Thermal Analytical

Techniques
Thermal Analytical Techniques
Thermal analysis is a group of Technique in Which a physical property Is
Measured as a function of temperature.

It is subdivided in five different techniques

Differential Thermal Analysis (DTA)

Thermal Gravimetric Analysis (TGA)

Thermo Mechanical Analysis (TMA)

Dynamic Mechanical Analysis (DMA)

Differential Scanning Calorimetry (DSC)

Differential Thermal Analysis (DTA)
DTA: The temperature difference between a sample and reference material is
measured as both are subjected to identical heat treatment.

APPLICATION
To Study the thermal behavior of Compounds.

EXAMPLE:
Heating Calcium Oxalate monohydrate in flow of air.
Two minima and one maximum observed in graph.
Differential Thermal Analysis (DTA)

APPLICATIONS : For identification purpose .

Determination of heat change.
Determination decomposition in various atmospheres.
Thermal Gravimetric Analysis (TGA)
TGA is used to measure weight changes in material with temperature .

APPLICATION:
Thermal Stability Determination of bonded Silicas
for use in Packing Columns by Thermogravimetric Analysis.

PROBLEM: Silica materials used as chromatography support material

gave inconsistent performance when packed in Columns.

ANALYSIS: Comparative TGA results .

Thermal Gravimetric Analysis (TGA)
Silica A(Superior material)
Silica B (Inferior material)

OBSERVATION:
Silica A(Superior material) exhibit a smaller total weight loss.
Silica B (Inferior material) exhibit a larger total weight loss.
CONCLUSION :
Either improve the Quality of silica B or by replacement with good quality silica.
 Thermo mechanical analysis (TMA)
TMA: Measurement of a change of a mechanical property of the sample
while it is subjected to a temperature.

APPLICATION: Effect of Residual Solvent Levels in Wire Coatings.

PROBLEM: Blistering and delaminating can occur due to residual solvent

in the adhesive coating.
 Thermo mechanical analysis (TMA)
Suspect sample. Softening temperature 49.5C
Control sample. Softening temperature 92.7C

CONCLUSION : Decrease in Softening temperature due to residual Solvent.

Dynamic Mechanical Analysis (DMA)

DMA: Is a technique used to study and characterized materials .It is most useful
for studying the viscoelastic behavior of polymers.

APPLICATION
Determination of Composite Cure.

PROBLEM: A good quality of thermo set composite materials such as brake

linings in vehicle are dependent on the degree of cure achieved.
 Dynamic Mechanical Analysis (DMA)

OBSERVATION: Reheating Material 1(Superior quality) does not show much

increase in the Tg.
CONCLUSION : Material 1(Superior quality) initially fully cured.
 Dynamic Mechanical Analysis (DMA)

OBSERVATION: Reheating Material 2(Inferior quality)show much increase

much increase in Tg.

CONCLUSION :Material 2(Inferior quality) initially not fully cured

 Basic Principles of Thermal Analysis
Modern DSC instrumentation consists of four parts:
Sample holder.
Sensors to measure a heat flow and temperature of the sample.
An enclosure to control parameters.
A computer to control data collection and processing.

Diagram of Differential scanning calorimetry

DSC Modern instrument used for thermal analysis

Cost :Range from 12 lakh to 75 lakh rupees

DSC sample cell
DSC sample pans
DSC Cross section
 Heat Flux DSC

Furnace Alumina block

Common alumina block containing sample
heating
and reference cells. coil

sample reference
Sensors pan pan

One for the sample and one for the reference.

inert gas
Temperature controller vacuum

Controls for temperature program and furnace

atmosphere
Thermocouples
 Power Compensation DSC
Individual Controller DP
heaters

Sample Reference
pan pan

Inert gas Inert gas

vacuum vacuum

Thermocouple DT = 0
Furnace
Separate blocks for sample and reference cells.

Sensors
Separate sensors and heaters for the sample and reference.

Temperature controller
Differential thermal power is supplied to the heaters to maintain the
temperature of the sample and reference .
Sample Preparation
Accurately-weigh samples (~3-20 mg)

Small sample pans of inert metals (Al, Pt, Ni, etc.)

The same material and configuration should be used for the sample and
the reference.

Ensure good thermal contact.

Avoid overfilling the pan to minimize thermal lag from the bulk of the
material to the sensor.

Small sample masses and low heating rates increase resolution.

Al Pt alumina Ni Cu quartz
 Recognizing Artifacts
Mechanical
Sample pan Cool air entry
Sample topples shock of
distortion Shifting of
over in pan measuring cell into cell
Al pan

Sensor
contamination

RT changes Intermittant
Electrical effects, closing of hole
power spikes, etc. in pan lid
Burst of
pan lid
Best Practices of Thermal Analysis
Small sample size.

Good thermal contact between the sample and the temperature-sensing

device.

Proper sample encapsulation.

Starting temperature well below expected transition temperature.

Slow scanning speeds.

Proper instrument calibration.

Use purge gas (N2 or He) to remove corrosive off-gases.

Avoid decomposition in the DSC.

When Exo Down
The Glass Transition Temperature
The glass transition is the temperature where the polymer goes from
a hard, glass like state to a rubber like state.

DSC defines the glass transition as a change in the heat capacity.

DSC the transition appears as a step transition and not a peak such as
seen with a melting transition.
 Heat Capacity
The computer will plot the difference in heat output of the two heaters
against temperature.

Heat absorbed by the polymer against temperature.

The heat flow is heat, q supplied per unit time, t.

The heating rate is temperature increase T per unit time, t.

Heat Capacity
We divide the heat flow q/t by the heating rate T/t. We end up with heat
supplied, divided by the temperature increase.

The amount of heat it takes to get a certain temperature increase is

called the heat capacity, or Cp
 Crystallization Temperature(Tc)
Polymer will have gained enough energy to move into very ordered.
arrangements, which we call crystals.

When polymers fall into these crystalline arrangements, they give off
heat. That is a latent heat of crystallization.

Heater under the sample pan.don't have to put much heat to keep the
temperature of the sample pan rising.
 Melting Temperature (Tm)

When polymer reach melting temperature, those polymer crystals begin

to fall apart. The chains come out of their ordered arrangements.

Polymer absorb heat There is a latent heat of melting.

Heater under the sample pan is going to have to extra heat into the
polymer .
When Exo up
Tc

Tg

Tm
 What can DSC measure?
Transitions.

Crystallization time and temperature.

Specific heat capacity.

Percent crystallinity.

Heats of fusion and reactions.

Rate and degree of cure.

Purity.
Differential Scanning Calorimetry (DSC)
DSC: The energy required to maintain zero temperature differential
between the sample and the reference is measured.

APPLICATION
Long term Stability Testing of Printing Inks By Differential Scanning
Calorimetric.

PROBLEM: Degradation (loss in finish quality) occurring in the ink

during Storage.
Differential Scanning Calorimetry (DSC)

Fig 1. Inferior Quality ink

Fig 2. Superior Quality ink

Aging is an exothermic process detectable by DSC. Exothermic

behavior observed is the result of degradation in ink.
Thermal stability of sample
Melting point Analysis of Phthalic Anhydride
MP of Standard Phthalic Anhydride is= 131C

MP 130.8C
% crystallinity determination
Sample a1 = HDPE Imported
Sample b2 = HDPE Local
5 1
a10609b2.001
a10609a1.001

119.62C
151.0J/g
0
0

-5 120.51C
156.5J/g
Heat Flow (mW)

Heat Flow (W/g)

-1

-10

-2

-15

127.53C

-3
-20

127.59C
-25 -4
20 40 60 80 100 120 140 160 180 200
Exo Up Temperature (C) Universal V4.5A TA Instruments

% crystallinity = Enthalpy of fusion of sample X 100

Enthalpy of fusion of 100% crystalline polymer
( Enthalpy of fusion of 100% crystalline polymer value is taken from literature)
 % Purity determination
sample a = Zinc Dust A = 98.56%
sample
0 b = Zinc Dust B = 94.16%
02608a.001
02608b1.001 420.38C
97.83J/g 424.06C

-2
Heat Flow (W/g)

-4

-6

-8
420.19C
102.4J/g

423.63C

-10
380 390 400 410 420 430 440 450
Exo Up Temperature (C) Universal V4.5A TA Instruments

% Metallic Zinc = Heat of Fusion of sample X 100

Heat of Fusion of std zinc (this value is taken from literature)

(heat of fusion Zn std literature. value =103.9 J/g)

Melting point Analysis of Phthalic Anhydride
MP of Standard Phthalic Anhydride is= 131C

MP 130.8C
Thank You