Thermal Analysis

By Deepak Poddar
Introduction
 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.

 Physical properties include mass, temperature, enthalpy,

dimension, dynamic characteristics, and others, and
depending on the physical properties to be measured, the
techniques of thermal analysis
The Family of
Thermal Analysis Techniques
DSC heat flow into and from a sample

DTA temperature difference versus temperature or time

TGA mass loss events due to decomposition or evolution of

volatiles

DMTA visco-elastic characteristics of samples for assessing

heat transfer through a sample
Thermal Analysis Techniques

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, dq/dt, is
measured

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
Thermal Analysis Techniques
Thermogravimetric Analysis (TGA)
 The change in mass of a sample on heating is measured

Dynamic Mechanical Analysis (DMA)

 Mechanical behavior of a sample subjected to a
specific temperature program is investigated under the
effect of a load which changes with time.
Differential Scanning Calorimetry
(DSC)
Definitions
 A calorimeter measures the heat into or out of a sample.
 A differential calorimeter measures the heat of a sample
relative to a reference.
 A differential scanning calorimeter does all of the above
and heats the sample with a linear temperature ramp.
 Endothermic heat flows into the sample.
 Exothermic heat flows out of the sample.
Principal
 DSC is a thermo-analytical technique in which the
difference in the amount of heat required to increase the
temperature of a sample and reference is measured as a
function of temperature and time in a controlled
atmosphere.
 The differences in heat flow occur with the occurrence of
two major events:
 The heat capacity of the sample which increases with
temperature (baseline)
 Transitions that occur in the sample (events superimposed on
the heat capacity baseline)
Amorphous vs. Crystalline
Glass Transition Temp (Tg)

The glass– liquid transition or glass transition for short is the

reversible transition in amorphous materials (or in amorphous regions
within semi crystalline materials) from a hard and relatively brittle
"glassy" state into a viscous or rubbery state as the temperature is increased.
Heat capacity (C)
C= c(Specific heat capacity) x m
M=Density x Volume
C (J/Kg oC) of
Water =2090
Ice =4186
Steam =1520
Melting temperature (Tm)
the temperature at which a materials melts. It is measured as
the peak temperature of an endothermic event.
Crystallization Temp (Tc)
 Temperature at which polymer starts to align its chains
while cooling. These chains fold together and form
ordered regions called lamellae, which compose larger
spheroidal structures named spherulites.
Typical DSC Curve
Instrumentation of DSC
What can DSC measure?
 Glass transitions
 Melting and boiling points
 Crystallization time and temperature
 Percent crystallinity
 Heats of fusion and reactions
 Specific heat capacity
 Oxidative/thermal stability
 Rate and degree of cure
 Reaction kinetics
 Purity
Thermogravimetric Analysis
(TGA)
TGA
 TGA is a technique in which the change of mass of a
substance is monitored as a function of temperature or
time as the sample specimen is subjected to a controlled
temperature program in a controlled atmosphere.
 Thermogravimetric Analysis (TGA) examines materials
between ambient and +1500°C.
Phenomena causing mass changes

 The measured weight loss curve gives information on:

 • changes in sample composition
 • thermal stability
 • kinetic parameters for chemical reactions in the sample
Instrumentation
Instrumentation of Thermogravimetry
 Microbalance: A microbalance is used to record a change in mass of sample.
 Deflection Balances
 Null-Point Balances
 Sample Holder or Crucible: It is attached to the weighing arm of microbalance.
Platinum, aluminium, quartz or alumina and graphite, stainless steel, glass, etc.
 Furnace (Heater/Boiler/Oven): The furnace should be designed in such a way that it
produces a linear heating range
 Temperature Measurement: It is done with the help of thermocouple,
 i.e. chromal or alumel (alloys of Platinum) thermocouples are used for
T=1100oC,
 tungsten or rhenium thermocouples are used for higher temperature
 Data Recording Unit: The output from the microbalance and furnace are recorded
using either chart recorder or a microcomputer (work station).
Types of TGA Curves
 Type A- this curves shows no mass change over the entire range of temperature.
 Type B- this curves shows that there is large mass loss followed by mass plateau and is formed
when evaporation of volatile product(s) during drying, desorption or polymerization takes
place.
 Type C- this curve shows the single-stage decomposition temperatures.
 Type D- this curve shows the multi-stage decomposition processes where reaction is resolved.
 Type E- this curve shows the multi-stage decomposition reaction where reaction is not
resolved.
 Type F- this curve shows the increase in mass in
the presence of an interacting atmosphere e.g.
surface oxidation reactions.
 Type G- this curve shows multiple reactions one
after the other e.g. surface oxidation reaction
followed by decomposition of reaction product(s).
Calcium oxalat monohydrate
Typical TGA curves
Factors affecting the TG curve
Application
 Compositional analysis
 Degradation onset temperatures
 Examine flame retardant properties of material
 Thermal Stability
 Product lifetime predictions
 Measurement of filler content
 Determination of moisture, volatiles and ash contents
 Material characterization
Differential Thermal Analysis (DTA)
 The material under study and an inert reference are made
to undergo identical thermal cycles.
 Any temperature difference between sample and reference
is recorded.
 In this technique the heat flow to the sample and reference
remain the same rather than the temperature.
Principle
 The basic principle involved in DTA is the temperature
difference (∆T) between the test sample and an inert
reference sample under controlled and identical conditions
of heating or cooling is recorded continuously as a
function of temperature or time, thus the heat absorbed or
emitted by a chemical system is determined.
 DTA technique requires to find out the difference in
temperature between a sample and a reference when the
heat flow is kept the same. The heat flow is maintained
throughout the experiment for reference as well as the
sample and observation is made in the phase changes and
changes in other thermal processes.
DTA
 If any reaction takes place in the sample, then the
temperature difference will occur between the sample and
the reference material.
 In an endothermic change (such as melting or dehydration
of the sample) the temperature of the sample is lower than
that of the reference material, (i.e) ∆T = -ve (for
endothermic process)
 In an exothermic change or process the sample
temperature is higher than that of the reference material,
(i.e) ∆T = + ve (exothermic process)
Peak interpretation
 Sharp Endothermic – changes in crystallinity or fusion
 Broad endotherms - dehydration reaction
 Physical changes usually result in endothermic curves
 Chemical reactions are exothermic
Phenomena causing changes in heat/
temperature
Instrumentation for DTA
Instrumentation for DTA
 Furnace sample and reference holder with thermocouple
assembly.
 Sample holder furnace(To heat the sample)
 Furnace temperature controller(to increase the furnace
temperature steadily)
 Furnace atmospheric control system(To maintain a
suitable atmosphere in the furnace and sample holder)
 Low level DC amplifier
 Recording device(Recorder)
Calcium oxalate monohydrate
 Decomposition of Calcium oxalate monohydrate
(CaC2O4.H2O), (a) in CO2 and (b) In air
 The thermogram of calcium oxalate monohydrate has
three peaks corresponding to the successive elimination of
H2O, CO and CO2.
 These three points of weight loss corresponding to the
three endothermic process
 Curve (b) represent the DTA diagram for the same
compound inn air, this peak represent the exothermic
burning of CO in air at the temp of the furnace.
Factors affect results in DTA
 Sample weight
 Particle/Sample size
 Heating rate
 Atmospheric conditions
 Conditions of sample packing into dishes
Applications
 DTA curves for two substances are not identical. Hence
they serve as finger prints for various substances.
 Quantitative identification and purity assessment of
materials are accomplished by comparing the DTA curve
of sample to that of a reference curve
 Used for the determination of heat of reaction, specific
heat and energy change occurring during melting etc.
 Impurities may be detected by depression of the M.P
Difference b/w DSC and DTA
DTA DSC
DTA curve is a curve of temperature The result of DSC is a curve of heat
difference between the sample material and flux or heat flow versus time or
the reference material versus temperature or temperature
time
DTA technique requires to find out the the difference is calculated between the
difference in temperature between a sample amount of heat needed to increase the
and a reference when the heat flow is kept temperature of the sample and the heat
the same. required to increase the temperature of
the reference
Quantative DTA equipment is that the latter is
mostly used for the qualitative
measurements
The sample holder in the DTA apparatus is DSC the technique is more sensitive
much cheaper, less sensitive
it allows simultaneous recording of changes DSC requires a constant mass during
in the sample mass the enthalpy change measurement
Difference b/w DSC and DTA
DTA DSC
DTA measures the temperature difference DSC directly measures the energy change
between the reference and the sample, of a sample
which is converted to enthalpy change
(∆H)
DTA is an older technique than DSC. DSC is more sophisticated and improved
than DTA.
DTA instrument can be used at very high DSC instrument may not work
temperatures and in aggressive
environments