Thermal Analysis Techniques

Thermal Analysis Techniques

•When a material is heated its structural and
chemical composition can undergo changes
such as fusion, melting, crystallization,
oxidation, decomposition, transition,
expansion etc.
•Using Thermal Analysis such changes can
be monitored in every atmosphere of
interest. The obtained in formation is very
useful in both quality control and problem
solving.
Types of thermal analysis
•TG (Thermo gravimetric analysis):
Weight
•DTA (Differential Thermal Analysis):
Temperature
•DSC (Differential Scanning Calorimetry):
temperature
 DTA (Differential Thermal Analysis)
 In Differential Thermal Analysis, the
temperature difference that develops
between a sample and an in reference
material is measured, when both are
subjected to identical heat treatments.
 •The related technique of Differential
Scanning Calorimetry relies on differences
in energy required to maintain the sample
and reference at an identical temperature
 INTRODUCTION
 This is a comparison method
 Analytical method for recording the
difference in temperature (∆T) b/w a
substance and an in reference material as a
function of temperature or time
 Any transformation–change in specific heat
or an enthalpy of transition can be detected
by DTA
 In DTA both test sample & an in reference
material (alumina)–controlled heating or
cooling programming
 If zero temperature difference b/w sample &
reference material–sample does not undergo any
chemical or physical change.
 If any reaction takes place temperature
difference (∆T) will occur b/w sample &
reference material
 A DTA curve can be used as a fingerprint
for identification purposes, for example,
 in the study of clays where the structural
similarity of different forms renders
diffraction experiments difficult to interpret
 Apparatus
 The key features of a differential thermal
analysis are as follows
1.Sample holder comprising thermocouples,
sample containers and a ceramic or metallic
block.
2.Furnace.
3.Temperature programmer
4.Recording system
DTA Instrumentation
 ∆T VS Temp.
 Sharp Endothermic–changes in crystallinity
or fusion Broad endotherms-dehydration
reaction Physical changes usually result in
endothermic curves Chemical reactions are
exothermic
 Key points in thermogram
 Sharp endotherm: crystalline rearrangemets,
fusion, solid state transition
 Broader endotherm: dehydration, melting of
polymers, slow reactions
 Narrow exotherm: crystallization
 Sharp exotherm: phase change
DTA curve for Mn(PH2O2)2.H2O (S)
 Advantages
 Instruments can be used at very high
temperatures
• instruments are highly sensitive
•characteristic transition or reaction
temperatures can be accurately
determined.
 Factors affect results in DTA
 Sample weight
 Particle size
 Heating rate
 Atmospheric conditions
 Conditions of sample packing into dishes.
 Applications

 Quantitative identification and purity

assessment of materials are accomplished by
comparing the DTA curve of sample to that to
reference curve
 Impurities may be detected by depression of
the M.P.
Differential Scanning
Calorimeter
Differential Scanning Calorimeter
Differential Scanning Calorimetry (DSC)

Exothermal dQ/dT
Temperature

 DSC measures differences in the amount of heat required to

increase the temperature of a sample and a reference as a
function of temperature
 Typical DSC Curve of a
Size: 23.4300 mg ThermoplasticDSCPolymer
Sample: PET80PC20_MM1 1min
Method: standard dsc heat
-cool-heat
File: C:...\DSC\Melt Mixed1\PET80PC20_MM1.001
Operator: SAC
Run Date: 05-Apr-2006 15:34
Comment: 5/4/06
1.5
Tm
Instrument: DSC Q1000 V9.4 Build 287

245.24°C

1.0 Tc
Tg
Heat Flow(W/g)

137.58°C
20.30J/g 228.80°C
22.48J/g
79.70°C
(I) 81.80°C
0.5
75.41°C

Cycle 1

144.72°C
0.0

-0.5
0 50 100 150 200 250 300
Exo Down Temperature(°C
) Universal V4.2E TA Instruments
 DSC: Applications
 Polymer characterization (PET)
 Gas adsorption/desorption
 Thermo gravimetry (TG)
 Thermo gravimetry is the measurement of
the mass of a sample as a function of
temperature or time.
 This method is useful for determining the
weight loss due to dehydration and
decomposition reactions.
 This changes in weight are a result of
rupture or formation of various physical and
chemical bonds.
 The graph plotted b/w weight loss vs
temperature is called “Thermogram”.
 Thermogram gives the information about-
-thermodynamics and kinetics of various
chemical reactions,
-the reaction mechanism,
-the reaction intermediate,
-and the final products.
TG Curve of Mn(PH2O2)2.H2O
 TGA: Instrumentation

 Sample and reference pans

 – Pt, Al, alumina, quartz, ceramic
 Microbalance (a thermobalance)
 Furnace
 high temperatures
 Thermocouple
 – Acts as a thermometer
 Purge‐gas system
 – Used for atmosphere control
 – Inert (N2, Ar) or reactive gas (O2, H2,
etc.)
 Computer system
 – Temperature program, data collection,
etc.
TGA: Thermo balance (simplified)
 TGA: Applications
•Thermogravimetric techniques have a very wide
field of application.
• Thermogravimetric analysis has also been involved
in determining the age of art treasures, particularly
paintings and in determining the stability of
explosives.
 The technique is commonly used to control the
dehydration procedures for crops.
 This is also used extensively in the
pharmaceutical industry in the examination of
drug stability and the rate of degradation of
certain drugs when expose to air.
 The most important application of TGA
methods are in the study of polymers.
 It provides different decomposition pattern
for different polymers.And from this pattern
we can identify the polymers.
 Q. Discuss the principle and working of
TGA. What useful result can you get by
this technique.
 Q. Draw and discuss TGA grams of the
maganese phosphinate
monohydrate[Mn(PH2O2)2.H2O (S)