Thermal Analysis

Dr. S. Anandhan,
Asst. Professor,
Dept. of Met. and Mat. Engg., NITK
What is thermal analysis?

"A group of techniques in which a physical property of a substance and/or its reaction products is
measured as a function of temperature whilst the substance is subjected to a controlled temperature
program"
R.C.Mackenzie, Thermochim. Acta, 1979, 28, 1.

Heat flow into a substance induces many physical and chemical changes which can help to identify and
characterize a sample
Thermal Analysis
A group of analytical techniques
Each technique defines a material property
TA Techniques

TA Use

Thermal Analysis is widely used

For a wide variety of Applications

Over a dozen thermal methods can be recognized, which differ in the properties measured and the
temperature programs

These are used for quality control and research applications on industrial products, such as polymers,
pharmaceuticals, clays and minerals, metals and alloys

Thermogravimetric Analysis (TGA) or Thermogravimetry

Thermogravimetry fundamentals
Principle

Changes in the mass of a sample are studied while the sample is subjected to a controlled temperature
programme.

The temperature programme is most often a linear increase in temperature, but, isothermal studies can
also be carried out, when the changes in sample mass with time are followed.

TGA is inherently quantitative, and therefore an extremely powerful thermal technique, but gives no
direct chemical information. The ability to analyze the volatile products du
during
ring a weight loss is of great
value

TGA + Mass Spectrometry: TGA
TGA-MS

TGA + Infrared Spectroscopy: TGA-FTIR
TGA
Processes that lead to weight gain or loss in TGA experiments

Instrumentation

Thermobalance/microbalance
 Balance sensitivity is usually around one microgram, with a total capacity of a few hundred
milligrams

Furnace

Temperature programmer
 A typical operating range for the furnace is ambient to 1500C, with heating rates up to
200C/min


Temperature sensor
 thermocouple placed close to the sample

Sample holder/pan

An enclosure for establishing the required atmosphere
 Reactive or inert

Microcomputer/microprocessor
 Instrument control
 Data acquisition and display

Balance/furnace configurations

Pans for TGA

aluminum, platinum, silica, and alumina

Data Analysis
Thermogram is graph of mass versus temperature. Sometimes given as % of original mass.

Draw tangents of the curve to find the onset and the offset points

mi, mf and m are fundamental properties ofthe sampleTi and Tf depend on operating variables
Typical TG curves

Derivative thermogram (DTG)

plots change in mass with temperature, dm/dt, and resolves changes more clearly.

Calibration
MASS - Use standard weights.
Use standard samples to check operation, but unwise to use them as weight standards.
TEMPERATURE Four approaches:

Observe deflection on Temperature/time curve

Curie-point standards

Drop-weight methods

In simultaneous-type units, use melting standards

DO NOT use decomposition events to define temperature.

Calibration using curie point

Factors affecting TG Analysis

heating rate and sample size
 increase in either of which tends to increase the decomposition temperature, and to decrease the
resolution between successive mass losses

particle size and packing of the sample

crucible shape

Gaseous atmosphere
 Nature
 flow rate
Effect of gaseous atmosphere

Polymers degrade at a lower temperature in presence of O2

Effect of heating rate

10 mg samples of PTFE, heated at 2.5, 5, 10 and 20 C/min in nitrogen

Important note

Careful attention to consistency in experimental details normally results in good repeatability.

On the other hand, studying the effect of deliberate alterations in such factors as the heating rate can give
valuable insight into the nature of the observed reactions.
Sources of error
A) MASS

Classical buoyancy

Effect temp. on balance

convection and/or turbulence

viscous drag on suspension

These are lumped together as the buoyancy correction, and if significant, can be allowed for by a blank run
B) TEMPERATURE

Temperature calibration difficult to carry out accurately.

Many methods exist, but none totally satisfactory.
Best accuracy from simultaneous TG-DTA or TG-DSC instrument.
NOISY OR ERRATIC RECORDS CAN ARISE FROM:

static

vibration

pressure pulses in lab.

uneven gas flow

Applications of TGA
Ability of TG to generate fundamental quantitative data from almost any class of materials, has led to its
widespread use in every field of science and technology. Key application areas are listed below:

Thermal Stability: related materials can be compared at elevated temperatures under the required
atmosphere. The TG curve can help to elucidate decomposition mechanisms.

Material characterization: TG and DTG curves can be used to "fingerprint" materials for identification or
quality control.

Compositional analysis: by careful choice of temperature programming and gaseous environment, many
complex materials or mixtures may be analyzed by selectively decomposing or removing their
components. This approach is regularly used to analyze e.g. filler content in polymers; carbon black in
oils; ash and carbon in coals, and the moisture content of many substances.

Simulation of industrial processes: the thermobalance furnace may be thought of as a mini-reactor, with
the ability to mimic the conditions in some types of industrial reactor.

Kinetic Studies: a variety of methods exist for analyzing the kinetic features of all types of weight loss or
gain, either with a view to predictive studies, or to understanding the controlling chemistry.

Corrosion studies: TG provides an excellent means of studying oxidation, or reaction with other reactive
gases or vapors.
Ex.1.Comparison of thermal stability of materials

Ex.2.Quantitative analysis of materials - % composition of a rubber sample

Ex.3.Quantitative analysis of materials - % composition of a composite used in making doors

Ex.4.Mechanism of thermal reactions

Ex.5. Effect of additives on thermal stability of materials

EX.6.Analysis of Chewing Gum with Auto Stepwise TGA

Chewing gum is a complex mixture of a number of components, including: PVAc (poly vinyl acetate),
natural elastomers, glycerin, softening agents, and carbonates, flavoring agents, sweeteners and
colorants.

The correct combination of the gum formulation provides
provides the end characteristics to the chewing gum,
including: stickiness, softness and chewability.

Sample is heated at a constant rate until a significant weight loss event is encountered.

Equipment automatically holds the sample under isothermal conditio
conditions
ns until
that the given component has essentially completed its given degradation.

becomes small, meaning


Heating is automatically resumed, at a constant rate, until the next significant weight loss event. By this
process, we are able to nicely resolve closely occurring decomposition events and provide better
quantitative analysis of a sample.

Standard TGA results for Doublemint chewing gum sample

TGA auto stepwise results for Doublemint chewing gum sample

References

D. A. Skoog et al., Principles of instrumental analysis, fifth edition, Harcourt Publishers, 2001.

http://www.anasys.co.uk/library/macrota.htm