Thermal analysis techniques

Common Definition of Thermal Analysis

A branch of materials science where the properties of

materials are studied as they change with temperatures.

Techniques:
• Differential Thermal Analysis
• Differential Scanning Calorimetry
• Thermogravimetric Analysis
• Dilatometry
• Thermomechanical Analysis
• Dielectric Thermal Analysis
• Evolved Gas Analysis
• Thermo-Optical Analysis
 Differential Thermal Analysis (DTA)

Can be conducted at
the same time with
TGA

 DTA measures temperature difference between a sample and

an inert reference (usually Al2O3) while heat flow to the
reference and the sample remains the same
 DTA
• Heating or cooling a test sample and an inert reference under
identical conditions, while recording any temperature difference
between sample and reference.

• This differential temperature is then plotted against time or

temperature (mostly).

• Changes in the sample which lead to the absorption or evolution of

heat can be detected relative to the inert reference.
 DTA
• Differential temperatures can also arise between two (inert) samples-when
their response to the applied heat treatment is not identical.

• DTA can therefore be used to study thermal properties and phase

changes which do not lead to a change in enthalpy.

• The baseline of the DTA curve should then exhibit discontinuities at the
transition temperatures and the slope of the curve at any point will
depend on the microstructural constitution at that temperature.

• A DTA curve can be used as a finger print for identification purposes, for
example, in the study of clays where the structural similarity of different
forms renders diffraction experiments difficult to interpret.

• The area under a DTA peak can be related to the enthalpy change and is
not affected by the heat capacity of the sample.
 Differential Scanning Calorimetry (DSC)

• As per ICTAC, DSC (Differential Scanning Calorimetry) is a

technique in which the heat flow rate (or thermal power) to the
sample is monitored against time or temperature while the
temperature of the sample in a specified atmosphere is
programmed.

What is ICTAC?

ICTAC is the International Confederation for Thermal Analysis

and Calorimetry which brings together national societies in the
field of thermal analysis and calorimetry (www.ictac.org)
 Differential Scanning Calorimetry (DSC)

Exothermal dQ/dT
Temperature

 DSC measures differences in the amount of heat required to

increase the temperature of a sample and a reference as a
function of temperature
Definitions (DSC)

• 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.
DSC: The Technique

• Differential Scanning Calorimetry (DSC) measures the

temperatures and heat flows associated with transitions in
materials as a function of time and temperature in a
controlled atmosphere.

• These measurements provide quantitative and qualitative

information about physical and chemical changes that
involve endothermic or exothermic processes, or changes
in heat capacity .
 Conventional DSC
Sample Empty

Metal Metal Metal Metal

1 2 1 2
Sample Reference
Temperature Temperature

Temperature
Difference =
Heat Flow

•A “linear” heating profile even for isothermal methods

What can DSC measures?
•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
 Principle of the thermal analysis technique

• Equipment
– Heating block
– Sample and inert
reference material
– Thermocouple

• Measurement

Heating

12
• In order to simply explain the principle of the thermal analysis
technique, consider a heating block (in copper for example)
with two holes.
• The metallic block is heated through a heating wire.
• The sample is introduced in one hole, and the inert reference
material in the other hole (most of the time dehydrated
alumina is used as an inert reference material)
• A same type of thermocouple is introduced on both sides into
the materials. A differential mounting of the thermocouples is
established in order to measure the difference of electromotive
force (emf) between the two sides.
• This difference of emf is related to a difference of temperature
according to the Oersted law. It is expressed as an electrical
signal, in microvolt.

• We will see now on the next slide what happens when the
block is heated at a controlled temperature.
 Principle of the thermal analysis technique

Heating of the sample and the inert reference material at a constant heating
rate

Difference between sample

Record of the furnace, sample and and inert reference material
inert reference material temperatures
temperatures 14
 Principle of the thermal analysis technique

- Tp is the controlled temperature delivered by the controller

to heat the metallic block, at a constant scanning rate. A
linear slope is obtained for Tp

- TR is the temperature recorded in the inert reference

material. Compared to Tp ,there is a shift in the temperature
curve corresponding to the thermal gradient of the material
and also the time of response of the furnace. After a certain
time, the TR curve becomes parallell to the Tp curve

15
-TE is the temperature recorded in the sample. The same shift is
noticed at the beginning of the heating phase. It is very close to
the shift observed for the inert reference material. After a certain
time a linear slope is obtained, following the slope of the Tp
curve.

-Now if the sample exhibits a melting during the investigated

temperature range, we will notice a melting plateau (horizontal
line) starting at the melting temperature of the sample.

-The TE temperature will remain constant during the whole

melting process (this is a thermodynamic property of melting).
When the melting process is finished, the TE temperature will
quickly change to follow again the linear slope.
 Endothermic and exothermic effects (1)

Heat Flux Which peak direction

for the endothermic
EXO
and exothermic
effect? Temperature (°C)

heating

cooling

ENDO

Time (sec)
See also evitherm Thermal 17
Analysis/Definitions
According to the thermal transformation, an endothermic or
exothermic effect is recorded.

In the case of an endothermic effect, it is needed to provide heat

to the system for its transformation. This will result in a
decrease of the temperature in the system during the
transformation.

In the case of an exothermic effect, the system provides heat

during its transformation. This results in an increase of the
temperature in the system.

In the case of a DTA curve, the endothermic peak is downwards

(decrease of ΔT) and the exothermic peak is upwards (increase
of ΔT).

In the case of a DSC curve, there is no real standardisation for

the endo and exo sides and according to the manufacturers,
both situations are found. So it is recommended to indicate on
the curve the endo/exo side that has been selected.
Most common endothermic effects
-melting, sublimation
-first order and second order phase transitions
-evaporation, dehydration
-denaturation (protein)
-gelatinization (starch with water)
-Pyrolysis

There is a particular endothermic transition, called glass

transition, that is not giving a peak. Glass transition (or
rubbery transition) is related to a variation of the
viscoelastic properties of the sample and is detected by a
variation of the DSC baseline. This variation corresponds
to a change in the heat capacity of the sample.
 Most common exothermic effects

-Crystallization
-Gelation (gel formation)
-Oxidation, combustion
-Decomposition, ignition, explosion
-Fermentation
-Most of the chemical reactions
-Polymerization, reticulation
 The calorimetric curve

Base line
Heat Flux
(mW)

Tf

Temperature (°C)

Area under the peak

Ti
corresponding to the heat
effect (expressed in mJ)

Time (sec)

See also evitherm Thermal Analysis/Units 21

 different parts of DSC curve
-Base line: Part of the recorded curve without any reactions or
transitions. This can be an isothermal baseline when the
temperature is maintained constant or a dynamic baseline when
the temperature is changed according to a controlled
temperature program

-Peak: portion of the curve which departs from and

subsequently returns to the baseline

-Peak area: area enclosed between the peak and the

interpolated baseline

The peak area corresponds to the integration of the variation of

the thermal power generated by the transformation of the
sample from the temperature, Ti of the start of the transition to
the temperature, Tf corresponding to the end of the transition:

Tf
Q= ∫ (dh/dt) dT
Ti
Specific heat capacity (at constant pressure)

The quantity of heat necessary to raise the temperature of a

unit mass of material by 1 K at constant pressure. It is indicated
by cp, and the following equation is obtained:

cp = m-1 . Cp = m-1 . (dQ / dT)p

where m is the mass of the material, Cp is the heat capacity and

dQ is the heat quantity necessary to raise the temperature of
the material by dT.
Subscript p indicates an isobaric process. cp is expressed in (kJ .
kg-1 . K-1) or in (J . g-1 . K-1).

This equation is valid in a temperature range where a material

shows no first order phase transition.

(dQ / dT) = (dt / dT ) . (dQ / dt)

= (heating rate)-1 . (heat flow rate)

So cp is equal to the ratio of the DSC heat flow signal by the

fixed heating rate and the sample mass.
 Pcalibration run
(dQ / dt) 2

3
Pspecimen run
mcal cpcal

I msp cpsp II

1 Pblank run

T
Each measurement consists of three runs at the same scanning
rate (cf. Figure):
(1) blank run (empty pans in sample and reference holder)
(2) calibration run (calibration/standard material in sample
holder and empty pan in reference holder)
(3) specimen run (specimen in sample holder and empty pan in
reference holder).
Based on the DSC principle (ISO 11357-1) and the definition of
the specific heat capacity, the following relation is obtained,
where P is the heat flow rate (dQ/dt) and the superscripts sp
and cal represent specimen and calibration material,
respectively, for the determination of the specimen Cp:

Cpsp = Cpcal [mcal (Psp –Pblank)] / [msp [(Pcal – Pblank)]

 Different calorimetric principles (DSC, calorimetry)

Heat Flux Plate DSC

Power compensated DSC Heat Flux Calvet DSC

26
 Different types of DSC principles

Heat Flux plate DSC: A technique in which the difference in heat

flow rate to a test sample and to a reference sample is analysed
while they are subjected to the same temperature variation
(heated or cooled). It is called a plate-DSC detector.

A low resistance heat flow path (metal disc) is used to connect

both the sample and reference. A single furnace is used in this
case.

Power compensated DSC: The temperatures of the sample and

reference are controlled independently using separate identical
furncaes. Temperatures of the specimen and a reference are made
identical by varying power input using seperate identical 2
furnaces.
DSC Thermogram

Oxidation
Heat Flow -> exothermic

Crystallisation Cross-Linking
(Cure)

Glass
Transition

Melting

Temperature
6
 Glass Transition
• The glass transition temperature,
Tg, is the temperature at which an
amorphous solid, such as glass or
a polymer or metallic glass,
becomes brittle on cooling, or soft
on heating.
• More specifically, it defines a
pseudo second order phase
transition in which a supercooled
melt yields, on cooling, a glassy
structure and properties similar to
those of cristalline materials e.g. of
an isotropic solid material.
 Exothermal How to observe Tg

Exothermal
Temperature

Experimental curves on heating after at 0.0084 K/min (1), 0.2 K/min (2)
0.52 K/min (3), 1.1 K/min (4), 2.5 K/min (5), 5 K/min (6), and 30 K/min (7).
 Differential Scanning Calorimetry
PET
2
Melting
1.5
ENDOTHERMIC
1 Glass Transition
Heat Flow (W/gm)

0.5

0
0 50 100 150 200 250 300 350
-0.5

-1

EXOTHERMIC Crystallization
-1.5
Temperature (C)

Sample: Polyethylene terephthalate (PET)

Temperature increase rate: 20°C/min
Temperature range: 30°C - 300°C
 Example DSC - PET
Sample: PET80PC20_MM1 1min
Size: 23.4300 mg
Method: standard dsc heat-cool-heat
DSC
File: C:...\DSC\Melt Mixed1\PET80PC20_MM1.001
Operator: SAC
Run Date: 05-Apr-2006 15:34
Comment: 5/4/06
Tm
Instrument: DSC Q1000 V9.4 Build 287
1.5

245.24°C

1.0 Tc
Tg
Heat Flow(W/g)

137.58°C
20.30J/g 228.80°C
22.48J/g
79.70°C(I) 81.80°C
0.5
75.41°C

Cycle 1

144.72°C
0.0

-0.5
0 50 100 150 200 250 300
Exo Down Temperature(°C) Universal V4.2E TA Instruments
 Experimental factors
• Specimen environment
• Composition
• Size and surface to volume ratio: packing state of powder
samples
• Rate of heating may saturate response capability of the
measuring system

• Peak temperature should not vary with sample size

• Lowering heating rate equivalent to reducing sample
weight: sharper peak with improved resolution

• For decomposition reaction can be useful to peak shape

and disposition but for kinetic analysis thermal gradient
should be minimized.
 Influence of Sample Mass
0
DSC Heat Flow (W/g)

Indium at Onset not

-2 10°C/minute influenced
Normalized Data 15mg by mass
10mg

4.0mg
-4
1.7mg

1.0mg
0.6mg
-6
150 152 154 156 158 160 162 164 166
706 Temperature (°C)
Effect of Heating Rate
on Indium Melting Temperature

-1
Heat Flow (W/g)

-2
heating rates = 2, 5, 10, 20 °C/min
-3

-4

-5
154 156 158 160 162 164 166 168 170
Temperature ( ° C)
6
DSC: Main Sources of Errors
•Calibration
•Contamination
•Sample preparation – how sample is loaded into a pan
•Residual solvents and moisture.
•Thermal lag
•Heating/Cooling rates
•Sample mass
•Processing errors
Sample Preparation : Shape
• Keep sample as thin as possible (to minimise thermal
gradients)
• Cover as much of the pan bottom as possible
• Samples should be cut rather than crushed to obtain a
thin sample (better and more uniform thermal contact
with pan)

99
Other DSC Techniques
Hyper-DSC
Based on principle that high heating rates give large broad transitions.
•Heating rates typically 400-500oC/min
•Need very small sample sizes (~nanograms)

Good for:
•A quick overview of new sample
•Picking out minute transition

Poor for:
•Accuracy: transitions can be shifted by as much as 40oC
•Repeatability: Very sensitive to thermal lag.
Other DSC Techniques
Modulated DSC

•Composite heating profile:

•Determines heat capacity and separates heat flow into that
due to reversible and non-reversible events.
62 62

Modulate +/- 0.42 °C every 40 seconds

Ramp 4.00 °C/min to 290.00 °C

60 60
Typical:
Heating rates: 0 - 50C

Modulated Temperature (°C)

58 58
Temperature (°C)

Modulation:
Period: 60 second 56 56

Amplitude: +/-10C
54 54

Note that temperature is not decreasing during

Modulation i.e. no cooling
52 52
13.0 13.5 14.0 14.5 15.0
Time (min)
Modulated DSC

Benefits
• Increased Sensitivity for Detecting Weak (Glass) Transitions
– Eliminates baseline curvature and drift
• Increased Resolution Without Loss of Sensitivity
– Two heating rates (average and instantaneous)
• Ability to Separate Complex Thermal Events and Transitions Into
Their Heat Capacity and Kinetic Components
• Ability to Measure Heat Capacity (Structure) Changes During
Reactions and Under Isothermal Conditions

Downside
• Slow data collection
Example MDSC

0.00 0.00

-0.02 -0.02 -0.02

-0.04 -0.04 -0.04

Nonrev Heat Flow (W /g)

Rev Heat Flow (W /g)

Heat Flow (W /g)

-0.06 -0.06 -0.06

-0.08 -0.08 -0.08

-0.10 -0.10 -0.10

-0.12 -0.12 -0.12

-0.14 -0.14
-50 0 50 100 150 200 250
Exo Up Temperature (°C) Universal V4.2E TA Instruments
Modulated DSC
Reversible Transitions
•Glass Transition
•Melting

Non-reversible
•Crystallisation
•Curing
•Oxidation/degradation
•Evaporation
 DSC vs. DTA
1.“DSC” stands for “Differential Scanning Calorimetry” while “DTA”
stands for “Differential Thermal Analysis.”
2. DSC is a technique in which the difference is calculated between the
amount of heat needed (heat flow) to increase the temperature of
the sample and the heat required to increase the temperature of the
reference while DTA is a technique in which the difference is
calculated between the temperatures required by the reference
and the sample when the heat flow is kept the same for both.
3. DSC is an instrument based on the DSC (the heat flow difference)
technique used to measure heat released or absorbed during the
transition phase while DTA is an instrument based on the DTA
(temperature difference) technique.
4. Both are used almost same purposes: glass transition, phase
changes, purity evaporation, melting, purity crystallization,
sublimation, polymerization, heat capacity, compatibility, pyrolysis,
etc. In DSC normally melting is avoided.
Thermogravimetric Analysis (TGA)

• A technique that
permits the
continuous
weighing of a
sample as a
function of
temperature and/or
as a function of
time at a desired
temperature
 TGA Applications: Inorganics

• Hydrates decomposition, drying phenomena

• Carbonates and other salts decomposition
• Kinetics and mechanisms of oxidation, and other solid-gas reactions
• Analysis of magnetic materials
• Etc.
 TGA Applications: Organics

• Identification of polymers and pharmaceutical agents

• Thermal stability of synthetic and natural polymers and other organics
• Analysis of polymer-matrix composites
• Kinetics and mechanism of solid organics – gas reactions
• Residual solvent determinations
TGA Applications: Oxidation of SWCNT
C+O2=CO2
Oxidation of amorphous
carbon Oxidation of catalyst
 Dilatometry
Correlation of Thermal Expansion with structure
• Materials expand by their
average bond length
increasing
• Expansion is governed by
the interatomic potential well
that binds the atoms and
ions together
• Tightly bound atoms reside
in deep energy wells that are
only slightly affected by
temperature
• More weakly bound atoms
reside in shallow energy
wells that are more affected
by temperature
• Glasses are disordered, so
expansion is isotropic 48
 Dilatometry
Measurement of the thermal expansion
• Expansion dilatometer
• Thermal mechanical analyzer
• Measures the length of the sample
– Typically a glass rod
– 0.5 cm x 1 cm
• As a function of temperature
• Linear Variable Differential Transducer (LVDT) accurately
converts distance changes of microns into millivolts.
• Thermocouple measures sample temperature
• Furnace provides sample heating and/or cooling
• Typically slow heating rate 3oC/min

49
Typical Pushrod Dilatometer

LVDT

50
 Thermal Expansion
1  L 
L   
L0  T  P
1  V 
V    V  3 L
V0  T  P

• For isotropic materials, homogeneous in three directions…

• Volume expansion coefficient is 3 times larger than linear

expansion

• Fine grained polycrystals are isotropic

51
 Determination of Linear
Thermal Expansion
1  L 
L   
L0  T  P
1  L(T2 )  L(T1 ) 
 L ~  
L0  T2  T1 P

• Determine L for several

temperatures

52