Thermal Analysis

SSK 4242
The Effect of Heat on Materials
Very important to human life – why ??? i) Weaker intra-molecular force

The effect of heat on materials: change in

molecular and atomic vibration and ionic movement

• Structural or shape change ▲

• Melting
• Decomposition a) CaCO3(s) CaO(s) + CO2(g)
b) NH4Cl(s) NH3(g) + HCl(g)
• Sintering
• evaporation

Oxidation: ii) Weaker inter-molecular force

2Ag(s) + ½O2 Ag2O(s)
4Al(s) + 3O2 2Al2O3(s)
C(s) + O2(g) CO2(g)
PbS(s) + 3O2(g) 2PbO(s) + 2SO2(g)
▲
a) BaCl2.2H2O(s) BaCl2(s) + 2H2O(g)
Reduction:
b) CuSO4.5H2O(s) CuSO4(s) + 5H2O(g)
a) CuO(s) + H2(g) Cu(s) + H2O(g)
b) SnO(s) + H2(g) Sn(s) + H2O(g)
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Thermal Events
In case more than one solid materials involved
in the heat treatment, more thermal events will
take place leading to:

• the formation of solid solution;

• the formation of an eutectic mixture;
• the formation of a new compound.
Table 1.1 Summary of the
heat effect on materials
Formation of a new compound:

Fe2O3(s) + MgO(s)
MgFe2O4(s) Table 1.2 The effect of
heat on solid materials

Double Decomposition:

NaCl(s) + AgBr(s)
AgCl(s) + NaBr(s)

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Table 1.2 The effect of heat on solid materials (Haines, 1995)

Effect Conclusion Example

Colour effect
Charred, burned with Organic, polymer Combustion of
little residues papers
Blackened with plenty Metal oxide is formed CuCO3 →
residues CuO + CO2
Metal changed into Oxidation 2 Mg + O2 →
powder 2 MgO

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Table 1.2 The effect of heat on solid materials (Haines, 1995) Cont’d.

Effect Conclusion Example

Melting Materials
Melt at low Covalent ? Organic
temperature
Melt at high Ionic salts NaCl
temperature

Sublime Materials
White sublimation The solid is easily NH4Cl
evaporated
Ammonium salts
Violet sublimation Iodine I2

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Table 1.2 The effect of heat on solid materials (Haines, 1995) Cont’d.

Effect Conclusion Example

Released Vapours
(characterised by other
tests)
Water droplets Hidrate CuSO4.5H2O
Oksigen Nitrate, chlorate 2KNO3 →
2KNO2 + O2
Nitrogen oxide (brown Nitrate 2AgNO3 →
fume) 2Ag + 2NO2 +
O2
Carbon dioxide Carbonate ZnCO3 → ZnO
+ CO2

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Table 1.2 The effect of heat on solid materials (Haines, 1995) Cont’d.

Effect Conclusion Example

Physical change
Maleable Plastic at greater than Tg
Expansion Normal expansion
(a) gradual Phase change
(b) abrupt
Swelling Some swelling materials Polyphosphate
Shrinkage Some strained polymers Fibres
No effect Oxide that is stable towards MgO, Al2O3
heat or very low temperature

Return
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Heat Capacity

All materials have their own heat capacities

…an ability for the materials to absorb and keep the heat energy …

Mechanisms of retaining heat energy:

a) Solid materials The heat energy is kept via atomic vibration about
a min position around the atom in the lattice

b) Metallic materials The heat energy is also kept via the electronic
movement of the metal

c) Liquid materials The heat energy is kept via the rotational

movement of the atoms, therefore liquids
generally have greater heat capacity than the
solid materials.

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Heat Capacity (Cp)
…the amount of heat that is required to raise the temperature of a body by 1 Kelvin…

• The absorbed heat is stored as enthalpy

• Cp is also a measure of the amount of enthalpy change when the body
temperature is raised by 1 Kelvin

Cp = ∆H / ∆T

Table 1.3 Parameters and

techniques in the
measurement of heat effect

Definition of Thermal Analysis:

Thermal analysis is defined as a group of techniques
where the properties of samples are monitored versus
time or temperature while the sample’s temperature is
controlled under certain atmosphere
International Confederation for Thermal Analysis and Calorimetry (ICTAC)

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Heat Capacity (Cp)
…the amount of heat that is required to raise the temperature of a body by 1 Kelvin…

• The absorbed heat is stored as enthalpy

• Cp is also a measure of the amount of enthalpy change when the body
temperature is raised by 1 Kelvin

Cp = ∆H / ∆T

Table 1.3 Parameters and

techniques in the
measurement of heat effect

Definition of Thermal Analysis:

Thermal analysis is defined as a group of techniques
where the properties of samples are monitored versus
time or temperature while the sample’s temperature is
controlled under certain atmosphere
International Confederation for Thermal Analysis and Calorimetry (ICTAC)

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Table 1.3 The parameters and techniques in the measurement of heat effect

Parameter Measuring Technique Abbreviation

Mass change with temperature Termogravimetry TG

Mass change with temperature change Derivative Termogravimetry DTG
Sample temperature change with Differential Thermal Analysis DTA
temperature
Enthalpy change with temperature Differential Scanning Calorimetry DSC

Dimensional change with temperature Termodilatometry

Change in mechanical properties with Thermomechanometry or TMA

temperature Dynamic Mechanical Analysis DMA
Change in optical properties with Thermoptometry/
temperature thermomicroscopy
Change in magnetic properties with Thermomagnetometry
temperature
Change in electrical properties with Thermoelectrometry
temperature

Return
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Temperature Control Programme

a) Heating or cooling at a constantly changing temperature
b) Heating at a constant temperature
c) Combination of (a) and (b) above.

Sample
• The material that is placed in the instrument at the beginning of
the experiment
• The reaction products

Thermogram

• The thermal analysis curve

• The experimental data in a graphic form

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Differential Thermal techniques:

These Involve measurement of the differential properties/values
between samples and the reference materials
Example: the differential thermal analysis (DTA) where the measured
parameter is the difference between the sample temperature
and the reference temperature

Derivative Thermal techniques:

These involve measurement or calculation of mathematical

derivation versus time

Example: the derivative thermogravimetry (DTG) that involves

measurement of the rate of mass loss (dm/dt) plotted versus
temperature, T.

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Measurement of Heat Effect

• Sample
• Reagent (Heat)
• Signal

Signal
Sample generating Heat
unit

Signal

Information about the sample

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Thermal Analysis Techniques, the Measured SSK 4242
Parameters and the Thermograms
The rate of mass change versus
the temperature change
Mass loss ∆m / ∆T
m

T T

a) Thermogravimetry (TG) b) Derivative Thermogravimetry (DTG)

The temperature difference between the

sample and the reference versus the
temperature change Heat flow versus the
temperature change
∆T
∆H / ∆T

T
T
c) Differential Thermal analysis (DTA) d) Differential Scanning Calorimetry (DSC)
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Conditions for Heat Effect Measurement

1. Measurement of the physical properties and the

sample temperature should be made
continuously,
2. Measurement and recording of both parameters
should be made automatically,
3. The temperature change of the sample
(increased or reduced) takes place at a constant
rate.

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Application of Thermal Analysis

Some examples of materials that can be studied by Thermal Analysis Methods

Asbestos Glass Catalysts

Liquid crystal Ceramics Metals and steels
Clay Minerals Explosives
Organic materials Inorganic chemicals Fats, oils and waxes
Organometallics Fertilizers Pharmaceuticals
Fuels Plastics Rubber
Textiles Foods Plant materials

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