Dr.

S P Sivapirakasam
Associate Professor
Department of Mechanical Engineering
NIT Tiruchirappalli
 Thermal Analysis Techniques
A group of techniques in which a physical property is measured as a function of
temperature, while the sample is subjected to a predefined heating or cooling
program.

Differential Thermal Analysis (DTA)

• the temperature difference between a sample and an inert reference material,

DT = TS - TR, is measured as both are subjected to identical heat treatments

Differential Scanning Calorimetry (DSC)

• the sample and reference are maintained at the same temperature, even during
a thermal event (in the sample)

• the energy required to maintain zero temperature differential between the

sample and the reference, dDq/dt, is measured

Thermo gravimetric Analysis (TGA)

• the change in mass of a sample on heating is measured

 Basic Principles of Thermal Analysis
Modern instrumentation used for thermal analysis usually consists of four parts:

1) sample/sample holder

2) sensors to detect/measure a property of the sample and the temperature

3) an enclosure within which the experimental parameters may be controlled

4) a computer to control data collection and processing

DTA Power compensated DSC Heat flux DSC

Property Derived Techniques Abbreviation

Mass Thermogravimetry TG

Temperature Differential thermal DTA

analysis

Enthalpy Differential scanning DSC

calorimetry
Heating Rate
The heating rate is the rate of temperature increase,
which is customarily quoted in degrees per minute
(on the Celsius or Kelvin scales). The heating or
cooling rate is said to be constant when the
temperature/time curve is linear.

Onset Temperature
The temperature at which chemical starts reacts
exothermically
 EXCHANGE OF GASES:
REACTING GASES IN,
PRODUCTS OUT

CONVECTION
THROUGH
SURROUNDING
ATMOSPHERE

RADIATION FROM
FURNACE WALL

CONDUCTION
THROUGH SAMPLE
PAN AND
INDICATION OF SAMPLE
INSTRUMENT
TEMPERATURE
A) INSTRUMENTAL B) SAMPLE-RELATED
• heating rate • mass
• furnace atmosphere and flow- • particle size
rate • sample history/pre-treatment
• geometry of pan and furnace
• packing
• material of pan
• thermal conductivity
• heat of reaction
 Differential Thermal Analysis (DTA)
Differential thermal analysis is carried out by heating
the sample together with a reference standard under
identical thermal conditions

It measures the
temperature
difference between
the sample and
reference substance
during the period
of heating.
The Basic Differential Thermal Analysis Apparatus
As soon as the sample changes state, crystal form,
melts, etc. the latent heat of phase transition will be
absorbed and the temperature of the sample will lag
behind that of the reference material.
In this way any change in state will be shown and the
temperature at which it occurs will be recorded.
The sample and the reference standard are placed in
containers situated in two cavities contained in a high
thermal capacity block.
Thermocouples are situated in the sample and the
reference materials and are connected in opposition
so only a temperature difference between the two will
be recorded.
A Typical Differential Thermo gram Showing a Single Change in State
 Differential Thermal Analysis
Advantages:

• instruments can be used at very high

temperatures

• instruments are highly sensitive

• flexibility in crucible volume/form

• characteristic transition or reaction

temperatures can be accurately determined

DTA
Disadvantages:

• uncertainty of heats of fusion, transition, or

reaction estimations is 20-50%
 Applications
A DTA curve can be used only as a finger print for
identification purposes but usually the applications of
this method are the determination of phase diagrams,
heat change measurements and decomposition in
various atmospheres.
DTA is widely used in the pharmaceutical and food
industries.
DTA may be used in cement chemistry, mineralogical
research and in environmental studies
DTA curves may also be used to date bone remains or
to study archaeological materials.
 Differential Scanning Calorimetry

• DSC differs fundamentally from DTA in that the sample

and reference are both maintained at the temperature
predetermined by the program.

• during a thermal event in the sample, the system will

transfer heat to or from the sample pan to maintain the
same temperature in reference and sample pans

• Two basic types of DSC instruments:

• power compensation and
• heat-flux
 Power Compensation DSC
individual
heaters
controller P

Sample holder
sample reference
pan pan
• Al or Pt pans

Sensors
inert gas inert gas
vacuum vacuum

• Pt resistance thermocouples thermocouple T = 0

• separate sensors and heaters for the sample and reference

Furnace

• separate blocks for sample and reference cells

Temperature controller

• differential thermal power is supplied to the heaters to maintain the

temperature of the sample and reference at the program value
 Heat Flux DSC
heating

Sample holder coil

• sample and reference are connected by sample reference

pan pan
a low-resistance heat flow path constantan
• Al or Pt pans placed on constantan disc chromel/alumel
Sensors wires
inert gas
vacuum thermocouples
• chromel-constantan area thermocouples (differential heat flow)
chromel wafer
• chromel-alumel thermocouples (sample temperature)

Furnace

• one block for both sample and reference cells

Temperature controller

• the temperature difference between the sample and reference is converted to

differential thermal power, dDq/dt, which is supplied to the heaters to maintain
the temperature of the sample and reference at the program value
 Modulated DSC (MDSC)
• introduced in 1993; “heat flux” design
Modulated DSC Heating Profile
• sinusoidal (or square-wave or
sawtooth) modulation is
superimposed on the underlying
heating ramp

• total heat flow signal contains all of

the thermal transitions of standard
DSC

• Fourier Transformation analysis is

used to separate the total heat flow
into its two components:
heat capacity (reversing heat flow) kinetic (non-reversing heat flow)

glass transition crystallization

melting decomposition
evaporation
enthalpic relaxation
cure
 What DSC can Tell us ?
 Glass Transitions
 Melting and Boiling Points
 Crystallization time and temperature
 Percentage Crystallinity
 Heats of Fusion and Reactions
 Specific Heat
 Oxidative/Thermal Stability
 Rate and Degree of Cure
 Reaction Kinetics
 Purity
DSC response of rocket composition
 Thermal decomposition kinetics in DSC

Thermal characterization of pyrotechnic compositions

is important for fixing operating limits for safe
chemical manufacturing process.

An Overview of DSC Kinetics

Borchardt and Daniel’s (1956) method

based on a single DSC scanning run uses the partial
areas under DSC curve to transform the data into degree
of conversion and the rate of heat evolution to determine
the instantaneous reaction rates
 Ozawa-Flynn-Wall method
Ozawa-Flynn-Wall method (1970) based on a minimum
of three DSC scanning runs at different rates (ASTM
698-79, 1984) utilize the relationship between the peak
temperature of the exotherm and the heating rates to
determine reaction kinetic parameters (activation
energy and frequency factor).
In this method starting from Heat flow rate equation
is given by
 Tm
d A 
E

   e RT .dt
0
f ( )  T 0

dα/dt = reaction rate,

α= pre-exponential frequency factor
β= heating rate
E =activation energy (kJ/mol K)
R= the gas constant,
T =Temperature of the sample and
f(α ) = a function of degree of conversion
Rearranging

R d (log  )
E
0.457 d (1 / T )

This is the Ozawa Flynn-Wall method.

 On the other hand, the Arrhenius frequency factor (A)
is given by:

( E / RTm ) 2
A  [  E  e ] /( R  T )
m
After the kinetic parameters E and A were obtained,
the thermodynamic parameters of activation can be
calculated from the following equations:

G
( )
A  e (  E / RT )    e RT

    RT 

G    T  S
 The Method of Kissinger

Kissinger (1957) method based on a minimum of three

DSC scanning runs at different rates (ASTM 698-79,
1984)
Thermal analysis and temperature profile analysis had
done by rate flow equation:
d
  K 1   
n

dt
α = Fractional Extent of reaction
n = Order of reaction
T = Temperature of profile
 Substituting k value in equation and integrating on
both sides we can get the equation as follows:
 Tm
A E
.dt 1   

e
n
0 d  
 T0
RT

In differential form

d ln
Tm 2   E
1 R
d
Tm
This is the Kissinger method
 Effect of Heating Rate
• many transitions (evaporation,
crystallization, decomposition, etc.) are
kinetic events

… they will shift to higher temperature

when heated at a higher rate

• the total heat flow increases linearly with

heating rate due to the heat capacity of the
sample

… increasing the scanning rate increases

sensitivity, while decreasing the scanning
rate increases resolution

• to obtain thermal event temperatures close DSC traces of a low melting polymorph collected
to the true thermodynamic value, slow at four different heating rates. (Burger, 1975)

scanning rates (e.g., 1–5 K/min) should be

used
 Difference between DSC and DTA
Differential Scanning Calorimetry Differential Thermal Analysis

1. difference is calculated between the 1. difference is calculated between the

amount of heat(enthalpy) temperatures.

2. Reference sample is same as the bomb 2. Reference sample is not same as bomb
sample sample

3. DSC is used in measuring melting, 3. DTA instruments are also used to

crystallization , heat capacity etc. measure a glass transition, phase changes,
purity evaporation,
 Applications
1. DSC is used widely for examining polymers to check
their composition
2. DSC is used in the study of liquid crystals.
3. to study the stability to oxidation of samples
4. DSC makes a reasonable initial safety screening tool.
In this mode the sample will be housed in a non-
reactive crucible (often gold, or gold plated steel),
and which will be able to withstand pressure
(typically up to 100 bar). The presence of an
exothermic event can then be used to assess the
stability of a substance to heat.