23, 10am-1200pm, 13-2137 No limit but
advance sign up required (see contact
below) Signup by 22-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.
Spectroscopic Instrumentation at CMSE Thurs Jan
31, 10am-1200pm, 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.
Preregister via e-mail. Contact Tim McClure,
13-4149, x8-6470, mtim_at_mit.edu