THERMOGRAVIMETRIC

ANALYSIS(TGA)
Contents:
 Introduction
 Principle
 Types
 Instrumentation
 Result Discussion
 Factors
 Applications
Thermal analysis
 Thermal analysis is a branch of materials science where the
properties of materials are studied as they change with
temperature.
 When matter is heated, it undergoes certain physical and
chemical changes.
 Physical changes include phase changes such as melting,
vaporization, crystallization etc.
 Chemical changes include reactions to form new products,
oxidation, decomposition etc.
 These physical and chemical changes take place over a wide
temperature range.
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Types of Thermal Analysis
S.no Name of the technique Abbreviation Instrument Parameter Graph
of the employed measured
technique
1 Thermogravimetery T.G Thermobalan Mass Mass or
ce weight vs
Temperature
or Time
2 Thermometric titration T.T Calorimeter Temperature Temperature
vs titrant
volume
3 Evolved Gas Detection E.G.D Thermal Thermal T.C vs
Conductivity Conductivity Temperature
Cell (T.C)
4 Electrical Conductivity E.C Electrometer Resistance (R) R or I vs
or Current(I) Temperature 4
Introduction of Thermogravimetric
Analysis(TGA)
 Thermogravimetric analysis or thermal gravimetric analysis
(TGA) is a method of thermal analysis in which changes in
physical and chemical properties of materials are measured as
a function of increasing temperature or as a function of time.
 "It is a technique where by weight of substance in an
environment heated or cooled at a controlled rate, is recorded
as a function of time or temperature.
 Measurements are used primarily to determine the
composition of materials and to predict their thermal stability.
 Processes occurring without change in mass (e.g. Physical
transitions ) cannot be studied by TG.

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Principle
A TG analysis is performed by
gradually raising the
temperature of a sample in a furnace as its weight is
measured on an analytical balance that remains outside of
the furnace. In TGA, mass loss is observed if a thermal event
involves loss of a component. Chemical reactions, such as
decomposition involve mass losses, whereas physical
changes such as melting do not.
The weight of the sample is plotted against temperature or
time to illustrate changes in the material such as loss of
solvent water of hydration in inorganic materials or
decomposition of the material.
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Types of TGA
There are different types of TGA available:
i. Isothermal or Static TGA: In this case, sample is maintained at
a constant temperature for a period of time during which
change in weight is recorded.
ii. Quasi-static TGA: In this technique, the sample is heated to a
constant weight at each of a series of increasing temperature.
iii. Dynamic TGA: In this type of analysis, the sample is
subjected to condition of a continuous increase in temperature
at a constant heating rate i.e. Usually linear with time.

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INSTRUMENTATION:

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Block Diagram of Thermobalance

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Components of Instrumentation

 Microbalance
 Sample Holder
 Furnace
 Furnace temperature Controller
 Recorder

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Microbalance:
 It is the most important component of Thermobalance.
 Microbalance is used to record a change in mass of

sample/substance

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Null Balances:

It consists of a sensor which detects the deviation from the

null point and restores the balance to its null point by means
of a restoring force.

Deflection Balances:
It involves the conversion of deviation directly into a record of
weight change.

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Sample Holder or Crucible
 The sample to be studied is placed in sample holder or
crucible. It is attached to the weighing arm of microbalance.
 There are different varieties of crucibles used. Some differ in

shape and size while some differ in materials used. They are
made from platinum, aluminum, quartz or alumina and some
other materials like graphite, stainless steel, glass, etc.
 Crucibles should have temperature at iment and must transfer

heat uniformly to sample.

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Different types of crucibles:
 Different types of crucibles are used for different materials.
 Flat crucibles with small lip are used for powdered sample

whereas walled crucibles are used for liquid samples.

Therefore, the form of crucibles used will determine the
temperature gradients in sample.

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Furnace:
 Temperature Range at which furnace is to be operated is up to
2000°C in some cases it may be up to 2400°C.
 Construction of furnace is such that, it allow easy access to the
sample holder and also to cool down rapidly after the completion of
run.
 Design of the furnace should be able to provide suitable smooth
input so that it can maintain either a linear heating programme or
fixed temp.
 For heating or maintaining temp inside furnace Nichrome and Pt-Rh
windings are to be used (1000°c & 1450°C ).
 Also Graphite tube furnace is used for obtaining higher temp, but
difficulty arises in the control and measurement of the temp
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Furnace temperature Controller

Maintains the control of throughout the process.

 It is brain of the thermobalance and directs the operation.
 It contains temperature sensor directly in contact with the

furnace, sending information to the programmer and thereby

controlling the electrical power sent to the furnace.

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Thermocouple:
. A thermocouple produces a temperature-dependent voltage
as a result of the thermoelectric effect, and this voltage can be
interpreted to measure temperature. Thermocouples are a
widely used type of temperature sensor.
Recorder:
A recorder records the change in weight in y axis and w.r.to
temperature on the x-axis. We get a thermogram.

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Sample Preparation
 Sample preparation has a significant effect in obtaining good
data.
 It is suggested that maximizing the surface area of the sample
in a TGA pan improves resolution and reproducibility of weight
loss temperatures.
 The sample weight affects the accuracy of weight loss
measurements.
 Typically 10-20mg of sample is preferred in most applications.
 Whereas, if the sample has volatiles 50-100mg of sample is
considered adequate.

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Working:
 A TGA consists of a container which is in the form of a
crucible for holding the sample (sample pan).
 a furnace for heating the given sample at a high temperature,

and an appropriate precision balance which can continuously

monitor the sample .
 That pan resides in a furnace and is heated or cooled during

the experiment.
 A sample purge gas controls the sample environment .

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 This gas may be inert gas such as Helium or Argon that
flows over the sample and exits through an exhaust.
 Finally the weight is recorded as a function of increasing

temperature.
 TGA instrument continuously weighs a sample as it is

heated to temperatures of up to 2000 °C .

 As the temperature increases, various components of the

sample are decomposed and the weight percentage of

each resulting mass change can be measured .
 Results are plotted with temperature on the X-axis and

mass loss on the Y-axis . The data can be adjusted using

curve smoothing.
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Factors:
 Two type of factors effect its functioning. These are:
 Instrumental factors
 Sample characteristics
Instrumental factors:
 Various types of instrumental factors are involved.
 Heating rate
 Effect of furnace atmosphere
 Sample Holder
Sample characteristics:

 Sample weight
 Sample particle size
 Heat of reaction
 Compactness of the sample
Explanation of instrumental factors:
 Effect of furnace atmosphere:
Decomposition temperature
Vacuum atmosphere
Inert Gas
It will remove entrapped air bubbles and help in the
decomposition.
Effect of heating rate:

Fast heating
rate High decomposition temperature

Slow heating Low decomposition temperature

rate
Effect of heating rate:
Sample holder:

Geometry Flat plates to deep crucibles

Glass
Materials Alumina
Ceramics
 Explanation of sample characteristics
 Weight of sample

Large
High decomposition
sample temperature
Sample particle size

 It effects as:

Small particle Fast decomposition

size Low temperature

Large particle slow decomposition

size High temperature
Heat of reaction
 Heat of reaction effects the difference between sample
temperature and furnace temperature.
 Endothermic or exothermic heat effect will cause the sample
temperature lead or lag the furnace temperature.
Compactness of the sample:

Compressed
High decomposition temperature
sample
Mechanism of weight change in TGA:
• Weight Loss:

Decomposition : Breaking apart of a chemical bond.

Evaporation : Loss of volatiles at elevated temperatures.

Reduction : interaction with hydrogen , ammonia etc(reducing

atmosphere).

Desorption : Separation of adsorbed parts from surface.

 Weight Gain :

Oxidation :interaction of sample with oxidizing atmosphere.

Adsorption

Absorption

All are kinetic processes.

Recording of results:
Results are recorded in form of TG curves that are plot of mass
change versus temperature or time.

TG curves are plotted with mass change on y-axis and

temperature or time on x-axis.
 TG curve description:
 The area (ATi) under TG Curve
is Plateau where no mass
Change occurs.

 Mass changes from

Temperature Ti to Tf .

 The temperature difference between Ti to Tf is reaction interval.

 The temperature where material loses its weight indicates
decomposition ,evaporation or desorption process.
 The temperature where no mass change occurs indicates its
kinetic stability.
 These temperature ranges indicate the physical properties of
compounds and hence use for their identification.
There are two temperatures of reaction.

 Ti (initial temperature) is the lowest temperature where mass

change begins.

 T f(final temperature)is the final temperature where process

has been completed.
 Calcium Oxalate Decomposition
 • 1 st Step

CaC2O4 •H2O (s) CaC2O4 (s) + H2O (g)

Calcium Oxalate Monohydrate Calcium Oxalate
 • 2 nd Step

CaC2O4 (s) CaCO3 (s) + CO (g)

Calcium Oxalate Calcium Carbonate
 • 3 rd Step

CaCO3 (s) CaO(s) + CO2 (g)

Calcium Carbonate Calcium Oxide
Applications:
 Thermal stability
 Kinetic studies
 Material characterization
 Analyze filler
 Curie point determination
 Analyze impurity content
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