DSC & TGA

Differential Scanning Calorimetry and Thermal Gravimetric Analysis

Pashaie.mokhtar7@gmail.com

Different Techniques
Thermometric Titration (TT)
Heat of mixing
Thermal Mechanical Analysis (TMA)
Thermal Expansion Coefficient
Dynamic Mechanical Analysis (DMA)
Viscoelastic Properties
Differential Scanning Calorimetric (DSC)
Heat flow during Transitions
Thermal Gravimetric Analysis (TGA)
Weight Loss due to decomposition
Derivative Thermogravimetric Analysis (DTG)
Differential Thermal Analysis (DTA)
Heat of Transitions
Temperature Programmed Desorption (TPD)
Temperature at which gas is desorbed from (catalyst) surface
Emission gas Thermoanalysis (EGT)

Basic Principle
Sample is heated at a constant heating rate
Samples Property Measured

Wt
Size
Heat Flow
Temp
Gas evolved

TGA
TMA
DSC
DTA
TPD

The adsorption of heat will be different in the two pans due to the different composition in the pan. In
order to keep the temperature of the two pans constant during the experiment, the system needs to provide
more or less heat to one of the two pans.

What is DSC?

DSC looks at how a materials heat capacity (Cp) is changed by temperature.

This allows the detection of transitions like melts, glass transitions, phase
changes, and curing.

Thermal properties of a polymer

Heat Capacity
The heat capacity (Cp) of a system is the quantity of heat needed to raise the temperature
of the system of 1 C. It is usually given in units of Joules/C. It can be derived introducing
two parameters, namely the heat flow and heating rate.

Glass Transition
In the two regimes, before and after the Tg, the polymers have different heat capacities: Usually
polymers have a higher Cp above the Tg. Due to this difference in Cp, the DSC is a valuable method
to determine the Tg.

Temperature in the middle of the inclined part of the graph is by definition the Tg.

Semi-crystalline

Totally crystalline

V
Tm

Totally glassy

Tg

Tm T

Tg

Crystallization
When polymers fall into these crystalline arrangements, they give off heat to the system, thus the
process is exothermic.

1. have confirmation of the occurrence of the crystallization;

2. determine the polymer's crystallization temperature (Tc) as the lowest point of the
dip;
3. gain insight into the latent energy of crystallization for the polymer by observing the

Melting
melting is an endothermic transition. The melting is a first order transition since when the melting
temperature is reached; the polymer's temperature does not rise until all the crystals have
completely melted.

the latent heat of melting can be measured from the area of the peak

Melting of Indium
0

Heat Flow (mW)

Extrapolated
-5
Onset
Temperature
-10

156.60C
28.50J/g

Indium
5.7mg
10C/min

Heat of
Fusion

-15

-20

Peak Temperature
-25
150
Exo Up

157.01C
155

160

Temperature (C)

165
Universal V4.0B TA Instruments

Glass Transition vs. Melting

Melting occurs only in a crystalline polymer, while the glass transition takes place to just to
polymers in the amorphous state.

DSC Instruments

Two types of DSC instrument have been widely used:

The heat flux DSC (e.g., TA DSC and Mettler DSC)

The power compensational DSC (Perkin-Elmer system)

Heat flux DSC:

Power compensated DSC

Modulated DSC

the same heat flux DSC cell is used, but a sinusoidal temperature oscillation (modulation) is overlaid on
the conventional linear temperature ramp, resulting heating rate is sometimes faster than the underlying
linear heating rate, and sometimes slower than the underlying rate

Experiment : Thermal behavior of PET

Determine on the PET sample
a. The glass transition, melting and crystallization
temperature;
b. The heat of crystrallization and melting.

Preparing sample:
Cut a piece of PET film from the plastic bottle, clean it with water and dry it.
Make a thin film with the weight 5-15 mg, (this is the normal sample weight
in DSC
experiment).
Keep the film flat enough and with suitable size for Aluminum pan.

Glass transition sensitivity

Tg is reversible

TGA
Thermal Gravimetric Analysis

continuous
measurement
of weight on a
sensitive
thermobalance
as sample
temperature
is increased in air or in
an inert atmosphere.

Photodiodes
Infrared LED
Meter movement
Balance arm
Tare pan
Sample platform
Thermocouple
Sample pan
Furnace assembly

Purge gas outlet

Heater
Elevator base
Purge gas inlet
Sample pan holder

Balance Purge
Quartz Liner

Off-Gases

Sample
Thermocouple
Sample
Pan

Purge Gas In
Furnace Core

Data are recorded as a thermogram of weight versus temperature

Some applications
evaporation of residual moisture or solvent
polymer decomposition
Thermal stability studies
characterize polymers through loss of a known entity
such as HCl from poly(vinylchloride) Thus weight loss can be correlated with
percent vinylchloride in a copolymer.
determining volatilities of plasticizers and other additives

 Heating a sample of Calcium oxalate

Ca(C204)*xH2O Ca(C204) *H2O + x-1 H2O
Ca(C204)*H2O Ca(C204) + H2O
Ca(C204) CaCO3 + CO
CaCO3 CaO + CO2

Thermal Degradation of Polyhydroxylated Nylon 6,6

15.0k

W eight Loss (TG), %

100 C
o
150 C
o
200 C
o
235 C

-20

-40

-6.3%
-6.9%
-19.0%
-50.0%

205 C

10.0k

DTG

TG

425 C

-60

5.0k

-80

DTG
0.0

-100
0

100

200

300

400
o

Temperature, C

500

600

Poly (4-dodecyl-1-4-aza heptamethylene-D-glucaramide)

Thermal decomposition.

166 C

372 C
o
1.3%/ C

-1.3%@150 C
-20

DTG (%/ C)

TG (% Weight Loss)

188 C
o
0.6%/ C

-40
-60

-80
o

-97.5%@400 C
-100

TGpercent
0

100

200

300

400
o

Temperature, C

500

600

Thermogravimetric analysis of a polymeric blend containing HDPE and

an inorganic filler (phosphogypsum)

% weight loss

-10
-20
-30
-40
-50
-60

TGpercentL
0

-62.8%

100 200 300 400 500 600 700 800

o

Temperature, C

Precipitated Zr5O8(SO4)2*15 H2O

Analysis of Filtrate from Precipitation

Precipitation
5ZrOCl2 + 2H2SO4 + xH2O
Zr5O8(SO4)2*15 H2O (s) + 10 HCl
Decomposition
Zr5O8(SO4)2*15 H2O (s) Zr5O8(SO4)2*14 H2O
(s) + H2O (v)
Zr5O8(SO4)2

5 ZrO2 (s) +2 SO2 (v)

% Polymer

= 64.4%

% Carbon Black = 3.4%

% Glass Fibre

= 32.2%