Thermal Analytical
Techniques
 

Therma
Thermall Analytical
Analytical Techniq
Techniques
ues
Thermal analysis is a group of Technique in Which a physical
a physical property Is
Measured as a function of temperature.
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)

 

Different
Differential
ial Thermal
Thermal Analys
Analysis
is (DT
(DTA)

DTA: The temperature difference between a sample and reference material is

DTA
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.
air.
•Two minima and one maximum observed in graph.
 

Different
Differential
ial Thermal
Thermal Analys
Analysis
is (DT
(DTA)

•
APPLICATIONS : For identification purpose
identification purpose .
Determination of heat change.
Determination decomposition in various atmospheres.
 

Thermal Gravimetric Analysis

Analysis (TGA)
TGA is used to measure weight changes in material with temperature .

APPLICATION:
Thermal Stability
Stability Determination
Determination of bonded Silicas
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
smaller total weight loss.
•Silica B (Inferior material) exhibit a larger total
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)

sample. Softening temperature 49.5°C
Suspect sample.
sample. Softening temperature 92.7°C
Control sample.

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

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

Analysis (DMA)

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

much increase in Tg.

:Material 2(Inferior quality) initially not fully cured

CONCLUSION :Material
 

Basic Principles of Thermal Analysis

Modern DSC instrumentation consists of four parts:
parts:
• Sample holder.
• Sensors to measure a heat flow and temperature of the sample.
• An enclosure
enclosure to control
control parameters
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.

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
• Sepa
Separa
rate
te sens
sensor
orss and
and hea
heate
ters
rs for
for the
the sampl
amplee and refe
refere
renc
nce.
e.

Temperature controller 
•

Differential thermal power is supplied to the heaters to maintain the

tem
tempe
pera
ratu
ture
re of the
the sam
sample and
and refe
refere
renc
ncee .
 

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.
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
Sample pan Mechanical
shock of Cool air entry
Sample topples 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 Pract
Practices
ices 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 Transi

ransition
tion Temper
emperature
ature
•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.

capacity.

•DSC the transition appears as a step transition and not a peak such as
seen with a melting transition.
 

Heat Capacity
•

The computer
against will plot the difference in heat output of the two heaters
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
•  per unit time,
time, t .
 

Heat Capacity
•

We divide
divid
supplied
supplied, e the heat
, divided byflow q/t by the heating
the temperature rate
increase.
increase . T/t. We end up with heat

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

called the heat capacity, or C p
 

Crystallization
Crystalliza tion Temper
emperature(T
ature(Tc)
c)
•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
Meltin g Tempera
Temperature
ture (Tm)
(Tm)

•When polymer reach

reach melting temperature,
temperature, those polymer
polymer crystals begin
to fall apart. The chains come out of their ordered arrangements.

• Polymer absorb heat There is a latent heat of melting.

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

differential
 between the sample and the reference is measured.

APPLICATION
Long term Stability Testing
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= 131 C
°

MP 130.8 C °
 

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

119.62°C
151.0J/g
0
0

-5 120.51°C
) 156.5J/g
)
W -1 g/
m( W(
w w
ol -10 ol
F F
t t
a a
e e
H -2 H
-15

127.53°C

-3
-20

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

% 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
 –
  ––– 02608b1.001 420.38°C
97.83J/g 424.06°C

-2

)g -4
/
W(
w
lo
F
t
a
e
H -6

-8
420.19°C
102.4J/g

423.63°C

-10
380 390 400 410 420 430 440 450
Exo Up Temperature
Temperature (°C) Uni versal V4.5A TA Instrum ents

% Metallic Zinc = Heat of Fusion of sample X 100

Heat of Fusion of std zinc (this value is taken from literatu
literature)
re)
 (heat of fusion Zn std literature. value =103.9 J/g)
 

Melting point Analysis of Phthalic Anhydride

MP of Standard Phthalic Anhydride is= 131 C °

MP 130.8 C °
 

Than
Th ank
k You