1. Materials Characterization Lab
www.mri.psu.edu/mcl
Thermal Analysis
R.I. Malek
Materials Characterization Laboratory
University Park, PA 16802

2. Materials Characterization Lab
www.mri.psu.edu/mcl
Personnel
• Raafat Malek, Director
• Magda Salama, Mass Spec, Thermal analysis.
• Tim Klinger, Mass Spec.

3. Materials Characterization Lab
www.mri.psu.edu/mcl
Outline
• Definition
• Uses
• Information Provided
• Techniques
• TGA,
• DTA, DSC, SDT,
• TMA, DMA
•Thermal Expansion, Diffusivity
• Instruments
• Some Applications
• Reaction Kinetics
•New Instruments

4. Materials Characterization Lab
www.mri.psu.edu/mcl
Definition
Thermal Analysis is a series
of techniques that measure
materials properties as a
function of temperature,
time and atmosphere.

5. Materials Characterization Lab
www.mri.psu.edu/mcl
Uses
Research and Development:
• Development and selection of new materials,
• Performance and evaluation of existing
materials.
Quality Control:
• Fingerprinting,
• Monitoring and certification.
• Troubleshooting.

6. Materials Characterization Lab
www.mri.psu.edu/mcl
Information Provided
• Melting Point,
• Glass Transition,
• Crystallinity,
• Curing and Cross-Linking,
• Heat Capacity,
• Stability,
• Purity,
• Composition,
• Modulus of Expansion,
• Reaction Kinetics.

7. Materials Characterization Lab
www.mri.psu.edu/mcl
Techniques

8. Materials Characterization Lab
www.mri.psu.edu/mcl

9. Materials Characterization Lab
www.mri.psu.edu/mcl

10. Materials Characterization Lab
www.mri.psu.edu/mcl

11. Materials Characterization Lab
www.mri.psu.edu/mcl

12. Materials Characterization Lab
www.mri.psu.edu/mcl
Instruments at MRL
TGA/MASS SPECTROMETER

13. Materials Characterization Lab
www.mri.psu.edu/mcl
Balance Purge in
Furnace
Purge
exit
Furnace
Purge in

14. Materials Characterization Lab
www.mri.psu.edu/mcl
New Mass Spectrometer

15. Materials Characterization Lab
www.mri.psu.edu/mcl

16. Materials Characterization Lab
www.mri.psu.edu/mcl

17. Materials Characterization Lab
www.mri.psu.edu/mcl
Some Applications
Percent Amorphous Carbon Left over During Nano Carbon Synthesis
Sample: AP8256R/365/90 File: C:...8256R36590.001
TGA-DTA
Size: 6.2373 mg Operator: Clascidia
Run Date: 18-Nov-02 15:18
Comment: 5C/min up to 800C in air
110 0.6
TGA/DTA
Determining the Percent of Amorphous
Carbon in Carbon Nano Tubes
Carbon Nano Tubes
100 0.4
Temperature Difference (°C/mg)
Amorphous Carbon
90 0.2
Weight (%)
80 0.0
70 -0.2
60 -0.4
0 200 400 600 800
Exo Up Universal V2.6D TA Instruments
Temperature (°C)

18. Materials Characterization Lab
www.mri.psu.edu/mcl
Reduction of Ferric Oxide by a Mixture of CO + CO2
Sample: Ferric Oxide File: C:...Ferric Oxide.001
TGA
Size: 28.8550 mg Operator: Malek
Run Date: 15-Oct-02 10:13
Comment: Purge with CO-CO2
102
TGA
Ferric Oxide
100
3.515%
98 (1.014mg)
Weight (%)
96
94 4.719%
(1.362mg)
92
90
0 200 400 600 800 1000
Universal V2.6D TA Instruments
Temperature (°C)

19. Materials Characterization Lab
www.mri.psu.edu/mcl
Thermal Decomposition of Gypsum in a Hermetic pan
Sample: Gypsum hermetic File: C:...New DataGypsum H
DSC
Size: 4.9000 mg Operator: Magda
Method: Magda1.myth Run Date: 21-Jul-00 10:02
1
DSC
Decomposition of Gypsum in a Hermetic Pan
179.37°C
97.05J/g
0 135.45°C
281.5J/g
Heat Flow (W/g)
193.26°C
-1
Hemihydrate -----> Anhydrous
(0.5 Molecules of Water Lost)
-2
-3
146.64°C
Dihydrate -----> Hemihydrate
(1.5 Molecules of Water Lost)
-4
0 50 100 150 200 250 300
Exo Up Universal V2.6D TA Instruments
Temperature (°C)

20. Materials Characterization Lab
www.mri.psu.edu/mcl
Reaction of Liquid Crystal and PMMA

21. Materials Characterization Lab
www.mri.psu.edu/mcl
New Rocket Fuel from Nano Aluminum Powder
Sample: Nano Al Powder for Rocket Fuel File: C:...OxygenNanotech-1.001
DSC-TGA
Size: 3.4587 mg Operator: Malek
Run Date: 1-Nov-02 08:50
Comment: Oxygenn Purge
160 10
549.12°C
140 0
Heat Flow (W/g)
53.45% (2Al --------> Al2O3)
519.20°C
Weight (%)
(1.849mg)
6723.J/g
120 -10
100 -20
80 -30
200 400 600 800 1000
Exo Up Universal V2.6D TA Instruments
Temperature (°C)

22. Materials Characterization Lab
www.mri.psu.edu/mcl
Barium Titanate System
Sample: 72 Air 1200 File: D:72a1200_pw_1.003
DSC
Size: 12.1000 mg Operator: Filimonov
Method: BaTiO3 Run Date: 13-Feb-02 16:17
Comment: s72 1.01BaO*TiO2 Air A3_49 1200c powder/Pt Instrument: 2920 DSC V2.4F
0.3
123.00°C
0.2
124.40°C
0.6033J/g
Heat Flow (W/g)
0.1
123.82°C
0.6213J/g
0.0
127.89°C
-0.1
0 50 100 150 200
Exo Up Universal V3.3B TA Instruments
Temperature (°C)

23. Materials Characterization Lab
www.mri.psu.edu/mcl
Reaction Kinetics
Arrheneus Equation
K = A exp(-Ea /RT)
K = Reaction Rate
A= Constant
Ea= Activation Energy
R= Gas Constant
T= Temperature

24. Materials Characterization Lab
www.mri.psu.edu/mcl

25. Materials Characterization Lab
www.mri.psu.edu/mcl
Decomposition of Calcium Oxalate at different heating rates
Third weight loss
70
60
Weight (%)
5C/min 10C/min
1C/min
0.05C/min 0.1C/min
50
40
30
500 550 600 650 700 750
Universal V2.6D TA Instruments
Temperature (°C)

26. Materials Characterization Lab
www.mri.psu.edu/mcl
TGA/MASS SPEC of Carbon

27. Materials Characterization Lab
www.mri.psu.edu/mcl
TGA/MASS SPEC OF NEW CARBON FUEL
30
––––––– Mass Spec/ Magda
100
m/e 44
TGA
25
m/e 41
20
80
m/e 43
Ion Current (nA)
Weight (%)
15
m/e 15
CO2 10
60
C3H7
CxHy
5
CH3
m/e 2
H2
C2H6
m/e 30
40 0
0 100 200 300 400 500 600
Temperature (°C) Universal V4.1D TA Instruments

28. Materials Characterization Lab
www.mri.psu.edu/mcl
Thermal Characterization is available according to International Standards:
Technique Industrial Standards
DSC, DTA ASTM C 351, D 3417, D 3418, D 3895, D 4565, E 793, E 794
DIN 51004, 51007, 53765, 65467
DIN EN 728
ISO 10837, 11357, 11409
Pressure DSC ASTM D 5483, D 6186, E 1782, E 1858, E 2009
TGA & STA (TGA-DSC/DTA) ASTM E 914, E 1131, E 1868
w. MS & FTIR / evolved gas analysis
DIN 51006
ISO 7111, 11358
DIL/TMA ASTM D 696, E 228, E 831, E 1363, E 1545, E 1824
Thermal Expansion & Sintering
DIN 53752
DMA ASTM D 4092, D 4065, D 4473, D 5023, D 5024, D 5026, D 5418, E 1640, E 1867
DIN 53440
DIN EN ISO 6721
DEA Dielectric Analysis ASTM E 2038, E 2039
Thermal Conductivity ASTM C 177, C 236, C 518, C 335, C 976, D 5470, E 1225, E 1530, F 433
ISO 8301, 8302
Flash / Thermal Diffusivity ASTM E 1461
DIN 30905
DIN EN 821

29. Materials Characterization Lab
www.mri.psu.edu/mcl
Thermal Analysis Books
• MACKENZIE, Differential Thermal Analysis, 1970
Vol. I Fundamentals
Vol. II Instrumentation and Techniques.
• Several books on specific materials.
• Thermal Analysis journals.
• North American Thermal Analysis Society (NATAS)

30. Materials Characterization Lab
www.mri.psu.edu/mcl
Acceptable sample forms:
Solids
Powders
Liquids

31. Materials Characterization Lab
www.mri.psu.edu/mcl
Gases used for regular thermal analysis:
Dry Air.
Nitrogen.
Argon.
Mix 40% Carbon Monoxide + 60% Carbon Dioxide.
Mix 5% Hydrogen + 95% Nitrogen or Argon.
Gases used for TGA/Mass Spec analysis:
Extra High Purity Argon or Nitrogen.

32. Materials Characterization Lab
www.mri.psu.edu/mcl
New Instruments
ASAP 2020 Accelerated Surface Area and Porosimetery Analyzer.
Unique Capability
• Two Independent
vacuum systems.
• Oil-free “dry” vacuum
pump.
• Intelligent degas
system.
• New long-duration
cryogen system.
• Automated selection of
gas
• Ability to connect to a
mass spec.

33. Materials Characterization Lab
www.mri.psu.edu/mcl
Ranges of pore sizes and techniques

34. Materials Characterization Lab
www.mri.psu.edu/mcl
Adsorption of gas on surface of solid
4
3
2
1

35. Materials Characterization Lab
www.mri.psu.edu/mcl
Adsorption Desorption Isotherm
Isotherm Linear Plot
(LICHRSP1) - Adsorption
(LICHRSP1) - Desorption
40
35
30
Quantity Adsorbed (cm³/g STP)
25
20
15
10
5
0
0.00 0.05 0.10 0.15 0.20 0.25 0.30 0.35 0.40 0.45 0.50 0.55 0.60 0.65 0.70 0.75 0.80 0.85 0.90 0.95 1.00
Relative Pressure (p/p°)

36. Materials Characterization Lab
www.mri.psu.edu/mcl
ASAP 2020 Chemisorption Option
Uses the static
volumetric technique to
determine the percent
metal dispersion, active
metal surface area,
size of active particles,
and surface acidity of
catalyst materials.

37. Materials Characterization Lab
www.mri.psu.edu/mcl
AutoChem II 2920

38. Materials Characterization Lab
www.mri.psu.edu/mcl
AutoChem II 2920
• Fully automated
catalyst
characterization.
• Probing active sites
On catalyst
surface.

39. Materials Characterization Lab
www.mri.psu.edu/mcl
AutoChem II 2920
• Adsorption
– Pulse
Chemisorption
• Temperature
Programmed Studies
– TPR
– TPD
– TPO

40. Materials Characterization Lab
www.mri.psu.edu/mcl
AutoChem II 2920
Residual Gas Analysis
• TCD - all gases
TCD
• Mass Spectrometer 100 200 300 400
– i-Propylamine (iPA)
– Ammonia (NH3) iPA
– Propylene (C3=) 100 200 300 400
NH3
• RGA confirms
decomposition of iPA 100 200 300 400
C3=
100 200 300 400

41. Materials Characterization Lab
www.mri.psu.edu/mcl
Thermal Analysis Charges
• Instrument Charge = $30/Sample.
• Training, data interpretation, sample set-up, etc) =
$30/hr.
• Consultation time to discuss your samples, data, etc is
free.

42. Materials Characterization Lab
www.mri.psu.edu/mcl
Campus resources- people
• Raafat Malek, 109 Materials Research Lab Building, Hastings Road
865-7341
rqm@psu.edu
• Jeff Shallenberger, 196 MRI Bldg
865-0337
jxs124@psu.edu
Other resources:
• www,mri.psu.edu/mcl/techniques/thermal.asp (links, applications, etc)
• MRI links to publications and abstract (Web of Science) searching
(www.mri.psu.edu/linkspubs/)
• The Libraries (http://www.lias.psu.edu/)