Thermogravimetric Analysis

(TGA) & Differential Scanning

Calorimetry (DSC)

Mark McKinnon
Lab Test Methods Day 2014

6/25/2014
 Background
Thermogravimetric Analysis (TGA)
Background

Governing Principles
Test method capable of measuring the mass
Operational Procedure evolution of a milligram-scale sample.
Data Analysis Gas atmosphere is well defined at all times during
the experiment.
Limitations
The atmospheric temperature is well-defined and
Sensitivity Analysis follows a pre-defined program.
Tips for Operation Data Collected:
Additional Information Mass of sample with respect to Time/Temperature.
Properties/Parameters Determined from Data:
Heterogeneous Reaction/Thermal Degradation Kinetics,
Temperature Range for Pyrolysis

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 Background
Differential Scanning Calorimetry (DSC)
Background

Governing Principles
Test method capable of measuring the heat flow
Operational Procedure rate to a milligram-scale sample.
Data Analysis Gas atmosphere is well-defined at all times during
the experiment.
Limitations
The atmospheric temperature is well-defined and
Sensitivity Analysis follows a pre-defined program.
Tips for Operation Data Collected:
Additional Information Heat flow to sample with respect to Time/Temperature.
Properties/Parameters Determined from Data:
Heat Capacity, Enthalpy of Melting/Fusion, Enthalpy of
Reaction/Thermal Degradation, Glass Transition
Temperature.

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 Governing Principles
Background
Heat Flux DSC
Governing Principles

Operational Procedure

0
Data Analysis

Limitations
Sensitivity Analysis
Power Compensation DSC
Tips for Operation
Power is varied such that:
Additional Information

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 Governing Principles
Background
TGA
Governing Principles
Micro-thermobalance measures any changes in the
Operational Procedure mass of the sample, whether due to adsorption of
oxygen, thermal degradation, oxidation, or other
Data Analysis heterogeneous reactions.
Limitations

Sensitivity Analysis

Tips for Operation

Additional Information

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 Governing Principles
Background
Netzsch Simultaneous Thermal Analyzer (STA)
Governing Principles
Incorporates TGA and DSC to measure mass
Operational Procedure change and heat flow rate simultaneously.
Data Analysis

Limitations

Sensitivity Analysis

Tips for Operation

Additional Information

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 Operational Procedure
Background
TGA & DSC
Governing Principles
1. Conduct baseline experiment with empty sample
Operational Procedure
crucible along a pre-defined temperature program in
a well-defined gas atmosphere.
Data Analysis 2. Prepare sample crucible by evenly packing sample
material into crucible and measure mass of entire
Limitations
crucible.
Sensitivity Analysis 3. Conduct experiment with sample along the same
temperature program in the same gas atmosphere as
Tips for Operation
in the baseline experiment.
Additional Information
4. Allow furnace to cool and clean the sample crucible
used in experiment.

Considerations:
Temperature, Heating Rate, Sample Size

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 Data Analysis
Background
TGA/DSC
Governing Principles

Operational Procedure

Data Analysis

Limitations

Sensitivity Analysis

Tips for Operation

Additional Information

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 Data Analysis
Background
TGA
Governing Principles

Operational Procedure

Data Analysis

Limitations

Sensitivity Analysis

Tips for Operation

Additional Information

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 Data Analysis
Background
TGA
Governing Principles
A general homogeneous reaction is of the form:
Operational Procedure
The rate of the reaction is assumed to be the product of a
Data Analysis rate constant k and a function of the concentration of
reactants and products. Where k is given by:
Limitations

/
Sensitivity Analysis

Tips for Operation

A similar analysis can be applied to heterogeneous
Additional Information reactions:

Concentration does not hold the same meaning with

heterogeneous reactions, and degree of reaction or
conversion is used:
/

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 Data Analysis
Background
TGA
Governing Principles
For constant heating rate measurements ( = ):
Operational Procedure

Data Analysis
1

Limitations 1
Sensitivity Analysis
1
Tips for Operation

Additional Information Where:
1

Many methods to determine A, E, and functional form of

or .

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 Data Analysis
Background
TGA/DSC
Governing Principles

Operational Procedure

Data Analysis

Limitations

Sensitivity Analysis

Tips for Operation

Additional Information

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 Data Analysis
Background
DSC
Governing Principles
Thermal events in the sample manifest as deviations from the
Operational Procedure baseline, most likely as exothermic or endothermic peaks.
Data Analysis

Limitations
Specific heat capacity is determined by comparing the heat
Sensitivity Analysis flow rate curves yielded from the sample and a standard
reference:
Tips for Operation

Additional Information

displacement

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 Limitations
Background
TGA
Governing Principles Only provides meaningful data when a change in mass
occurs.
Operational Procedure
Some liquids can be measured, but this is generally very
Data Analysis difficult to do.
Limitations Very small samples are used, so non-homogeneous
materials generally cannot be tested
Sensitivity Analysis
DSC
Tips for Operation
Very sensitive to any change in the sample or
Additional Information crucible.
Requires very good thermal contact with bottom of
sample crucible
Very sensitive to heating rate

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 Sensitivity Analysis
Background
TGA and DSC are both sensitive to the
Governing Principles heating rate and sample masses and either
Operational Procedure can result in shifts in the temperature.
Data Analysis
1.2 0.006
Limitations
1 0.005

Sensitivity Analysis

NormalizedMLR
0.8 3K/min 0.004
10K/min
Mass

Tips for Operation 30K/min 10K/min

0.6 0.003 30K/min
3K/min

Additional Information 0.4 0.002

0.2 0.001

0 0
300 400 500 600 700 800 900 1000 1100 1200 300 500 700 900 1100
Temperature(K) Temperature(K)

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 Tips for Operation
Background Make sure sample and reference crucibles are perfectly
Governing Principles
clean prior to tests.

Operational Procedure
For heat capacity determination make sure that
Data Analysis orientation of sample and reference crucibles are
consistent between all replicant tests.
Limitations

Sensitivity Analysis Make sure the crucible material will not react or interfere
Tips for Operation
with the sample material and vice versa.

Additional Information
Always build in an isothermal period prior to linear heating
to allow the sample to reach equilibrium with the furnace
conditions.

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 Additional Information
Background Brown, Michael E. 1988. Introduction to Thermal Analysis:
Governing Principles
Techniques and Applications. New York, NY: Chapman and
Hall
Operational Procedure

Data Analysis Hohne, Gunther, Hemminger, Wolfgang F., Flammersheim, H.J.

2003. Differential Scanning Calorimetry 2 ed. New York, NY:
Limitations Springer
Sensitivity Analysis

Tips for Operation

Additional Information

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Thank you!
Questions?

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