THERMAL METHODS OF ANALYSIS

DIFFRENTIAL THERMAL ANALYSIS (DTA)

THERMO GRAVIMETRIC ANALYSIS (TGA)
DIFFERENTIAL SCANNING CALORIMETRY (DSC)

Dr. B. Madhu Harika

CONTENTS

 Introduction
 Types of Different Thermal Analysis
 TGA
 Principle
 Instrumentation
 Application
 DTA
 Principle
 Instrumentation
 Application
 DSC
 Principle
 Instrumentation
 Application
 Factor affecting to Thermal analysis
 References
INTRODUCTION
 THERMAL ANALYSIS –
Techniques in which a physical (thermal)
property of a substance is measured as a
function of temperature while the
substance is subjected to a controlled
temperature variation.1

THERMAL ANALYSIS means the analysis of

a change in a property of a sample, which
is related to an imposed temperature
alteration.2
When matter is heated, it undergoes
ƒ1) Physical Changes:- Phase change
such as melting Vaporization,
crystallization, transition between
crystal structures, change in
microstructures in metal alloy &
polymers,
2) Chemical Changes:- include reaction
to form new products, oxidation,
decomposition, dehydration, corrosion
 TYPES OF DIFFERENT THERMAL ANALYSIS
Properties Techniques Methods Abbreviations

Mass Thermogravimetry Thermogravimetric TGA

Analysis
Pressure Thermomanometry Thermomanometric TMA
Analysis
Electric Properties Thermoelectrometry Thermoelectric Analysis TEA

Optical Properties Thermooptometry Thermooptometric TOA

Analysis
Dimensions or Thermomechanometry Thermomechanical TMA
Mechanical Analysis
Properties
Temperature Thermometry Heating & Cooling Curve --
Analysis
Temperature Differential Thermometry Differential Thermal DTA
Difference Analysis

Heat flow Differential Scanning -- DSC

Difference Calorimetry
THERMOGRAVIMETRIC ANALYSIS (TGA)
Principle:-
The mass of a sample in a controlled atmosphere is
recorded continuously as a function of temperature or
time as the temperature of the sample is increased
(usually linearly with time).

 Measurements of changes in sample mass with temperature.

 The temperature is increased at constant rate for known initial
weight of substance & change in weight are recorded as function
of temperature at different interval of time.
 Note that mass is a measure of the amount of matter in a
sample, whereas weight refers to the effect of the gravitational
force on a mass.
 A plot of mass or mass percentage as a function of time is called
a thermogram or a thermal decomposition curve.
INSTRUMENTATION

1. Thermobalance
2. Furnace
3. Sample Holder
4. Temperature
measurement
5. Computer-Data
acquisition ,
processing &
control system
THERMOBALANCE
 The usual range of thermobalance, is from 1
to 1000 mg, with usual sample weighing
between 5 to 20 mg.
 It provide electronic signal to record the

change in mass.
Types of Thermobalance
 1) Null Point type balance

 2) Deflection type balance

• Important features of thermobalance
• 1) It should be Accurate.
• 2) It should be sensitive enough to study small
changes in weight of sample.
• 3) The rate of heating should be linear and
reproducible.
• 4) Capable of heating sample up to 15000C.
• 5) It could cover wide range of temperature.
• 6) Should have high degree of mechanical
strength.
• 7) Should have rapid response to weight
change.
 Null Point type balance
• In the null point balance system, when
there is a change in weight, the balance
beam will deviate from its usual position.
• A sensor detects this deviation and
initiates a force that will restore the
balance to the null position.
• This restoring force is proportional to the
change in weight.
 Deflection balance :
• When balance arm is deflected by a change in weight,
the relative illumination of photocells from light source
changes due to the movement of shutter attached to the
balance beam, resulting in flow of compensating current
through one of the pair of photocells.
• The current produced is proportional to the change in
sample weight and after amplification is passed to the
coil thus restoring it to its original position.
• There are two types of deflection balances,
– (i) Beam type and
– (ii) Cantilever type
VARIOUS POSITION OF BALANCE IN FURNACE
FURNACE

 Furnaces for TGA cover the range from ambient

temperature to l000°C,although some can be used
for temperatures up to 1600°C.
 Heating rates can often be selected from
0.1°C/min to 100°C/min.
 Some units can heat as rapidly as 200°C/min.
 Insulation and cooling of the exterior of the furnace
is required to avoid heat transfer to the balance.
 Nitrogen or argon is usually used to purge the
furnace and prevent oxidation of the sample.
SAMPLE HOLDER

 Samples are typically contained in

sample pans made of platinum,
aluminum, or alumina.
 Platinum is most often used because

of its inertness and ease of cleaning.

TEMPERATURE MEASUREMENT

 Thermocouple-
Wires- Platinum,
Rhodium, Chromium, Nickel

 Resistance Thermometers-
The electrical resistances of metallic conductors increase with
rising temperature
TG CURVE
Type (i) curves: The sample undergoes no
decomposition with loss of volatile products over
the temperature range shown.
Type (ii) curves: The rapid initial mass-loss
observed is characteristic of desorption or drying.
Type (iii) curves: represent decomposition of the
sample in a single stage.
Type (iv) curves: indicate multi-stage decomposition
with relatively stable intermediates.
Type (v) curves: represent multi-stage
decomposition, but in this example stable
intermediates are not formed.
Type (vi) curves: show a gain in mass as a result of
reaction of the sample with the surrounding
atmosphere.
Type (vii) curves: are not often encountered. The
product of an oxidation reaction decomposes
again at higher temperatures
APPLICATIONS
 Determination of purity & thermal stability
of primary & secondary standards.
 Determination of composition of complex

mixture & decomposition

 For study of sublimation behavior of

compound
 To study reaction kinetics
 Determination of Dehydration /

Desolvation
DIFFERENTIAL THERMAL ANALYSIS

Principle:-
Differential thermal analysis (DTA) is a technique in which the
difference in temperature between a substance and a
reference material is measured as a function of
temperature while the substance and reference material are
subjected to a controlled temperature program.

The differential temperature is plotted against temperature or time

is called DTA curve.
Both sample & reference material heated in controlled condition.
If any reaction (physical or Chemical changes ) takes place
temperature difference (∆T) will occur between sample &
reference material.
REFERENCE MATERIAL
 The reference material should have the following
characteristics:
(i) It should undergo no thermal events over the operating
temperature range.
(ii) It should not react with the sample holder or
thermocouple,
(iii) Both the thermal conductivity and the heat capacity of
the reference should be similar to those of the sample.
For inorganic samples- Alumina, and carborundum, SiC,
For organic compounds- octyl phthalate and silicone oil.
INSTRUMENTATION
1. Furnace
2. Sample Holder
3. Temperature
measurement
4. Computer-Data
acquisition ,
processing &
control system
FURNACE
 Both sample & reference material
match thermally & arranged
systematically with the furnace, so
that both are heated or cooled in
identical manner.
 The metal block surrounding the well

act as heat sink.

 Temperature of the heat sink slowly

increases by using internal heater.

 Its temperature range from ambient

temperature to l600°C
SAMPLE HOLDERS
 Sample holder called crucible are made up
of metallic (Aluminum , Platinum) &
ceramic (silica).
 Sample are usually 1- 10 mg for analysis.
 The dimension of two crucibles & cell well

are as nearly identical as possible.

TEMPERATURE MEASUREMENT
 Pair of thermocouples used in DTA.
DTA CURVE
 The initial decrease in T is due to the glass
transition. The glass transition temperature Tg
is the characteristic temperature at which
glassy amorphous polymers become flexible
or rubberlike.
 The two maxima are the result of exothermic
processes in which heat is evolved from the
sample, thus causing its temperature to rise.
 When heated to a characteristic temperature,
many amorphous polymers begin to
crystallize as microcrystals, giving off heat in
the process. Crystal formation is responsible
for the first exothermic peak
 The minimum labeled "melting" is the result
ofan endothermic process in which heat is
absorbed by the analyte.
 The second peak in the figure is endothermic
and involves melting of the microcrystals
formed in thc initial exothermic process. The
third peak is exothermic and is encountered
only if the heating is performed in the
presence of air or oxygen.
 The final negative change in ∆T results from
the endothermic decomposition of the polymer
to produce a variety of products.
APPLICATIONS
 DTA is a widely used tool for studying and characterizing
polymers. The types of physical and chemical changes in
polymeric materials that can be studied by DTA.
 DTA is also used in the ceramics and metals industry.
 DTA is used to study decomposition temperatures, phase
transitions, melting and crystallization points, and thermal
stability.
 An important use of DTA is for the generation of phase
diagrams and the study of phase transitions.
 The DTA method also provides a simple and accurate way of
determining the melting, boiling, and decomposition points of
organic compounds.
DIFFERENTIAL SCANNING CALORIMETRY
Principle:-
 Differential Scanning Calorimetry (DSC) is a Thermal Analysis

technique in which the heat flow rate (power) to the sample is

monitored against time or temperature while the temperature
of the sample, in a specified atmosphere, is programmed.

 It is measure heat into or out of sample.

 Differences in heat flow occur with the occurrence of two
major events-
1) The heat capacity of the sample which increses with
temperature
2) Transitions occur
INSTRUMENTATION
1. Furnace
2. Sample Holder
3. Temperature
measurement
4. Computer-Data
acquisition ,
processing &
control system
INSTRUMENTATION
 Typesof DSC
1) Power-compensated DSC
2) Heat-flux DSC
3) Modulated DSC
POWER-COMPENSATED DSC
In power-compensated DSC, the
temperatures of the sample and reference
are kept equal to each other while both
temperatures are increased or decreased
linearly. The power needed to maintain
the sample temperature equal to the
reference temperature is measured.
HEAT-FLUX DSC
 In heat-flux DSC, the difference in heat
flow into the sample and reference is
measured while the sample temperature is
changed at a constant rate. Both sample
and reference are heated by a single
heating unit.
MODULATED DSC
 Modulated DSC (MDSC) uses the same
heating and cell arrangement as the heat-
flux DSC method. In MDSC, a sinusoidal
function is superimposed on the overall
temperature program to produce a micro
heating and cooling cycle as the overall
temperature is steadily increased or
decreased.
DSC CURVE
APPLICATIONS
 Glass Transition Temperatures :-
Determination of the glass transition temperature T, is one of the most
important applications of DSC. The physical properties of a polymer
undergo dramatic changes at Tg, where the material goes from a
glassy to a rubbery state. At the glass transition, the polymer
undergoes changes in volume and expansion, heat flow and heat
capacity. The change in heat capacity is readily measured by DSC.
 Crystallinity and Crystallization Rate:-

In most cases DSC is one of the easiest methods for determining

levels of crystallinity.
Reaction Kinetics:- Many chemical reactions, such as polymer
formation reactions, are exothermic and readily monitored by DSC
methods.
FACTOR AFFECTING TO THERMAL
ANALYSIS
Instrumental
1) Furnace Heating rate-↑es heating rate , ↑es decomposition
2) Furnace atmosphere- pure intert gas like N2

Sample characteristics
1) Sample particle size
2) Weight of sample
REFERENCES
1. Douglas A. Skoog, Principles of
Instrumental Analysis, 6th Edition, 894-904.
2. Michael E. Brown ,Introduction to Thermal
Analysis Techniques and Applications, 2nd
Edition.
3. Gurdeep Chatwal , Instrumental methods
of chemical analysis : Analytical
Chemistry.
THANK YOU