Thermal

Materials Characterization Labwww.mri.psu.edu/mcl

Materials Characterization LaboratoryUniversity Park, PA 16802

R.I. Malek

Thermal Analysis


Personnel

• Raafat Malek, Director

• Magda Salama, Mass Spec, Thermal analysis.

• Tim Klinger, Mass Spec.


Outline• Definition• Uses• Information Provided• Techniques

• TGA, • DTA, DSC, SDT,• TMA, DMA•Thermal Expansion, Diffusivity

• Instruments

• Some Applications

• Reaction Kinetics

•New Instruments


Thermal Analysis is a series of techniques that measure materials properties as a function of temperature, time and atmosphere.

Definition


UsesResearch and Development:• Development and selection of new materials,

• Performance and evaluation of existing materials.

Quality Control:• Fingerprinting,

• Monitoring and certification.

• Troubleshooting.


Information Provided• Melting Point,

• Glass Transition,

• Crystallinity,

• Curing and Cross-Linking,

• Heat Capacity,

• Stability,

• Purity,

• Composition,

• Modulus of Expansion,

• Reaction Kinetics.


Techniques






Instruments at MRL

TGA/MASS SPECTROMETER


Balance Purge in

FurnacePurge in

FurnacePurge exit


New Mass Spectrometer




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


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


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


Thermal Decomposition of Gypsum in a Hermetic pan


Reaction of Liquid Crystal and PMMA


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


New Rocket Fuel from Nano Aluminum Powder


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


Reaction KineticsArrheneusArrheneus EquationEquation

K = A exp(-Ea /RT)

K = Reaction Rate

A= Constant

Ea= Activation Energy

R= Gas Constant

T= Temperature



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


TGA/MASS SPEC of Carbon


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


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:


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)


Acceptable sample forms:

Solids

Powders

Liquids


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.


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.


Ranges of pore sizes and techniques


1

2

34

Adsorption of gas on surface of solid


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


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.


AutoChem II 2920


• Fully automated catalyst characterization.

• Probing active sitesOn catalyst surface.

AutoChem II 2920


• Adsorption– Pulse

Chemisorption• Temperature

Programmed Studies– TPR– TPD– TPO

AutoChem II 2920


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


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.


Campus resources- people• Raafat Malek, 109 Materials Research Lab Building, Hastings Road

865-7341

[email protected]

• Jeff Shallenberger, 196 MRI Bldg

865-0337

[email protected]

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/)

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