“PHARMACEUTICAL CHEMISTRY”

Thermogravimetric Analysis
(TGA)
 Thermogravimetric Analysis
Theory, Operation, Calibration
and Data Interpretation
 Contents
S. No Contents
1 Definitions and review of instrument

2 Balance, furnace and heat exchanger

3 Mass and temperature calibration

4 Purge gas considerations, Baseline considerations

5 Sample preparation and pan selection

6. Examples and data interpretation

7. Application
 Thermal Analysis Techniques

• Thermal analysis is a branch of materials science

where the properties of materials are studied as they
change with temperature
• On heating material undergo structural and chemical
changes.
• Changes are fusion, melting, crystallization,
oxidation, decomposition, transition, expansion and
sintering (The process of compacting and forming a
solid mass of material by heat).
• Thermal analysis can gathered useful information in
both quality control and research.
 Types of thermal analysis

• Thermogravimetric analysis: (TG)

(Monitor change in mass of sample)

• Differential Thermal Analysis (DTA)

(Measure sample temperature relative to a reference,
for the same heat transferred)

• Differential Scanning Calorimetry (DSC)

(Difference in the amount of heat required to increase
the temperature of a sample and reference are
measured as a function of temperature)
 Introduction of TGA

• Thermogravimetric Analysis (TGA) measures the

amount and rate of change in the weight of a material
as a function of temperature or time in a controlled
atmosphere.

• Measurements are used primarily to determine the

composition of materials and to predict their thermal
stability at temperatures up to 1000 °C.

• The technique can characterize materials that exhibit

weight loss or gain due to decomposition, oxidation, or
dehydration.
 What TGA Can Tell You

• Thermal stability of materials

• Oxidative stability of materials
• Composition of multi-component systems
• Estimated lifetime of a product
• Decomposition kinetics of materials
• The effect of reactive or corrosive
atmospheres on materials
• Moisture and volatiles content of
materials
 Principle of Thermal Gravimetric
Analysis (TGA)

The basic principle involved

in DTA is the temperature
difference (∆T) between the test
sample and an inert reference
sample under controlled
conditions of heating or cooling,
recorded continuously as a
function of temperature or time,
thus the heat absorbed or emitted
by a chemical system is
determined.
Instrumentation of TGA
 Instrumentation for TGA/Block Diagram

The TGA apparatus consists of the following components

• The heart of the instrument is the balance… Rigorous
demands for microbalance in variable temperature
environment.
• Programmable furnace
• Sample and reference holder with thermocouple assembly.
• Furnace temperature controller
• Furnace atmospheric control system (To maintain a
suitable atmosphere in the furnace and sample holder)
Instrumentation for TGA/Block Diagram
 TGA: How the balance works

• Deflection or null balance

• TGA balance operates mostly on a null-
balance principle. At the zero, or “null”
position equal amounts of light shine on
the 2 photodiodes.
• If the balance moves out of the null
position an unequal amount of light shines
on the 2 photodiodes. Current is then
applied to the meter movement to return
the balance to the null position.
• The amount of current applied is
proportional to the weight loss or gain.
 Mechanisms of Weight Change in TGA

• Weight Loss:
• Decomposition: The breaking apart of chemical bonds.
• Evaporation: The loss of volatiles with elevated
temperature.
• Reduction: Interaction of sample to a reducing
atmosphere (hydrogen, ammonia, etc.)
• Desorption.
• Weight Gain:
• Oxidation: Interaction of the sample with an oxidizing
atmosphere.
• Absorption.

All of these are kinetic processes (i.e. there is a rate at

which they occur).
 Thermal Gravimetric Analysis

Advantages:
• Instruments can be used for rapid
determination
• Required small amount of sample
• Weight error is minimal due to no need of
sample removal (in build balance is present)
• Highly sensitive and versatile
• Simple and can study many type of chemical
reactions

Disadvantages:
• Relatively low accuracy and precision
• Not useful for overlapping reactions
• Sample may decompose or oxidized
 Heart of the analysis – Microbalance

cavities for the sample and reference

Sample Reference

Unit is set in an oven- control

pressure

Temp of the block is

raised Oven/ Furnace

Temp of the sample and

reference rise Sample

No Weight. difference – no physical or chemical change

If any reaction – difference in ∆W
Factors effecting TGA Curve
Instrument factors
Sample factors
 How is a TGA Thermal Curve displayed?

• The abscissa (X-axis) can be displayed as time or

temperature and the ordinate (Y-axis) can be displayed as
weight (mg) or weight percent (%).
120

100
2.4 %

80
W e ig h t (% )

60 49.7 %

40

20 99.1 %

-20
0 50 100 150 0.017% 250
200 300 350 400
Temperature (°C)
 TGA Performance Criteria

• Baseline
• Drift
• Affected by TGA construction, balance quality, and buoyancy
effect (minimized through proper construction techniques and
purge gas control)
• Sensitivity
• Affected by TGA balance quality
• Reproducibility
• Affected by balance quality, temperature control, and construction
quality
• Temperature Accuracy
• Affected by thermocouple placement, calibration stability, purge
gas interaction
 TGA Performance

• TGA Performance is primarily a function

of balance sensitivity and baseline stability
• Balance sensitivity is optimized through
design and construction techniques
• Baseline stability is a function of
instrument design, as well as purge gas
control
• TGA resolution is primarily a function of
heating rate, but can be optimized using
Hi-Res TGA
 Quantifying TGA Baseline Performance

Unnormailzed Sample Mass

Drift

Temperature or Time
 TGA: Calibrations

• Mass (Verify monthly)

(Balance calibration)

• Temperature (Verify monthly)

(Furnace calibration, Temperature calibration utilizes Curie
point Reference Materials. Curie point
Reference Materials are materials that upon heating lose
their affinity for magnetism)

• Platform (Perform if there is a problem picking up pans.)

 TGA: Temperature Calibration

Vertical Balance Configuration

Tare

Sample
%
Offset
Furnace
temp
Attraction of Sample to Magnet
Magnet Results in Initial Weight Gain
 What is the best way to prepare a sample for TGA?

This depends on the nature of sample.

• The sample size should be between 2 and 50 mg.
• minimum amount of sample needed is 1 mg.
• If possible, cover the bottom of the pan with the
sample material.
• The sample pans, ceramic or platinum, can
accommodate liquids, powders, films, solids or
crystals.
• Many small pieces of sample are better than one large
chunk. It is better to have a large surface area exposed
to the sample purge.
 Measurement of Result: An Example
Calcium Oxalate
Sample: calcium oxalate File: 111301.001
Size: 6.9610 mg TGA Operator: cgs
Method: Ramp Run Date: 13-Nov-01 10:16
Instrument: TGA Q50 V2.34 Build 127
120 6

12.57% Water

D e r iv . W e ig h t ( % / m in )
(0.8753mg)
19.47% Carbon Monoxide
100 (1.355mg)
4
W e ig h t ( % )

30.07% Carbon Dioxide

80
(2.093mg)

60

0
40

20 -2
0 200 400 600 800 1000
Temperature (°C) Universal V3.4A TA Instruments

This TGA plot shows the decomposition of calcium oxalate monohydrate, in air at a
heating rate of 10 K/min. The decomposition occurs in three mass-loss steps (black
curve) with the release of water (12.5%), carbon monoxide (19.4%) and carbon dioxide
(30.07%).
General Considerations
(Experimental Effects)
 TGA Curves are not ‘Fingerprint’ Curves

Because most events that occur in a TGA are kinetic in nature

(meaning they are dependent on absolute temperature and time
spent at that temperature), any experimental parameter that can
effect the reaction rate will change the shape / transition
temperatures of the curve.
These things include:
• Pan material type, shape and size.
• Ramp rate.
• Purge gas.
• Sample mass, volume/form and morphology.
 Effect of Sample Size on Decomposition Temperature
Polystyrene 17.6 mg
100 Polystyrene 10.2 mg
Polystyrene 5.4 mg
Polystyrene 2.7 mg

80

60
Weight (%)

40

20

0 100 200 300 400 500 600

Temperature (°C) Universal V4.2D TA Instruments
 Effect of Heating Rate on Decomposition Temperature
Polystyrene 20°C/min
100 Polystyrene 10°C/min
Polystyrene 5°C/min
Polystyrene 1°C/min

80

60
Weight (%)

40

20

0 100 200 300 400 500 600

Temperature (°C) Universal V4.2D TA Instruments
 Deviation in Heating Rate
120 3

100

15 2

D eriv. Tem perature (°C /m in)

80

Deriv. W eight (% /°C )

W eight (% )

60 10 1

40

Usually means that the 5 0

20
sample touched the
thermocouple

0 -1
430 440 450 460 470 480
Temperature (°C)
 TGA: Kinetic Analysis

• The rate at which a kinetic process proceeds depends not only on the
temperature the specimen is at, but also the time it has spent at that
temperature.

• Typically kinetic analysis is concerned with obtaining parameters such as

activation energy (Ea), reaction order (k), etc. and/or with generating predictive
curves.
 TGA: Kinetic Analysis

Activation energy (Ea) can be defined as the minimum

amount of energy needed to initiate a chemical process.

Ea
State 1

State 2

With Modulated TGA, Ea can be

measured directly.
 Applications

TGA is used in the research & development of various

substances and engineering materials

TGA can be used to evaluate the thermal stability of a

material

Trace analysis

For the quality control and assurance of raw materials

and incoming goods as well as for failure analysis of
finished parts, especially in the polymer processing
 Applications in Field of Pharmacy

 Purity and composition identification of

minerals and pharmaceutical products

 Polymeric material identification useful in

new drug formulation and improvement of
new dosage forms.

 To study chemical state of catalyst.

 Analysis of bound and unbound water in

pharmaceuticals specially some
magnesium laxatives