Introduction to TG/DTA/DSC

Thermal Processing Technology Center

Illinois Institute of Technology
 Outline
• Introduction
• Theory of TG/DTA/DSC
• Application of TG/DTA/DSC
• TG/DTA/DSC in Metallurgy application
• Experiment difficulty
 Application of Thermal Analysis in
Material Research
• The almost universal applicability of thermal analysis
technique has led to their use in nearly every field of
science, with a strong emphasis on solving problems in
materials technology and engineering, as well as
"pure" scientific investigations.

• The change in physical properties of a substance

subjected to a controlled temperature program as a
function of temperature is measured.

• Techniques Include TG, DTA, DSC, DMA, TMA

 Introduction to TG
• Thermogravimetry is a technique measuring the
variation in mass of a sample when it undergoes
temperature scanning in a controlled atmosphere.
This variation in mass can be either a loss of mass
(vapour emission) or a gain of mass (gas fixation).
 Introduction to DTA
• Differential thermal analysis is a technique measuring
the difference in temperature between a sample and a
reference (a thermally inert material) as a function of
the time or the temperature, when they undergo
temperature scanning in a controlled atmosphere.
The DTA method enables any transformation to be
detected for all the categories of materials.
 Introduction to DSC
• Differential scanning calorimetry is a technique
determining the variation in the heat flow given out or
taken in by a sample when it undergoes temperature
scanning in a controlled atmosphere.
With heating or cooling any transformation taking place
in a material is accompanied by a exchange of heat ;
DSC enables the temperature of this transformation to
be determined and the heat from it to be quantified.
 Theory of TG (Thermogravimetry)
• Measure the mass of sample as a function of temperature
• Determine sample purity, decomposition behavior, chemical kinetics
Theory of DTA (Differential Thermal Analysis)

• The temperature difference between reference and sample

is monitored as a function of temperature
 Theory of DSC (Differential Scanning Calorimetry)
• The difference in heat flow to or from a sample and to or from a
reference is monitored as a function of temperature or time, while the
sample is subjected to a controlled temperature program

Power compensated DSC

 Theory of DSC (Differential Scanning Calorimetry)
Temperatures are measured in thin plates in contact with those,
thereby measuring the difference in heat flow from crucible. This
gives a signal proportional to the difference in heat capacities
between the sample and reference and thus the instrument will work
as DSC.

Heat flux DSC

Different principles of DSC signal
detection
Different principles of DSC signal
detection
The difference between DTA and DSC
DTA
Temperature difference is measured, amplified and recorded. The peak
area can be converted to heat only if a suitable reference is used
DSC
The temperature difference is controlling the electrical power to the
sample and reference in order to keep them at the same temperature.
The peak area directly corresponds to the heat consumed or produced by
the sample

Modern DTA (also called heat flow DSC)

Temperatures are measured in thin plates in contact with those, thereby
measuring the difference in heat flow from crucible. This gives a signal
proportional to the difference in heat capacities between the sample and
reference and thus the instrument will work as DSC.
 Application of TG

• Study thermal degradation

• Chemical reaction resulting in changes of mass such
as absorption, adsorption, desorption
• Sample purity
 Application of DTA

• Primarily used for detection of transition temperature

• Sample purity
 Application of DSC
• Determination important transition temperatures
• Determine heat of fusion of a crystal phase and the
degree of crystallization
• Study crystal kinetic
• Determine heat capacity
• Determine heat of formation
• Sample purity
 Summary
TG DTA DSC
Theory Measure the mass of Measure temperature Measure heat flow
sample difference between difference between
reference and sample reference and sample

Application TG DTA DSC

Mass change Yes No No

Qualitative analysis of No Yes Yes

Heat change

Quantitative analysis of No No Yes

heat change
Program experiment temperature
DSC curve
TG-DTA curve of CuSO4-5H2O
 Cp determination
• Instruments calibrated by a standard

Heat flow ( µ V)

Ab
Ac As
mc × (As − Ab)
Cp = Cpc ×
ms × (Ac − Ab)
T

time
 Metallurgy Application
Phase transformation and melting of Iron
Heat Flow/ 
918.6 C 1400.6 C 1533.7 C
Exo
-10

769 C
-20
1404 C
1

924 C 3
-30

1 : Point de curie Results 2

• Different events may be observed

-40 2 : Transition alpha --> Gamma
3 : Transition Gamma --> Delta
4 : Fusion during the heating :
-50
• at 769°C : curie point
-60
• at 924°C : α → γ transition
• at 1400.6°C γ → δ transition
-70 • at 1533.7°C : melting of iron
4

-80
1551 C

200 400 600 800 1000 1200 Temperature/

 Metallurgy application
Oxydation of a steel in the scanning mode
TG./ % DTG/ %/min

0.08
Results
Above 700
C a
0.5 0.06 mass gain is
observed : the
DTG shows two
0.04
steps in the
oxidation.
0.0 TG 0.02
Below 700
C a
mass loss is
DTG
observed.
0.00

Temperature/

200 400 600 800 1000 1200
 Metallurgy application
Reduction of a steel at 1200
C
TG/ % Temperature/

0.1 1300

Results

T At 1000
C a small mass gain

-0.0 1200
is observed due to traces of
O2 and H2O. But when the
temperature of 1200
C is
reached a strong mass
-0.1 1100 decrease corresponding to the
steel reduction is observed.

-0.2 TG 1000

2.0 2.5 3.0 3.5 4.0 Time/ h

 Metallurgy application
Isothermal transformation of a high speed steel
Heat Flow/ mW Temperature/

Exo
9

600

8
Temperature Results

500
When the temperature is
7 First heating stable at 560
C a low
exotherm can be observed,
6
Second heating
the DSC curve decreases
400
slowly.
5
After the isotherm of 3 hours
300 the same sample is cooled
4
then heated a second time in
the same conditions.
3
200
The difference between the
two successive traces
2
correspond to the sample
100 transformation at 560
C.
1

0.5 1.0 1.5 2.0 2.5 3.0 Time/ h

 Metallurgy application
Melting of a Cu-Ti intermetallic compound

Heat Flow (µV)

Exo
50
Results

0
A double peak of melting is
monitored.
1 2

-50
The onset peak of the first
932.9°C
fraction is 925
C.

The top of the second fraction

-100
is 978
C.
Onset point 1 : 925,2 °C
Onset point 2 : 968.3 °C
Enthalpy / J/g : 183.6 (Endothermic effect) (34.0 + 149.6) The total heat of melting is
-150
183.6 J.g-1.

-200

-250 978.1°C

500 600 700 800 900 1000 Temperature (°C)

 Metallurgy aplication
Melting of Pb-Sn alloy
H E AT F L OW /m W
E xo

Results
-5
1 2
The melting curve presents
two peaks. In fact only pure
substances melt presenting a
-10 Ent h : - 53. 891 J/ g
unique peak : generally alloys
T . On s e t : 183. 5 C present a more complex
Ent h1 : - 20. 2 1 2 J / gmelting curve. In this case Pb
Ent h2 : - 33. 6 7 9 J / gan Sn present an eutectic at
-15 Top of peak1 : 186. 9 C 183.5
C. The end of melting
Top of peak2 : 213. 2 C corresponds to the liquids
curve. M 119 presents the
phase diagram of Pb-Sn
-20 system.
Sn/ Pb : 86/ 14
- - - - - - - - - - - - -

-25

T E MP E R ATU RE /°C

-30 175 200 225 250 275 300 325

 Metallurgy application
Phase diagram of Pb-Sn system
T E M P E R A T U R E /°C

Results
325

The onset
300 temperature
of the melting
curve
275
generally
corresponds
250 to the
eutectic
temperature
225
of the
system. The
200 temperature
of liquids is
given by the
175
top of the
peak of
0 20 40 60 65 80 86 100
melting.
38
Pb Sn
 Experiment difficulty
Explanation of experiment result
• Some curves might not be smooth and sharp

System error
• The error of commercialized instrument is about 5%
• The measured thermodynamic property can be applied to modeling
only if the error is less than 1%
Crucible material Condition
Crucible selection Pt Nonmetallic sample
• Crucible should not Al2O3 Metallic sample
• react with sample
W Reacting gas

Temperature setting BN Metallic sample

• The higher temperature, the more problems
- high sample vapor pressure
- high sample diffusivity
- short life time
 Setaram calorimeter

Setsys1750:
TG
TG/DTA
TG/DSC
 Thermal analytical techniques, abbreviation and
properties investigated

Technique Abbreviation Physical Properties

• thermodilatometry - length
• Thermogravimetry TG(TGA) mass
• Derivative thermogravimetry DTG mass
• Differential Thermal Analysis DTA temperature
• Differential Scanning Calorimetry DSC enthalpy
• Thermomechanical Analysis TMA dimension
• Dynamic Mechanical Analysis DMA stiffness & damping
• Thermally Stimulated Current TSC dipole alignment/relaxation
• Dielectric Analysis DEA dielectric permittivity/loss factor
• Evolved Gas Analysis EGA gaseous decomposition products
• Thermo-optical Analysis TOA optical properties