Thermal Methods

• Theory
• Instrumentation

• Thermal methods
 Physical properties of a substance are evaluated as
a function of temperature
 May include reaction products
 Temperature is controlled
 Methods
 Thermogravimetry
 Differential thermal analysis
 Differential scanning calorimetry

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 Thermogravimetric (TGA)
• Thermogravimetry is one of the oldest thermal
analytical procedures
 has been used extensively in the study of polymeric
systems
• involves monitoring the weight loss of the sample in a
given atmosphere as a function of temperature
 N2, O2, air, He
 Ambient to 1000 °C
 Can record the first derivative of the mass loss

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 Thermogravimetric
• MS can be coupled to TGA
 On line analysis
 Evolution of gas
• evaluation of the thermal decomposition kinetics of materials
 Polymers
 Resins
 rubbers
 provides information on thermal stability
• provide information on the bulk composition of compounds
 Oxidation
 heat resistance
 the amount of water
 compositional analysis
 measurement of ash content in a sample

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20-4
 Analysis of Resin
100
7.831%
95 152.19 °C

90
Weight loss (%)

85

80

75

70

65
0 100 200 300 400 500
Temperature (°C)

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Table 10. Phenomenological data on the thermal decomposition of the phenolic resins

Resin T1, ˚C T2, ˚C Weight loss at 500˚C, %

PF 241.62 - 17

CF 148.84 - 40

RF 152.19 - 32

CQF 145.48 221.53 30

RQF 155.54 292.51 24

Table 11. Phenomenological data on the thermal decomposition of the metal complexes of phenolic
resins

Resin T1, ˚C T2, ˚C T3, ˚C T4, ˚C Weight

complex loss
at 500˚C,
%
PF-Eu 243.42 - - - 18

CF-Eu 172.31 445.06 - - 29

RF-Eu 193.55 457.36 - - 32 20-6
CQF-Eu 163.37 290.80 361.22 431.65 25
RQF-Eu 172.31 300.00 361.22 451.77 26
 Differential thermal analysis
• temperature difference between a substance and a
reference material is measured as a function of
temperature
 substance and reference material are subjected
controlled temperature
 emissions of heat (exothermic)
 absorptions of heat (endothermic)
* comparison with a passive material such as
alumina
• Can be used to identify samples
 Clay materials
• Peak areas depend upon sample mass and enthalpy
 A=-kGmH
 A= peak area, G is geometry factor, k is
constant related to thermal conductivity 20-7
New Zealand Halloysite. Premium

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 Differential Scanning Calorimetry
• Differences in heat flow are measured as a function of
temperature
 Sample and reference
 Energy difference measured
• Power Compensated DSC
 Two furnaces
 Heat flow evaluated
 Difference in power input montiored
 In watts
• Useful for glass transition temperatures
• Purity of drug samples

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 Automated methods
• Automatic
 No feedback
• Automated
 Includes feedback
• Different methods
 Discrete/batch
 sample remains isolated throughout
 Continuous
 sample introduced into stream
* Simpler instrumentation
* more efficient

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 Flow Injection Analysis
• Samples carried by flow
• Flow can have
chromatographic
properties
 Good behavior in
system

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20-13
Diffusion processes

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