THERMAL METHODS OF ANALYSIS

• Thermal analysis is a group of techniques in which a

physical property of a substance and/or its reaction
products is measured as a function of temperature while
the substance is subjected to a linear increase in
temperature @ 5 or 10 C.

• In this course, you will study three methods

Differential thermal analysis (DTA)
Differential Scanning Calorimetery (DSC)
ThermoGravimetric analysis (TGA)
• Reference Temperatures
• Melting point/ Freezing Temperature
• Glass transition temperature
• Phase transition temperature
• Boiling point
• Critical temperature
• Boyle Temperature
• Process Temperature
• Softening temperature
• Flow temperature
• Tack temperature
• The softening point is the • In VICAT bench method, it is the
temperature at which a material minimum temperature at which
softens beyond some arbitrary the material sticking on the hot
softness. It can be determined metallic bench starts converting
by itself into droplets.
• The Vicat method (ASTM-D1525) • The Melt Flow Index (MFI) is a
• Heat Deflection Test (ASTM-D648) measure of the ease of flow of the
melt of a thermoplastic polymer. It is
• Ring and ball method (ASTM E28-67/E28-99
or ASTM D36 or ASTM D6493 - 11) defined as the mass of polymer, in
grams, flowing in ten minutes
through a capillary of a specific
In VICAT bench method, it is the minimum diameter and length by a pressure
temperature at which the material starts
leaving a trail of its own on the hot metallic applied via prescribed alternative
bench whose temperature rise linearly along gravimetric weights for alternative
the length. prescribed temperatures
• Tack is defined as the ability of an Tack is a complex property
adhesive to form a bond with a • Bond formation depends on:
surface after brief contact under • Adherend surface properties - material,
light pressure. wettability or surface energy, roughness,
porosity.
• It is often thought of as a simple • Preparation - cleanliness, pre-
property to measure although in treatments, coating weight and
reality tack depends on such a uniformity, adhesive application, open or
drying time, environmental conditions
complex interaction of different experienced priorto bonding.
factors that no single value can • Physical and Chemical properties of the
characterize tack. adhesive - type, functional groups,
flowproperties, surface energy.
• Tack depends very strongly on • Bonding process - contact pressure,
the method by which it is duration of contact, rate of pressure
measured. change, thermal history, penetration
into surface.
 Differential Thermal Analysis (DTA)
• Principle: The basic principle involved is: the difference of
temperature (∆T) between the test sample(TS) and an inert reference
sample(TR) under controlled and identical conditions of heating or
cooling is recorded continuously as a function of temperature or time.
• The heat absorbed and emitted by a chemical system can be
estimated or determined.
• The changes are two types- exothermic and endothermic
• If endothermic- ∆T = TR – TS = +ve or TS – TR = -ve
• If exothermic- ∆T = TR – TS = -ve or TS – TR = +ve
Main Components of Therma Analyzer
• Furnace
• Sample and reference holder
• Temperature Indicator (Thermocouples)
• Environment control devices( Gas cylinder & regulator)
• Thermal Management system ( auto voltage regulator)
• Signal Pre- amplifier and Main amplifier
• Data Recorder/ Computer/ X-Y plotter
 TG/DTA Data of Calcium Oxalate
50 to 800°C @10°C/min, Nitrogen @150ml/min, Sample Weight
0.965mg, Platinum Pans, Data Interval 0.5sec
What can DSC measure?
•Glass transitions
•Melting and boiling points
•Crystallisation time and temperature
•Percent crystallinity
•Heats of fusion and reactions
•Specific heat capacity
•Oxidative/thermal stability
•Rate and degree of cure
•Reaction kinetics
•Purity

Technical Group Talk

DSC Thermogram

Oxidation
Heat Flow -> exothermic
Crystallisation Cross-Linking
(Cure)

Glass
Transition

Melting

Temperature
6

Technical Group Talk

 Influence of Sample Mass
0

Indium at Onset not

-2 10°C/minute influenced
Normalized Data 15mg by mass
10mg

4.0mg
-4
1.7mg
DSC Heat Flow (W/g)

1.0mg
0.6mg
-6
150 152 154 156 158 160 162 164 166
706 Temperature (°C)

Technical Group Talk

Effect of Heating Rate
on Indium Melting Temperature

-1
Heat Flow (W/g)

-2
heating rates = 2, 5, 10, 20°C/min
-3

-4

-5
154 156 158 160 162 164 166 168 170
Temperature ( ° C)
6

Technical Group Talk

Thermogravimetric Analysis (TGA)
• An Internationally accepted definition of
thermogravimetry

"It is a technique where by

weight of substance in an
environment heated or cooled
rate is recorded as a function of
time or temperature.
Wt vs temperature
 Type Of Thermogrvimetry
1. Isothermal / Static Thermogravimetry
2. Quasistatic Thermogravimetry
3. Dynamic Thermogravimetry
1.Isothermal/ Static Thermogravimetry: In this technique
the sample weight is recorded as a function of time at
constant temperature.
2.Qasistatic Thermogravimetry: In this technique the sample
is heated to constant weight at each of the series of
increasing temperature.
3. Dynamic Thermogravimetry: In this technique a sample is
heated in an environment whose temperature is changing
in predetermine manner generally at linear rate.

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Thermogravimetric Curve:
 A to B - Thermal stability
of material.
A
B  B to C -Weight loss.
 C – Procedural
decomposition
temperature.
 D- Final temperature
D
C

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Factor Affecting TGA Curve:

A. Instrumental factor:- B. Sample Characteristic:-

1. Effect of sample mass
1. Heating Rate 2. Effect of sample particle size
2. Furnace atmosphere 3. Effect of heat reaction
3. Sample Holder 4. Compactness of sample
5. Previous history of sample

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Instrumentation

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Components of Instrumentation:
A. Recording balance
B. Sample Holder
C. Furnace
D. Furnace temperature programmer/Controller
E. Recorder
F. Thermobalance

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Balance:-
Recording balance

1. Deflection balance
i. Beam type
ii. Spring/ Helical type
iii. Cantilever type
iv. Torsion type

2. Null balance
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1. Deflection balance:-
i. Beam type:-
A conversion of beam
deflection about the fulcrum
into a suitably identifiably
weight change.

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ii.Spring/Helical type:-

An elongation or contraction of
spring with weight change. This
changes the length of the
spring .

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iii. Cantilever type:-

• One end of the beam is fixed &

other end on which the sample
is placed, is free to undergo
deflection.

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iv. Torsion type:-

• In this type of balance the beam

is attach to torsion wire.
• The wire is fixed at one or both
ends so that deflection of beam
are proportional to weight
change.

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2. Null point balance:-
• In this balance there should be a
sensor to detect the deviation of
the balance to detect the null
position .

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Sample Holder:-
Types of sample holder:-
1.Shallow Pans
2.Deep crucibles
3.Loosely covered crucibles
4.Restort cups

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1.Shallow Pan:
Used for such sample necessary to eliminate diffusion
as a volatile material.
2. Deep Crucible:
Used to study industrial scale calcination & surface area
measurement.
3.Loosely curved crucible:
Used in self generated atom study.
4. Retord cups:
Useful in boiling point study.

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Furnace:-
 Position of furnace with respect to balance:

A B C

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The choice of furnace heating element and type of furnace depend
upon the rang being studies:-

Temperature Material
 1100˚c  Nichrome
 1100-1500˚c  Platinum /Alloy of rhodium
 1100- 1750 ˚c  Tungsten

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Temperature Measurement:-
 The most common method is thermocouple.
 The temperature 1100,chromel/alumel thermocouple are made up of
alloys of Pt and rhodium are used.
 Higher temperature tungsten or rhenium thermocouple are used.

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E. Recorder:-
Two Types:-
A. Time-base potentiometric strip chart recorder
B. X-Y recorder
Advantage:-
1. To check the heating rate of the furnace for linearity.
2. X,Y recorder we get curve having plot of weight directly against
temperature.

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Thermobalance:-
 It records continuously weight change of the sample as a function of
temperature.
 The sensitivity of balance depends on the size of the sample used.
 The temperature recorded to an accuracy of better than ±1%
 The weight loss recovered to an accuracy ±1%
 In market large number of balance are available.

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A Stanton Redcroft TG-750 Balance:-

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Advantage of TG- 750 over other balance:-
 Requires only small sample weight than other balance.
 It maintain fast heating rates with good resolution.
 Cooling time is very short.
 It useful for isothermal studies.

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Applications:-
 Purity and thermal stability.
 Solid state reaction.
 Decomposition of organic and inorganic compound.
 Determining composition of material.
 Corrosion of metals in various atmosphere.
 Pyrolysis of coal , petroleum and wood.
 Roasting and calcination of minerals.
 Evaluation of gravimetric precipitates.
 Oxidative and Reductive stability.
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