THERMOGRAVIMETRY ANALYSIS

(TGA)
 THERMAL ANALYSIS TECHNIQUES are those in
which a physical property of a substance or its reaction
products is measured as a function of temperature.
 Usually, the substance is subjected to a controlled program
during the analysis.
Sr.no Name of Abbreviati on Instrument Parameter Graph
technique of the employed measured
technique

1. Thermogravimetry TG Thermobalanc e Mass Mass vs.

Temp or
Time

2. Differential Thermal DTA DTA apparatus ∆T ∆T

analysis vs.Temp

3. Differential DSC Calorimeter dH. dt dH/dt vs.

Scanning Temp
Calorimetry
THERMOGRAVIMETRIC ANALYSIS (TGA)
Universally accepted definition is:
 ‘‘It is a technique whereby the weight of a substance, in an
environment heated or cooled at a controlled rate, is recorded
as a function of time or temperature.’’
 From the above definition , it follows that the basic requirements
are a method of heating (or cooling ) and a means of weighing.
There are three types of TGA:-
a) Isothermal or static TGA:- In this technique the sample weight
is recorded as a function of time at constant temp.
b) Quasi-static TGA:- In this technique the sample is heated to
constant weight at each of a series of increasing temperatures.
c) Dynamic TGA:- In this technique, the sample is heated in an
environment whose temp. is changing in a predetermined
manner, generally at a linear rate.
➢ In a TGA, the mass of a sample in a controlled atmosphere is
recorded continuously as a function of temp or time as the
temperature of the sample is increased (usually linearly with
time). A plot of mass or mass percentage as function of time is
called a thermogram or a thermal decomposition curve.
➢ TGA curves are characteristic of a given compound or
material due to the unique sequence of physical transitions
and chemical reactions that occur over definite temperature
ranges.
➢ The rates of these thermally induced processes are often a
function of the molecular structure. Changes in weight result
from physical and chemical bonds forming and breaking at
elevated temperatures.
INSTRUMENTATION:
 It consists of :-
1. The balance
2. Sample holders
3. The furnace
4. Recorder
5. Thermobalance
 1. THE BALANCE :-
Requirements of a good balance-
i. Its accuracy , sensitivity, reproducibility and capacity
should be similar to those of analytical balance.
ii. It should have an adequate range of automatic weight
adjustment.
iii. It should have a high degree of mechanical and
electronic stability.
iv. It should have a rapid response to weight changes.
v. It should be unaffected by vibration.
vi. The balance should be simple to operate and versatile.
 Recorder balances are of two types:
 1. Deflection-type instruments and
 2. Null-type instruments.
 Deflection Balances:
They are of following types:
 I. Beam Type- There occurs a conversion of beam
deflection about the fulcrum.
 ii. Helical Type- There occurs an elongation or
contraction of the spring with weight change. Transducers
are used for recording these changes in length of the
spring.
 iii. Cantilevered Beam- One end of beam is fixed and the
other end on which sample is placed is free to undergo
deflections.
 iv. Torsion Wire- Beam is attached to a taut wire
which acts as a fulcrum.
 Null-Point 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; either electrical or mechanical weight loading is
applied to the beam.
2.SAMPLE HOLDERS:-
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 (or ceramic),
quartz or alumina and some other materials like graphite,
stainless steel, glass, etc
 Different types of sample holders are as follows-
1. Shallow pans- These are used for such samples in which
diffusion is the rate controlling step. Volatile substances
produced during reaction must escape out which is determined
as weight loss.
 2. Deep Crucibles: These are used in such cases where side
reactions are required such as in study of industrial scale
calcinations, surface area measurements, etc.

 3. Loosely covered Crucibles: These are used in self-generated

atmospheric studies. Rate of temperature or weight loss is not
important because the studies are done isothermally.

 4. Retort Cups: These are used in boiling point studies. It

provides single plate of reflux for a boiling point determination.

 Different types of crucibles are used for different materials i.e.

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.
Alumina Crucible
Alumina Crucible (Ceramic Crucible) is the most commonly used crucible in
TGA experiments. It is relatively stable for most samples and doesn’t react
with the samples. In the range of room temperature to 1650°C, the alumina
crucible has no thermal reaction.
The melting point of the aluminum oxide crucible exceeds 1700℃, which
can be used repeatedly.
Under normal circumstances, the crucible used in the TGA
experiment is 70 µL alumina crucible, but sometimes other special
crucibles are also required for thermogravimetric experiments.
For a better synchronized DSC curve, can use a 40 µL aluminum
crucible with a temperature below 600 degrees Celsius.
If the sample has very few volatile components or is very uneven,
use as many samples as possible in this case. At this time, use a
larger crucible, such as 150 µL alumina crucible or 900 µL alumina
crucible.
3. FURNACE:-
The furnace and control system should be designed to produce a
linear heating rate over the whole working range of furnace.
 The choice of furnace heating element and type of furnace
depend the temp range being studied.
 For 1100˚C – Kanthal or Nichrome wire.
 For 1100˚C to 1500˚C- Platinum , alloy of platinum or rhodium
 For 1500˚C to 1750˚C-Platinum-rhodium alloy
 Above 1750˚C- Tungsten or molybdenum
 4. TEMPERATURE MEASUREMENT-
 i. Thermocouple is placed near the sample container and
has no contact with sample container. This arrangement in
not preferred in low-pressures.
 ii. The thermocouple is kept inside the sample holder
but not in contact with it. It responds to small
temperature changes only.
 iii. Thermocouple is placed either in contact with sample
or with sample container. This method is best and
commonly employed position of thermocouple in a
Thermobalance
5. RECORDER:
The recording systems are mainly of 2 types:
 1. Time-base potentiometric strip chart recorder.
 2. X-Y recorder.
 In some instruments, light beam galvanometer,
photographic paper recorders or one recorder with
two or more pens are also used.
 In the X-Y recorder, we get curves having plot of
weights directly against temperatures.
 However, the percentage mass change against
temperature or time would be more useful.
6. THERMOBALANCE-
A good thermobalance should have-
1. Should be capable of continuously recording the
weight changes.
2. Should cover a wide range of temp.
3. Temp should be recorded to an accuracy of better than
±1%
4.Recorded temp should be e
ideally the sample temp.
5.The wt. loss should be
recorded to an accuracy of
±1%.
FACTORS AFFECTING RESULTS-
INSTRUMENTAL FACTORS:
 HEATING RATE: If a substance is being heated at a fast
heating rate, the temperature of decomposition will be higher
than that obtained at a slower rate of heating.
 Eg.:- for a 10% decomposition of polystyrene, the
temperatures are : 375˚C for a heating rate of 1˚C / min and
394 ˚C for a heating rate of 5˚C / min
 EFFECT OF FURNACE ATMOSPHERE:
 The test samples are generally heated in the presence of an
inert gas, in order to remove the gases formed during sample
heating and also to prevent the occurrence of any undesirable
reactions. The common atmospheres involved in
thermogravimetry are as follows:
 1. Static air: In this type air from atmosphere is
allowed to flow through the furnace.
 2. Dynamic air: In this type compressed air from a cylinder
is allowed to pass through the furnace at a measured flow
rate.
 3. Inert atmosphere: Nitrogen gas (oxygen free) is used as inert
environment.
 SAMPLE HOLDER:
The geometry of the sample holder can change the slope of TG
curve. Sample holders range from flat plates to deep crucibles of
various capacities.

Materials used in their construction may vary from glass,

alumina, and ceramic compositions to various metals and
metallic alloys. When the atmosphere is solely the gas, the
shape of crucible has no effect on the slope of the curve.
Generally shallow dish is preferred as there is a rapid exchange
of gases between sample and the surrounding atmosphere.
 SAMPLE CHARACTERISTICS:
 Weight of the sample: If a large sample is used, there occurs a
deviation from linearity as the temperature rises, especially for an
exothermic reaction.
 Eg.: Evolution of CO during decomposition of calcium oxalate to
CaCO3.
 Sample particle size: With the particle size of smaller dimension
the decomposition takes place earlier, while with greater particle
size the decomposition proceeds only at higher temperatures.
 Eg.: TGA studies showed that Mg(OH)2 prepared by precipitation
method has a different temperature of decomposition from that of
the naturally occurring material. This factor shows that one should
be sure of the previous history of the sample
 Heat of reaction: This effect was studied by
Newkirk. The heat of reaction alters the difference
between the sample temperature and the furnace
temperature. If the heat effect is exothermic or endothermic,
this will cause the sample temperature to lead or lag behind
the furnace temperature.
 Compactness of the sample: A compressed sample will
decompose at higher temperatures than a loose sample.
TGA curve:

• The instrument used for

themo-gravimetry is a
programmed precision
balance for rise in temperature
known as Thermo-balance.

• Results are displayed by a plot

of mass change versus
temperature or time and are
known as Thermogravimetric
curves or TG curves.

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TGA curve:

• TG curves are normally plotted with the mass change (Dm) in

percentage on the y-axis and temperature (T) or time (t) on the
x-axis.

• There are two temperatures in the reaction, Ti(procedural

decomposition temp.) and Tf(final temp.) representing the
lowest temperature at which the onset of a mass change is seen
and the lowest temperature at which the process has been
completed respectively.

• The reaction temperature and interval (Tf-Ti) depend on the

experimental condition; therefore, they do not have any fixed
value.
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TGA curve of AgNO3 :

27
CLASSIFICATION OF TGS CURVES
Interpretation of TG Curves:
Types of TG Curves :TG curves are classified according to their shapes into
seven types.
Type A-this curves shows no mass change over the entire range of temperature.
It can be concluded that the decomposition temperature for sample is greater
than the temperature range of instrument.
Type B-this curves shows that there is large mass loss followed by mass
plateau and is formed when evaporation of volatile product(s) during drying,
desorption or polymerization takes place. If a non-interacting atmosphere is
present in the chamber, type B curve will change into type A curve.
Type C-this curve shows the single-stage decomposition temperatures (Ti and
Tf).
Type D-this curve shows the multi-stage decomposition processes where
reaction is resolved.
Type E-this curve shows the multi-stage decomposition reaction where reaction
is not resolved.
Type F-this curve shows the increase in mass in the presence of an interacting
atmosphere e.g. surface oxidation reactions.
Type G-this curve shows multiple reactions one after the other e.g. surface
oxidation reaction followed by decomposition of reaction product(s).
ADVANTAGES AND DISADVANTAGES:-
•Any type of solid can be analyzed, with minimal sample
preparation (e.g. powders, pellets, chunks, flakes etc)
• Minimum sample size ( at least 0.1mg)
• Qualitative or quantitative analysis
• Solid (or initially solid) samples only
•Data interpretation not always straightforward. Analysis in
combination with other techniques is often helpful.
APPLICATIONS:
 • Thermal stability/degradation investigation of organic or
inorganic materials, e.g. polymers, composites, glasses,
metals, minerals etc.
• Thermal stability/degradation investigations in inert
or oxidative atmospheres, or in vacuum
• Determination of organic/inorganic content of mixtures
• Curing kinetics (e.g, adhesives, polymers)
•Chemical composition measurements (using appropriate
reference standards, accurate quantification of sample
composition can be determined)
• Phase transition measurement (e.g. glass transition, clustering,
crystallinity, melting point)
 Thermal Stability
 Material characterization
 Compositional analysis
 Used to analyze filler content in polymers; carbon black in
oils; ash and carbon in coals.
 Kinetic Studies
 Corrosion studies
 Automatic Thermogravimetric Analysis
 Evaluation of gravimetric precipitates
 Evaluation of suitable standards
 Testing of purity of samples
 Curie point determination