DSC Introduction and training

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????? ?? (DSC, TGA DMA)
PerkinElmer Thermal Specialist ??? Tiffany
Kang Tiffany.Kang_at_perkinelmer.com
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• Differential Scanning Calorimetry (DSC)
• Thermogravimetric Analysis (TGA)
• Thermomechanical Analysis (TMA)
• Dynamic Mechanical Analysis (DMA)

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DSC Heat flow vs. Temp Tm, Tc, Tg DH, curing time, curing degree Reaction rate, kinetics
TGA Weight Loss vs. Temp - Decomposition temperature Wt percentage Oxidative time
TMA Dimensional Change vs. Temp CTE (a1, a2) Tg Softening point
DMA Viscoelastic property vs. Temp Storage/Loss/Complex Modulus (E, E, E) tan d Viscosity and master curve
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• Type of Polymer Chain Structure

Type Structure
Example
Poly(vinyl chloride), Polystyrene Polypropylene
Polypropylene Poly(imidazol pyrrolones)
Linear Branched short chain Long chain
branching Ladder
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• Type of Polymer Chain Structure (Continued)

Type Structure
Example
Phenol-formaldehyde resins Two crosslinked
polymers not bonded to each other Crosslinked
epoxy with vinyl polymer
Star Network Interpenetrating network (IPN)
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Amorphous vs. Crystalline?
Amorphous Thermoplastic
Crystalline Polymer
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Semi-Crystalline Polymer

• Semi-crystalline polymers contain both amorphous
  AND crystalline phases
• Properties dominated by both Tg and Tm
• Semi-crystalline polymers can exhibit additional
  crystallization during heating

Semi-Crystalline Polymer
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Thermosetting Polymer
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Schematic Results in Thermal Analysis
Quality of sample process
DSC(Ex?) TGA TMA DMA

-Solid Melting

• Crystalline
• Semi-crystalline
• -Amorphous
• -Semi-crystalline
• -General
• -Liquid
• -Unspecific

Recrystallization Sublimation Solid-solid
transition Glass transition Softening without
Tg Post-crosslinking Decomposition Ligand
release Evaporation Chemical reactions Determinati
on of
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DSC Technique Differential Scanning Calorimetry
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Question?

• PE??HDPE, LLDPE?LDPE
• - ???????
• - ???????
• - ???????????
• ????????
• ????????????
• ???????????
• ???????
• DSC????????

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What is DSC ?

• ????????
• ( Differential Scanning Calorimeter )
• ???????????????????????????????????????,??????
  ????????????????,??????,?????????????,???????????

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Thermal Analysis applications - DSC
Diamond DSC

• Principle
• Heat flow change vs. temperature
• Measures
• Phase transition (Tg, Tm, Tc) and heat
• Curing reaction and other chemical reactions

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Polymer Transitions
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DSC Thermal Curve of PET
? ?
? ?
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DSC for curing studies

• Detection of Tg
• Onset of cure
• Maximum rate of cure (peak maximum)
• End of cure
• Heat of cure

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DSC???????????
???? Phase Transition ??? ?H
?????? Tg ??? ?H
?? Melting point ??? Ea
????? Crystal Temperature ?????? O.I.T.
?????? Cold Crystal Temperature ????? Dynamic
??? Crystallinity ?? Curing
??? Crystal Energy ?? Purity
????? Crystal Period ?? Cp
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DSC?????
??? Heat Flux DSC
???? Power Compensation DSC

• ????DH
• ????????
• ????

• ??DT
• ?DH kDT??DH
• ????

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TGA Technique Thermogravimetric Analyzer
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Thermal Analysis applications - TGA
Pyris 1 TGA

• Principle
• Weight change vs. temperature
• Measures
• Compositions and wt
• Thermal stability and decomposition temp.

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TGA Design Concept
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TGA Thermal Curves
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TGA ?????
????

• Temperature control device
• - Furnace, Thermocouple
• Weight measurement device
• -Null Balance

Detector
Torque Motor
Tare Weight
Sample
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TGA?????

• TGA-FTIR/TGA-MS
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• TGA-GC/MS
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• ??????

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TGA for compositional analysis

• Molding compound contains epoxy and filler
• Epoxy can be burned off and residue is inert
  reinforced filler
• TGA provides accurate and reproducible
  compositional data on molding compound

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Pyris 1 TGA

• Features
• Most sensitive balance in the world with 10-7 g
  sensitivity
• Isothermal and isolated balance chamber for
  better stability
• Isolation convection of balance and sample purge
  gas to have best sensitivity and stability
• Ion discharge component for keeping from
  electrostatic disturbance
• Variety of sample pans for sample decomposition
  analysis

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TMA/DMA Technique Mechanical Analyzer
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Thermal Analysis applications DMA/TMA
DMA 8000

• Principle
• Viscoelastic properties vs. temperature
  (DMA)
• Dimensional change vs. temperature (TMA)
• Measures
• Glass transition point
• Storage, Loss modulus and tan delta
• Coefficient of thermal expansion (CTE)

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What is DMA ?

• DMA (Dynamic Mechanical Analyzer)
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• ??????????,?????????????????,??????????,??????
  ????

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• E Storage Modulus
• ????
• ????
• E Loss Modulus
• ????
• ????
• tan d E / E

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??????? DMA

• ??????
• ex. ??(Modulus), ??(Viscosity), ???(tan d)
• ??????
• ex. b,g- transition, Tg?DSC/TMA?????
• ???(Activation Energy)??
• ????????
• ex. Creep Recovery, Time-temp. superposition
  
• ????????????
• ex. Curing process, controlled humidity,
  Solvent Immersion

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DMA????Sine Wave????, ????????
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Idealized DMA Scan
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Frequency effects things too

• Transitions shift
• Behavior changes

More elastic
E
?
More fluid
Frequency
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So frequency can act like temperature
E
E
Frequency
Temperature
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DMA ??...
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DMA ???????
Total Force
Force motor
Static Force
Dynamic Force
LVDT
Frequency
f
Storage Modulus
Amplitude
K
Fixtures
Hold Sample
Position
Loss Modulus
d
Phase
Thermocouple
Furnace Options from -190 to 600 C
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Options Single Cantilever Dual Cantilever 3
Point Bending Tension Compression Shear Quartz
Shear Material Pocket
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Exclusive Material Pockets
Sample in Pocket
Pocket closed sealed
Pocket open

• Applications
• Powders like drugs, excipients, foods, natural
  products, etc.
• Gels
• Uncured adhesives
• Coatings
• Samples that cant support their own weight

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DMA mode for mechanical properties change

• This plot shows DMA results (E and tan delta)
  for cured substrate
• DMA gives the most sensitive measure of Tg
• DMA results show that substrate is incompletely
  cured as 2 split peak was found in tan delta
  around Tg

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DMA most sensitive indicator of cure

• This plot shows DMA results on completely cured
  and slightly under-cured PCBs
• Under-cured PCB exhibits a slight increase in E
  above Tg making the board unacceptable

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TMA mode for dimensional change

• Plot shows results on TMA expansivity of
  substrate
• 1st heat shows that the board contains built in
  stresses as a result of processing
• Stresses are released at Tg
• 2nd heat shows classic TMA Tg free of stress
  relief effects

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???? Tg ?? -- ???????
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???? -- ????
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???? -- ????
Epoxy Resin
Endothermic
30 mw
Range
20 oC/min
Heating Rate
32.76 mg
Weight
Run 1
62.8 oC
D
H
Heat Flow (mW)
113.3 oC
Run 2
40
80
120
160
200
240
280
T (oC)
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???? -- ??????
DSC Heat Flow
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??? Filler

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??(Carbon)????
??????????????????????????????????,???????????????
???????
?????,??????????????????Polymer?Carbon???????52??2
9?????Y????
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TGA/FTIR/Interface System

• ????????
• ?????????--??????????
• ?????TG-IR??--TimeBase Software

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TGA/FTIR Software
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TGA/FTIR Software
TGA Weight loss vs.FTIR Spectrum weight vs Time
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Thank you for your attention !