Principles of Thermal Analysis

Definition of Thermal Analysis

A group of techniques in which a property of the sample is monitored against time or temperature while the
temperature of the sample, in a specified atmosphere, is programmed.

It is stated in gFor Better Thermal Analysis and Calorimetryh, 3rd Edition, published in 1991 by ICTAC
(International Confederation for Thermal Analysis and Calorimetry).

This defines Thermal Analysis includes all the methods of measuring the sample properties while the sample
temperature is program-controlled.

Figure 1. Block diagram of Thermal Analysis instrument

Figure 1 shows the configuration of Thermal Analysis instrument.

Thermal Analysis instrument includes the followings:

 Detection Unit: Furnace, sample and reference holder, and sensor, heat and cool the sample in the furnace,
and detects the sample temperature and property.
 Temperature Control Unit: Controls the furnace temperature.
 Data Recording Unit: Records the signals of sensor and sample temperature, and analyzes them.
Temperature control, data recording and analysis are all computer-controlled. The combination of the furnace
and sensor enables the various types of the measurement techniques. This computer can be connected to the
several instruments which has the other types of measurement techniques, enables the simultaneous
measurement and analysis.

Table 1 shows the measurement techniques for each property. Each technique is called DTA, DSC, TG, TMA and DMA.

Abbrev. TA Measurement Technique Property Unit

DTA Differential Thermal Analysis Difference temperature °C or µV*

 DSC Differential Scanning Calorimetry Enthalpy W = J/sec

TG Thermogravimerty Mass gram

TMA Thermomechanical Analysis Deformation meter

Dynamic Mechanical
DMA Elasticity Pa = N/m2
Analysis

*
Thermocouple electromotive force.

Table 2 shows which effects and properties found in various materials are measured in each technique.

Technique
Phenomenon/Property
DSC TG TMA DMA

Melting ⚪ — Δ Δ

Glass transition ⚪ — ⚪ ⚪

Crystallization ⚪ — Δ ⚪

Reaction (Curing / Polymerization) ⚪ Δ ⚪ ⚪

Sublimation / Evaporation / Dehydration Δ ⚪ — —

Thermal decomposition Δ ⚪ — —

Thermal expansion / Thermal shrinkage — — ⚪ —

Thermal history ⚪ — ⚪ ⚪

Specific heat capacity ⚪ — — —

⚪:
Measurement Object
Δ:
Some compatible
—:
Not measured
The main application areas of DSC concern the determination of the melting, the glass transition, the
crystallization, the chemical reactions, the thermal history, and the specific heat capacity. Though the
sublimation, the evaporation, and the thermal decomposition can also be measured, this technique is not
usually used because of the mass change by the decomposition and the corrosion of the sensor by the
decomposed gas.
 TG measures the mass changes by the evaporation, the dehydration, the decomposition, and the oxidation
reaction. By the simultaneous measurement by TG connected with DTA, the exothermic and the endothermic
phenomena can be measured from DTA.

TMA measures the phenomena caused by deformation including the thermal expansion, the thermal
shrinkage, the glass transition, and the curing reaction. Though the melting and @the crystallization can
measured, there is case of the adhesion of the sample to the probe by the melting.

DMA measures the changes in the molecular motion and the molecular structures such as the relaxation, the
crystallization, and the curing reaction. It also measures the melting at the early stage until the melt flow
occurs.

Definitions of Thermal Analysis and Viscoelasticity

1. Definitions of Thermal Analysis
2. Definitions of Differential Scanning Calorimetry (DSC)
3. Definitions of Thermogravimerty (TG)
4. Definitions of Differential Thermal Analysis (DTA)
5. Definitions of Thermomechanical Analysis (TMA)
6. Definitions of Dynamic Mechanical Analysis (DMA)

 Descriptions

Principle of Differential Scanning Calorimetry (DSC)

Definitions of Differential Scanning Calorimetry (DSC)

DSC is the generic term for the following two measurement methods.

 Heat Flux DSCs

A technique in which the temperature of the sample unit, formed by a sample and reference material, is varied
in a specified program, and the temperature difference between the sample and the reference material is
measured as a function of temperature.
 Power Compensation DSC
A technique in which difference of thermal energy that is applied to the sample and the reference material per
unit of time is measured as a function of the temperature to equalize their temperature, while temperature of
the sample unit, formed by the sample and reference material, is varied in a specified program.

*
This is definition of DSC by JIS (Japanese Industrial Standard)

Description of DSC
 Figure 1. Block diagram of Heat Flux DSC

DSC is a commercially available instrument which has two (2) types: Heat Flux Type and Power Compensation
Type. Figure 1 shows the block diagram of Heat Flux DSC as an example. Heat Flux DSC comprises the
sample and reference holder, the heat resistor, the heat sink, and the heater. Heat of heater is supplied into
the sample and the reference through heat sink and heat resistor. Heat flow is proportional to the heat
difference of heat sink and holders. Heat sink has the enough heat capacity compared to the sample. In case
the sample occurs endothermic or exothermic phenomena such as transition and reaction, this endothermic or
exothermic phenomena is compensated by heat sink. Thus the temperature difference between the sample
and the reference is kept constant. The difference the amount of heat supplied to the sample and the reference
is proportional to the temperature difference of both holders. By calibrating the standard material, the unknown
sample quantitative measurement is achievable.

DSC enables the measurements of the transition such as the glass transition, melting, and crystallization.
Furthermore, the chemical reaction such as thermal curing, heat history, specific heat capacity, and purity
analysis are also measurable. Recently, with the development of the highly-functional polymeric material, these
thermal properties analysis needs are increasing dramatically. DTA and DSC detect the temperature
differences between the sample and the reference; however, DSC can perform the quantitative measurement
of the amount of heat on top.

Principle of Thermogravimetry (TG)

Definitions of Thermogravimetry (TG)

A technique in which the mass of the sample is monitored against time or temperature while the temperature of
the sample, in a specified atmosphere, is programmed.

*
This is definition of TG by ICTAC.
Definitions of Simultaneous Thermogravimetry and Differential Thermal Analysis (TG/DTA, TGA/DTA)

A method in which thermogravimetry and differential thermal analysis are combined and measured
simultaneously by a single apparatus.

*
This is definition of TG-DTA by JIS (Japanese Industrial Standard)
As defined above, TG is a technique that measures mass change in a sample, and it is used to detect
evaporation, decomposition, oxidation and other effects of temperature change that cause mass changes.

Description of TG/DTA

Figure 1. Block diagram of horizontal differential TG/DTA

Figure 1 shows the The balance beams for the sample and the reference are located in the furnace. The
masses of the sample and the reference are measured by the sensitivity-calibrated drive coils separately. The
mass difference is sent as TG signal. By the differential mass measurement, the effects of the beam
expansion, the convection flow, and buoyant force are cancelled. Thus the highly sensitive thermogravimetry
measurement is achieved. The mass measurement of the sample and the reference by the independent drive
coils enables the easy adjustment of the TG baseline drift electrically.

Also, thermocouple is located in each holder which enables the simultaneous DTA signal output.

TG can be utilized for the analysis of the thermal decomposition, the oxidization, the dehydration, the heat
resistance, and kinetics analysis. By combining with the other measurement technique, variety of information
can be achieved from one sample. In particular, TG/DTA simultaneous measurement instrument is most
common.

Principle of Differential Thermal Analysis (DTA)

Definitions of Differential Thermal Analysis (DTA)

A technique in which the difference in temperature between the sample and a reference material is monitored
against time or temperature while the temperature of the sample, in a specified atmosphere, is programmed.

*
This is definition of DTA by ICTAC.

Description of DTA
 Figure 1. Block diagram of DTA

Figure 1 shows the block diagram of DTA.

The sample and the reference are placed symmetrically in the furnace. The furnace is controlled under a
temperature program and the temperature of the sample and the reference are changed. During this process,
a differential thermocouple is set up to detect the temperature difference between the sample and the
reference.
Also, the sample temperature is detected from the thermocouple on the sample side.

Figure 2 Measurement principles of DTA

Graph (a) shows the temperature change of the furnace, the reference and the sample against time.
Graph (b) shows the change in temperature difference (ΔT) against time detected with the differential
thermocouple.
ΔT signal is referred to as the DTA signal.

Matters that do not change in the measurement temperature range (usually α-alumina) are used as reference.

When the furnace heating begins, the reference and the sample begin heating with a slight delay depending on
their respective heat capacity, and eventually heat up in according to the furnace temperature.
ΔT changes until a static state is reached after the heating begins, and after achieving stability, reaches a set
amount compliant with the difference in heat capacity between the sample and the reference. The signal at the
static state is known as the baseline.
When the temperature rises and melting occurs in the sample, for example, the temperature rise stops as
shown in graph (a) and the ΔT increases. When the melting ends, the temperature curve rapidly reverts to the
baseline.
At this point, the ΔT signal reaches the peak, as shown in graph (b).
From this, we can detect the samplefs transition temperature and the reaction temperature from the ΔT signal
(DTA signal).
In graph (b), the temperature difference due to the samplefs endothermic change is shown as a negative
direction and the temperature difference due to the samplefs exothermic change is shown as a positive
direction.

Principle of Thermomechanical Analysis (TMA)

Definitions of Thermomechanical Analysis (TMA)

A technique in which a deformation of the sample under non-oscillating stress is monitored against time or
temperature while the temperature of the sample, in a specified atmosphere, is programmed. The stress may
be compression, tension, flexure or torsion.

*
This is definition of TG by ICTAC.

Description of TMA

Figure1 shows the Block Diagram of a TMA.

The sample is inserted into the furnace and is touched by the probe which is connected with the Length
Detector and the Force Generator. The thermocouple for temperature measurement is located near the
sample.

The sample temperature is changed in the furnace by applying the force onto the sample from the Force
Generator via probe.

The sample deformation such as Thermal Expansion and Softening with changing temperature is measured as
the probe displacement by the Length Detector. Linear Variable Differential Transformer (LVDT) is used for
Length Detection sensor.
 Figure 1. Block diagram of TMA

There are several types of the probe for TMA. The choice is dependent on the measurement purpose.

Figure 2. TMA Probe types

(a) Expansion/Compression Probe:

It is used for the measurement of the deformation by the thermal expansion and the transition of the sample
under the compressed force is applied.

(b) Penetration Probe:

It is used for the measurement of the softening temperature.

(c) Tension Probe:

It is used for the measurement of the thermal expansion and the thermal shrinkage of the sample such as the
film and the fiber.

The materials of probes are quartz glass, alumina, and metals. The choice is dependent on the temperature
range and/or the measurement purpose.
 In case of the TMA which enables the dynamic force control on top of the static force control, the measurement
of the Stress-Strain, the Creep, the stress relaxation, and the DMA measurements can be performed.

rinciple of Dynamic Mechanical Analysis (DMA)

Definitions of Dynamic Mechanical Analysis (DMA)

 A technique in which the sample's kinetic properties are analyzed by measuring the strain or stress that is
generated as a result of strain or stress, varies (oscillate) with time, applied to the sample.
 Static Viscoelasticity Measurement
A technique in which the change in stress or strain is measured under uniform stress or strain that remains
constant across time.

*
These are definitions of DMA by JIS

Description of DMA

Figure 1 shows the Block diagram of DMA.

The sample is clamped in the measurement head of the DMA instrument. During measurement, sinusoidal
force is applied to the sample via the probe. Deformation caused by the sinusoidal force is detected and the
relation between the deformation and the applied force is measured. Properties such as elasticity and viscosity
are calculated from the applied stress and strain plotted as a function of temperature or time.

Figure 1. Block diagram of DMA (Tension mode)

DMA is used for measurement of various types of polymer materials using different deformation modes. There
are tension, compression, dual cantilever bending, 3-point bending and shear modes, and the most suitable
type should be selected depending on the sample shape, modulus and measurement purpose.

Viscoelastic properties such as:

-Storage modulus: E', G' (purely elastic component)
-Loss modulus: E", G" (purely viscous component)
-Loss tangent: tanδ (=E"/E'),
can be measured by DMA, and their dependence on temperature and frequency can be analyzed.

Figure 2. DMA Deformation modes

Analysis of the glass transition temperature and temperature dependence of the modulus can be measured by
the temperature dispersion measurement. By performing simultaneous measurement of temperature
dispersion and frequency dispersion, relaxation phenomena such as glass transition, side-chain relaxation and
local mode relaxation can be observed. This approach allow us to obtain information about molecular structure
and molecular motion of polymers.