Download - Thermal
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Materials Characterization Labwww.mri.psu.edu/mcl
Materials Characterization LaboratoryUniversity Park, PA 16802
R.I. Malek
Thermal Analysis
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Materials Characterization Labwww.mri.psu.edu/mcl
Personnel
• Raafat Malek, Director
• Magda Salama, Mass Spec, Thermal analysis.
• Tim Klinger, Mass Spec.
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Materials Characterization Labwww.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
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Materials Characterization Labwww.mri.psu.edu/mcl
Thermal Analysis is a series of techniques that measure materials properties as a function of temperature, time and atmosphere.
Definition
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Materials Characterization Labwww.mri.psu.edu/mcl
UsesResearch and Development:• Development and selection of new materials,
• Performance and evaluation of existing materials.
Quality Control:• Fingerprinting,
• Monitoring and certification.
• Troubleshooting.
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Materials Characterization Labwww.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.
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Materials Characterization Labwww.mri.psu.edu/mcl
Techniques
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Materials Characterization Labwww.mri.psu.edu/mcl
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Materials Characterization Labwww.mri.psu.edu/mcl
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Materials Characterization Labwww.mri.psu.edu/mcl
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Materials Characterization Labwww.mri.psu.edu/mcl
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Materials Characterization Labwww.mri.psu.edu/mcl
Instruments at MRL
TGA/MASS SPECTROMETER
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Materials Characterization Labwww.mri.psu.edu/mcl
Balance Purge in
FurnacePurge in
FurnacePurge exit
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Materials Characterization Labwww.mri.psu.edu/mcl
New Mass Spectrometer
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Materials Characterization Labwww.mri.psu.edu/mcl
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Materials Characterization Labwww.mri.psu.edu/mcl
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Materials Characterization Labwww.mri.psu.edu/mcl
Amorphous Carbon
Carbon Nano Tubes
Determining the Percent of Amorphous Carbon in Carbon Nano Tubes
TGA/DTA
-0.4
-0.2
0.0
0.2
0.4
0.6
Tem
pera
ture
Diff
eren
ce (°
C/m
g)
60
70
80
90
100
110
Wei
ght (
%)
0 200 400 600 800
Temperature (°C)
Sample: AP8256R/365/90Size: 6.2373 mg
Comment: 5C/min up to 800C in air
TGA-DTAFile: C:...\8256R36590.001Operator: ClascidiaRun Date: 18-Nov-02 15:18
Exo Up Universal V2.6D TA Instruments
Percent Amorphous Carbon Left over During Nano Carbon Synthesis
Some Applications
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Materials Characterization Labwww.mri.psu.edu/mcl
TGAFerric Oxide
3.515% (1.014mg)
4.719% (1.362mg)
90
92
94
96
98
100
102
Wei
ght (
%)
0 200 400 600 800 1000
Temperature (°C)
Sample: Ferric OxideSize: 28.8550 mg
Comment: Purge with CO-CO2
TGAFile: C:...\Ferric Oxide.001Operator: MalekRun Date: 15-Oct-02 10:13
Universal V2.6D TA Instruments
Reduction of Ferric Oxide by a Mixture of CO + CO2
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Materials Characterization Labwww.mri.psu.edu/mcl
DSCDecomposition of Gypsum in a Hermetic Pan
Hemihydrate -----> Anhydrous(0.5 Molecules of Water Lost)
Dihydrate -----> Hemihydrate(1.5 Molecules of Water Lost)
146.64°C
135.45°C281.5J/g
193.26°C
179.37°C97.05J/g
-4
-3
-2
-1
0
1
Hea
t Flo
w (W
/g)
0 50 100 150 200 250 300
Temperature (°C)
Sample: Gypsum hermeticSize: 4.9000 mgMethod: Magda1.myth
DSCFile: C:...\New Data\Gypsum HOperator: MagdaRun Date: 21-Jul-00 10:02
Exo Up Universal V2.6D TA Instruments
Thermal Decomposition of Gypsum in a Hermetic pan
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Materials Characterization Labwww.mri.psu.edu/mcl
Reaction of Liquid Crystal and PMMA
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Materials Characterization Labwww.mri.psu.edu/mcl
53.45% (2Al --------> Al2O3)(1.849mg)
549.12°C
519.20°C6723.J/g
-30
-20
-10
0
10
Hea
t Flo
w (W
/g)
80
100
120
140
160
Wei
ght (
%)
200 400 600 800 1000
Temperature (°C)
Sample: Nano Al Powder for Rocket FuelSize: 3.4587 mg
Comment: Oxygenn Purge
DSC-TGAFile: C:...\Oxygen\Nanotech-1.001Operator: MalekRun Date: 1-Nov-02 08:50
Exo Up Universal V2.6D TA Instruments
New Rocket Fuel from Nano Aluminum Powder
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Materials Characterization Labwww.mri.psu.edu/mcl
123.00°C
124.40°C0.6033J/g
127.89°C
123.82°C0.6213J/g
-0.1
0.0
0.1
0.2
0.3
Hea
t Flo
w (W
/g)
0 50 100 150 200
Temperature (°C)
Sample: 72 Air 1200Size: 12.1000 mgMethod: BaTiO3Comment: s72 1.01BaO*TiO2 Air A3_49 1200c powder/Pt
DSCFile: D:\72a1200_pw_1.003Operator: FilimonovRun Date: 13-Feb-02 16:17Instrument: 2920 DSC V2.4F
Exo Up Universal V3.3B TA Instruments
Barium Titanate System
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Materials Characterization Labwww.mri.psu.edu/mcl
Reaction KineticsArrheneusArrheneus EquationEquation
K = A exp(-Ea /RT)
K = Reaction Rate
A= Constant
Ea= Activation Energy
R= Gas Constant
T= Temperature
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Materials Characterization Labwww.mri.psu.edu/mcl
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Materials Characterization Labwww.mri.psu.edu/mcl
10C/min5C/min1C/min0.1C/min0.05C/min
30
40
50
60
70
Wei
ght (
%)
500 550 600 650 700 750
Temperature (°C) Universal V2.6D TA Instruments
Decomposition of Calcium Oxalate at different heating ratesThird weight loss
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Materials Characterization Labwww.mri.psu.edu/mcl
TGA/MASS SPEC of Carbon
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Materials Characterization Labwww.mri.psu.edu/mcl
TGA m/e 44
m/e 43
m/e 41
m/e 30
m/e 15
CO2
C3H7
CxHy
CH3
H2
C2H6
m/e 2
0
5
10
15
20
25
30
Ion
Curr
ent
(nA
)
40
60
80
100
Wei
ght
(%)
0 100 200 300 400 500 600
Temperature (°C)
Mass Spec/ Magda–––––––
Universal V4.1D TA Instruments
TGA/MASS SPEC OF NEW CARBON FUEL
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Materials Characterization Labwww.mri.psu.edu/mcl
Technique Industrial Standards
ASTM C 351, D 3417, D 3418, D 3895, D 4565, E 793, E 794
DIN 51004, 51007, 53765, 65467
DIN EN 728
DSC, DTA
ISO 10837, 11357, 11409
Pressure DSC ASTM D 5483, D 6186, E 1782, E 1858, E 2009
ASTM E 914, E 1131, E 1868
DIN 51006
TGA & STA (TGA-DSC/DTA) w. MS & FTIR / evolved gas analysis
ISO 7111, 11358
ASTM D 696, E 228, E 831, E 1363, E 1545, E 1824 DIL/TMA Thermal Expansion & Sintering
DIN 53752
ASTM D 4092, D 4065, D 4473, D 5023, D 5024, D 5026, D 5418, E 1640, E 1867
DIN 53440
DMA
DIN EN ISO 6721
DEA Dielectric Analysis ASTM E 2038, E 2039
ASTM C 177, C 236, C 518, C 335, C 976, D 5470, E 1225, E 1530, F 433 Thermal Conductivity
ISO 8301, 8302
ASTM E 1461
DIN 30905
Flash / Thermal Diffusivity
DIN EN 821
Thermal Characterization is available according to International Standards:
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Materials Characterization Labwww.mri.psu.edu/mcl
Thermal Analysis Books
• MACKENZIE, Differential Thermal Analysis, 1970
Vol. I FundamentalsVol. II Instrumentation and Techniques.
• Several books on specific materials.
• Thermal Analysis journals.
• North American Thermal Analysis Society (NATAS)
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Materials Characterization Labwww.mri.psu.edu/mcl
Acceptable sample forms:
Solids
Powders
Liquids
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Materials Characterization Labwww.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.
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Materials Characterization Labwww.mri.psu.edu/mcl
ASAP 2020 Accelerated Surface Area and Porosimetery Analyzer. New Instruments
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.
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Materials Characterization Labwww.mri.psu.edu/mcl
Ranges of pore sizes and techniques
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Materials Characterization Labwww.mri.psu.edu/mcl
1
2
34
Adsorption of gas on surface of solid
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Materials Characterization Labwww.mri.psu.edu/mcl
Relative Pressure (p/p°)0.000.00 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
Qua
ntity
Ads
orbe
d (c
m³/g
STP
)
00
5
10
15
20
25
30
35
40
(LICHRSP1) - Adsorption(LICHRSP1) - Desorption
Isotherm Linear Plot
Adsorption Desorption Isotherm
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Materials Characterization Labwww.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.
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Materials Characterization Labwww.mri.psu.edu/mcl
AutoChem II 2920
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Materials Characterization Labwww.mri.psu.edu/mcl
• Fully automated catalyst characterization.
• Probing active sitesOn catalyst surface.
AutoChem II 2920
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Materials Characterization Labwww.mri.psu.edu/mcl
• Adsorption– Pulse
Chemisorption• Temperature
Programmed Studies– TPR– TPD– TPO
AutoChem II 2920
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Materials Characterization Labwww.mri.psu.edu/mcl
Residual Gas Analysis• TCD - all gases• Mass Spectrometer
– i-Propylamine (iPA)– Ammonia (NH3)– Propylene (C3=)
• RGA confirms decomposition of iPA
100 200 300 400
TCD
100 200 300 400
NH3100 200 300 400
iPA
100 200 300 400
C3=
AutoChem II 2920
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Materials Characterization Labwww.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.
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Materials Characterization Labwww.mri.psu.edu/mcl
Campus resources- people• Raafat Malek, 109 Materials Research Lab Building, Hastings Road
865-7341
• Jeff Shallenberger, 196 MRI Bldg
865-0337
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/)