THERMAL METHODS

Dr.A.Thirunavukkarasu, M.Tech., PG Dip. (Bio-stat), Ph.D.

Assistant Professor of Industrial Biotechnology
Government College of Technology
Coimbatore, India
Principle of Thermal Analysis

A group of techniques in which a property of the sample is

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

Dr.A.Thirunavukkarasu, M.Tech., PGDBS, Ph.D.

 Block Diagram

Temperature Detection Recording

control Unit Unit Unit

Dr.A.Thirunavukkarasu, M.Tech., PGDBS, Ph.D.

• DTA

Dr.A.Thirunavukkarasu, M.Tech., PGDBS, Ph.D.

• DTA
• Differential Thermal Analysis

Dr.A.Thirunavukkarasu, M.Tech., PGDBS, Ph.D.

• DTA
• Differential Thermal Analysis
• Difference temperature

Dr.A.Thirunavukkarasu, M.Tech., PGDBS, Ph.D.

• DTA
• Differential Thermal Analysis
• Difference temperature

• DSC

Dr.A.Thirunavukkarasu, M.Tech., PGDBS, Ph.D.

• DTA
• Differential Thermal Analysis
• Difference temperature

• DSC
• Differential Scanning Calorimetry

Dr.A.Thirunavukkarasu, M.Tech., PGDBS, Ph.D.

• DTA
• Differential Thermal Analysis
• Difference temperature

• DSC
• Differential Scanning Calorimetry
• Enthalpy

Dr.A.Thirunavukkarasu, M.Tech., PGDBS, Ph.D.

• DTA
• Differential Thermal Analysis
• Difference temperature

• DSC
• Differential Scanning Calorimetry
• Enthalpy

• TGA

Dr.A.Thirunavukkarasu, M.Tech., PGDBS, Ph.D.

• DTA
• Differential Thermal Analysis
• Difference temperature

• DSC
• Differential Scanning Calorimetry
• Enthalpy

• TGA
• Thermogravimetry

Dr.A.Thirunavukkarasu, M.Tech., PGDBS, Ph.D.

• DTA
• Differential Thermal Analysis
• Difference temperature

• DSC
• Differential Scanning Calorimetry
• Enthalpy

• TGA
• Thermogravimetry
• Mass

Dr.A.Thirunavukkarasu, M.Tech., PGDBS, Ph.D.

Principle of Thermogravimetry (TG)

A technique in which the mass of the sample is monitored

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

Dr.A.Thirunavukkarasu, M.Tech., PGDBS, Ph.D.

TG
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).

A plot of mass or mass percentage as a function of time is called a

thermogram or a thermal decomposition curve.

Dr.A.Thirunavukkarasu, M.Tech., PGDBS, Ph.D.

Instrumentation

Dr.A.Thirunavukkarasu, M.Tech., PGDBS, Ph.D.

Instrumentation
1. A sensitive microbalance, called a Thermobalance

Dr.A.Thirunavukkarasu, M.Tech., PGDBS, Ph.D.

Instrumentation
1. A sensitive microbalance, called a Thermobalance

2. A Furnace

Dr.A.Thirunavukkarasu, M.Tech., PGDBS, Ph.D.

Instrumentation
1. A sensitive microbalance, called a Thermobalance

2. A Furnace

3. A Purge-gas System for providing an inert, or sometimes

reactive atmosphere

Dr.A.Thirunavukkarasu, M.Tech., PGDBS, Ph.D.

Instrumentation
1. A sensitive microbalance, called a Thermobalance

2. A Furnace

3. A Purge-gas System for providing an inert, or sometimes

reactive atmosphere

4. A Computer System for instrument control, data acquisition,

and data processing.
Dr.A.Thirunavukkarasu, M.Tech., PGDBS, Ph.D.
Thermobalance
• Capacity : less than 1 mg to 100 g.

• Sensitivity : can detect changes in mass as small as 0.1 μg.

Note : Only sample holder must be housed in the furnace, the

rest of the balance must be thermally isolated from the furnace.

Dr.A.Thirunavukkarasu, M.Tech., PGDBS, Ph.D.

Dr.A.Thirunavukkarasu, M.Tech., PGDBS, Ph.D.
How it Works?
• A change in sample mass causes a deflection of the beam, which
interposes / interferes a light shutter between a lamp and one of two
photodiodes.
• The resulting imbalance in the photodiode current is amplified &
transformed into mass or mass-loss information by the data-processing
system.

Dr.A.Thirunavukkarasu, M.Tech., PGDBS, Ph.D.

• Also, amplified photodiode current is fed into coil E, which is
situated between the poles of a permanent magnet F.

• The magnetic field generated by the current in the coil restores

the beam to its original position.

• In most cases mass versus temperature data can either be

plotted in real time or stored for further manipulation or
display at a later time.

Dr.A.Thirunavukkarasu, M.Tech., PGDBS, Ph.D.

Furnace
• Range
• Ambient temperature to 1000°C, sometimes upto 1600°C.

• Heating rates
• 0.1°C/ min to 100°C/min. sometimes 200°C/min.

• Insulation and cooling of the exterior of the furnace is required to

avoid heat transfer to the balance.

Dr.A.Thirunavukkarasu, M.Tech., PGDBS, Ph.D.

Purge Gas System
• Nitrogen or Argon is usually used to purge the furnace and
prevent oxidation of the sample.

• For some analyses, it is desirable to switch purge gases as the

analysis proceeds

• Most newer TGA instruments use digital flow controllers for

the purge gas flow monitoring

Dr.A.Thirunavukkarasu, M.Tech., PGDBS, Ph.D.

Sample Holders
• Pans made of platinum, aluminum, or a ceramic such as alumina.
• Pt is most often used because of its inertness and ease of cleaning.
• Volumes : 40 μL to more than 500 μL.
• Ceramic pans are best for high-volume, low-density samples (e.g.,
foams) and for materials that react with platinum.
• Aluminum pans are inexpensive substitutes, but cannot be used for
temperatures exceeding 600°C.
• Autosamplers.
• The sample-pan taring, loading, and mass measurement; the furnace heating
and cooling; and the pan unloading are totally automatic.

Dr.A.Thirunavukkarasu, M.Tech., PGDBS, Ph.D.

Temperature Control and Data Processing
• The temperature recorded in a thermogram is ideally the actual
temperature of the sample.

• This temperature can, in principle, be obtained by immersing a small

thermocouple directly in the sample.

• Not followed
• catalytic decomposition of samples,
• potential contamination of samples, and
• mass measurement errors resulting from the thermocouple leads.
Dr.A.Thirunavukkarasu, M.Tech., PGDBS, Ph.D.
Temperature Control and Data Processing
• A small thermocouple located as close as possible to the sample
container.

• The recorded temperatures then generally lag or lead the actual

sample temperature.

• With modern control systems, it is possible to achieve excellent

agreement between the specified temperature program and the
temperature of the sample.
Dr.A.Thirunavukkarasu, M.Tech., PGDBS, Ph.D.
Applications
• Quantitative
• Decomposition and oxidation reactions and physical processes
as vaporization, sublimation, and desorption.
• Compositional analysis
• Decomposition profiles of multicomponent systems.
• Characteristic for each kind of polymer and can sometimes be used for
identification purposes
• Determination of moisture levels

Dr.A.Thirunavukkarasu, M.Tech., PGDBS, Ph.D.