Concept, instrumentation and applications

Thermal methods
In the beginning ...
Melting point determination
The melting point of a substance is a key property that helps to determines the working range of that substance. The melting point can
help to determine the identity of a substance and is related to the purity of the substance.

Thermometer

Fisher-Johns melting point apparatus

Sample
Modern melting
point apparatus

Thiele’s tube melting point apparatus

Introduction
Well-known thermal methods
Introduction
This section focus on thermal methods that mainly give information about the chemical properties of matter. In these methods the
sample is subjected to a temperature programme while measuring the value of a temperature dependant variable.

Thermal analysis is especially useful in the analysis of polymers , food and pharmaceuticals .
A very brief introduction to polymers
Addition polymerisation

Condensation polymerisation
A very brief introduction to polymers
Orientation of side chains in space
A very brief introduction to polymers
Relationship between the structures and properties of polymers

The chains of stereoregular polymers are able to pack closely in a regular fashion and thus form crystalline regions. The intermolecular forces
between chains in these regions are larger than in other parts of the polymer.

Crystalline polymers tend to have greater mechanical strengths, higher melting points, and higher densities than amorphous polymers. They are
usually much less transparent because light is reflected or scattered at the boundary between the crystalline and amorphous parts of the polymer.

No polymer is completely crystalline. There are always amorpous regions present.

A very brief introduction to polymers
Relationship between the crystallinity and properties of polymers
A very brief introduction to polymers
Summary of the difference between amorphous and semi-crystalline polymers

Two temperatures, Tg and Tm, often characterise a polymer’s behaviour on heating:

Tg, the glass transition temperature, is the temperature at which a hard amorphous polymer becomes soft. A fully crystalline material has no Tg.
however, since all polymers have some amorphous regions polymers will all have a Tg value.

Tm, the melt transition temperature (melting point), is the temperature at which the crystalline regions of the polymer melt to become amorphous.
More ordered polymers have higher Tm values. which a hard amorphous polymer becomes soft.
A very brief introduction to polymers
Classification of polymers
Which properties are measured with thermal analysis techniques?
Specific heat capacity Cp
The specific heat value is essential in calculating energy transfers
for coolant and heating systems. It describes the amount of energy
that must be supplied or withdrawn from a material in order to
increase or decrease its temperature by a given amount.

In the food manufacturing industry, the specific heats of soups,

stews, juices milk, and other fluids are carefully measured to
assure that adequate pasteurisation or sterilisation can be
accomplished to assure food safety in the thermal processing of
packaged foods. Knowledge of the specific heat capacity of a
material is, therefore, important in the design of processes such as
chilling, freezing, warming, sterilisation and cooking.

Sterilisation
Thermogravimetric analysis [TGA]
The concept
The change in mass of a sample on heating is measured.

Instrumentation
In general, the balance is designed so that a change in sample weight
generates an electrical signal proportional to the weight change. The
electrical signal is transformed into weight or weight loss by the data
processing system and plotted on the y-axis of the thermal curve.

Electrobalance for a TGA instrument

As the mass changes during heating, the balance arm tips, resulting in a
change in the amount of light reaching the photocell. This generates a
Layout of a TGA instrument current to restore the arm position. The current is proportional to the
change in mass of the sample.
Thermogravimetric analysis [TGA]
Applications
Determination of correct drying temperatures for precipitates in gravimetric analysis.
Identification of gasses given off when the temperature of a sample is increased.

Decomposition of calcium oxalate monohydrate, CaC2O4·H2O.

Thermogravimetric analysis [TGA]
Applications
Determination of the thermal stability of organic compounds and polymers (fibres, plastics, rubbers).

TGA thermal curves showing the decomposition temperatures of some common

polymers: polyvinylchloride (PVC); polymethylmethacrylate; (PMMA), high-density High capacity TGA
polyethylene (HDPE), polytetrafluoroethylene; (PTFE) and polyimide (PI).
Thermogravimetric analysis [TGA]
Applications
Mass detector in kinetic studies, for example in the investigation of the oxidation of metals.

Derivative thermogravimetry
The first derivative of the TGA curve is plotted against temperature.

DTG

TGA and DTG thermal curves of a pure sample of hydrated

o
sodium silicate. The TGA mass loss from 50 – 150 C
shows water loss, but does not give much detail. The first
derivative plot (DTG) clearly shows three separate mass
TGA losses due to water bound in different forms.
Differential thermal analysis [DTA]

Most manufacturers no longer make true DTA systems but have integrated DTA and TGA systems. These systems are being replaced
by TGA-DSC instruments.

Basic operating principle

The temperature difference between a sample and an inert reference material (DT = Ts - TR ) is measured as both are subjected to identical heat
treatments

Any process in the sample (S) that absorbs or liberates

heat, will show up as a temperature difference between
the sample and reference (R).
Differential scanning calorimetry [DSC]
Basic operating principle
The sample and reference are maintained at the same temperature, even during a thermal event in the sample.

The heat flows required to maintain zero temperature differential between the sample and the reference is measured.

Video 1
DSC-TGA

Any process in the sample (S) that absorbs or liberates heat, will require that heat be added to the sample or the reference (R) to
maintain a zero temperature difference.
Sample preparation and handling
Accurately weigh samples (~3-20 mg)

Small sample pans of inert or treated metals (Al, Pt, Ni, quartz, graphene, etc.)

Video 2
Sample preparation

The same material and configuration should be used for the sample and the reference.

Material should completely cover the bottom of the pan to ensure good thermal contact

Avoid overfilling the pan to minimise thermal lag from the bulk of the material to the sensor

Smaller sample masses and low heating rates increase resolution.

Sample preparation and handling
Hermitically (airtight) sealed pan versus unsealed pan - it makes a big difference
The figure shows the thermal curves of obtained by analysing a hydrated active pharmaceutical ingredient (API).

Crystallisation

Melting

Hermitically
Hermitic pan sealed pan
with pinhole

Melting Melting

This pinhole allows water of hydration to escape from the pan, which also caused the conversion of the crystalline material into an amorphous form.
The amorphous form crystallized near 120 °C and then melted near 174 °C.
Differential scanning calorimetry [DSC]
Influence of sample mass on melting point
Differential scanning calorimetry [DSC]
Influence of heating rate on melting point
Calibration
Heat flow
Use of calibration standards of known heat capacity, such as sapphire, slow accurate heating rates (0.5–2.0°C/min), and similar sample and
reference pan weights

Calibrants
High purity Metals
Accurately known enthalpies
Thermally stable In 156.6 °C; 28.45 J/g; Sn 231.9 °C; Al 660.4 °C
Video 3
Light stable
Calibration
Non-hygroscopic Inorganics
Unreactive (pan, atmosphere) KNO3 128.7 °C; KClO4 299.4 °C

Organics
Polystyrene 105 °C; benzoic acid 122.3 °C; 147.3 J/g;
anthracene 216 °C; 161.9 J/g
Differential scanning calorimetry [DSC]
What can be determined with DSC?
Cross-linkage
Glass transitions
Melting and boiling points
Crystallisation time and temperature

Percent crystallinity

Heats of fusion and reaction (DH)

Specific heat capacity (Cp) Bakelite® - an example of a highly cross-linked polymer
Oxidative (thermal) stability
Curing is the formation of cross linkages byween polymer
Rate and degree of curing
chains or different parts of the same polymer chain.
Reaction kinetics

Purity

DTS and DSC curves have the same shape but uses different units. DSC can reveal the same information as DTA, with that added
advantage of accurate quantitative measurement of DH and Cp.
Differential scanning calorimetry [DSC]
Analysis of polymers

DSC DTA

Idealised DSC and DTA curve of a semi crystalline polymer with the ability to crosslink.
Differential scanning calorimetry [DSC]
Glass transition, melting point and decomposition temperature

Amorphous polymer Semi-crystalline polymer

Peak absent

A 100% crystalline material will have no Tg value.

Differential scanning calorimetry [DSC]
Glass transition
At the glass transition temperature, Tg, a polymer goes from a glassy, rigid state to a rubbery state as the temperature now permits
large-scale molecular motion.

Appears as a step (endothermic direction) in the DSC curve.

Differential scanning calorimetry [DSC]
Heat of fusion and heat of reaction

The heat of fusion and heat of reaction is determined by integrating the melting point curve.

DSC curve of polyethylene terephthalate (PET).

Tg = 78.89oC, crystallisation begins at 137.16oC,
and the energy released is 36,36 J·g-1. Melting
o -1 Crystalisation
begins at 232,32 C and 40,13 J·g is released.
Integral = 36.36 J·g-1

Calibration
The DSC must be calibrated using a substance with a known DH value, for example indium.
Differential scanning calorimetry [DSC]
Heat capacity

Calibration
The DSC must be calibrated using a substance with a known Cp value, such as saphire.
Differential scanning calorimetry [DSC]
Purity determination using DSC
Impurities lower the melting point of an eutectic system.

Purity determination by DSC is based on Van’t Hoff equation [Physical Chemistry].

Applies to dilute solutions, i.e., nearly pure substances (purity ≥98%)

Note melting point onset Note different melting points

benzoic acid
Differential scanning calorimetry [DSC]
Determination of percentage crystallinity

The heat of fusion is a useful measure of the percent crystallinity of a polymer.

The percent crystallinity is calculated from calibration with either a 100% crystalline sample or a sample of known crystallinity.

The first two samples in the table above are identical in percent crystallinity and in their melting behaviour; the third sample, however, has a lower
percent crystallinity and a sharper melting profile (compare the melt onset and melt peak temperature columns). This tells the polymer chemist that
sample 3 has been processed differently and will have different physical and mechanical properties than samples 1 and 2.
Differential scanning calorimetry [DSC]
Heating a sample more than once
Analysis of the acetaminophen [Active pharmaceutical ingredient (API) in paracetamol].

H
HO N
1 Video 4
O Summary of DSC

Acetaminophen