Thermal Analysis

SSK 4242
Instrumentation Concept of Thermal Analysis

Gas outlet

Furnace Temperature programmer

Thermocouple

Sample Detector amplifier and

data collection

Detector device Display:

computer/recorder

Gas inlet Ref: Haines 1995

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 Thermal Analysis
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Thermal Analysis Curves (Thermograms)

Tf
The normal shapes of thermal
analysis curves which shows
the initial temperature (Ti), the Ti
final temperature (Tf) and peak
temperature (TP)

Signal
Tp

Temperature, oC

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 Thermal Analysis
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Computer in Thermal Analysis

Computer becomes an important component that plays the

following roles in modern thermo analysis instruments :

 as a means to provide operational instructions during

thermal analysis experiment

 collection and interpretation, storage and retrieval of

operational and experimental data

 user friendly instrument that makes modern thermal

analysis experiments more interesting, convenient, and
yet more precise and accurate.

 Simulation of the behaviour of the instrument and the

sample under certain conditions

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 Thermal Analysis
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Thermal analysis methods are less specific….

Many analytical methods give results that are

characteristics to the particular samples. For example, IR
produces spectrum of a polymer that is characteristics of
that polymer which is less influenced by the sampling
method, or the instrument used, or the time when the
experiment is carried out.

Thermal analysis, on the other hand, is “less specific” which

produces result that is dependent of the experimental
conditions. This is due to the dynamic nature of the thermal
analysis process.

Lecture 2 4-Nov-04 4
 Thermal Analysis
Factors that Influence
SSK 4242
the Thermal Analysis
The Dynamic of Results

Thermal Analysis Gas flow

Process
Liberated
gas or
volatile
products

Furnace Furnace

Sample
holder

Heat flow

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 Fa Thermal Analysis
th ct SSK 4242
Re e T ors
In thermal analysis instrument, the signal su he th
lt rm at
generated by the sensor depends on: s al In
An flu
al en
ys ce
is
 The extent of the reaction and the rate of reaction
 The extent to which the measured properties have changed
and the rate of the changes
 The heat transfer by conduction
 Heat convection
 The radiation of heat within and around the instrument
 Reaction of the sample with the environment

Thermal analysis reports must include statement on:

 All the experimental conditions involved in the experiment,

 Comparison between sample can only be made on the basis
that all conditions of the experiments are the same,
 Any differences must be clearly stated in detail in the reports.

Lecture 2 4-Nov-04 6
 Thermal Analysis
Factors that Influence
In thermal analysis … the Thermal Analysis
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Results

The signal generated by the thermal sensor depends on:

 The rate of reaction and the extent of the reaction

 How far the measured changes have taken place and the rate of
change
 Heat transfer by conduction
 Heat convection
 Heat radiation within the instrument
 Reaction of the sample with its surrounding environment

 The thermal analysis report should mention all the experimental

conditions used in the experiment.

 Comparison between samples can only be made if the

experimental conditions for the samples involved are the same.
Any discrepancy must be clearly spell out.

Lecture 2 4-Nov-04 7
 Thermal Analysis
Factors that Influence
Sample Factor the Thermal Analysis
Results
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a) Sample history: b) Diluent material:

 Information regarding the original  An inert material only should be
source of the sample and any pre- used as the diluent in thermal
treatment received by the sample analysis
 The sample : diluent composition
c) The following should be known
information (if known)  The diluent may influence the
should also be stated in thermal conductivity of the sample.
terms of:
 Purity
 Chemical composition d) Particle size:
 Chemical formula  Particle size may influence the
thermogram, particularly when this
involves surface reaction.

e) Trace contamination
 This may become catalyst to the decomposition reaction and change
the order of reaction.

Lecture 2 4-Nov-04 8
 Thermal Analysis
Factors that Influence
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the Thermal Analysis
Sample Holder/Crucible Results

a) Sample holder material

 Should not react with the sample during the experiment.
 Aluminium
 Platinum
 Silica
 Alumina
 Changing the sample holder may change the rate of heat flow
due to heat conductivity differences of the sample holder
materials.

See Sample Holders

b) Sample holder geometry
 A wide and shallow crucible will facilitate absorption of reactant
gas into the sample and diffusion out of the gaseous or volatile
products
 A narrow and deep crucible will prevent the free movement of
the gasses.

Lecture 2 4-Nov-04 9
 Thermal Analysis
Factors that Influence
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the Thermal Analysis

The Effect of Heating Rate Results

a) The rate of heating (dT/dt) may be programmed:

 At a fix rate of 0 K/min: isothermal condition
 At a rate of 10 K/min: normal rate (commonly used)
 At a high rate of 100 K/min: used in simulation of combustion
process of materials.

b) Thermal analysis may also be carried out by cooling.

c) The following process normally proceed to reach a finite value:

 Rate of heat transfer,
 Physical changes, and
 Most reactions

Every sample reacts differently when heated or cooled at different

heating/cooling rates.

Lecture 2 4-Nov-04 10
 Thermal Analysis
Factors that Influence
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the Thermal Analysis
Thermal Lag Results

… where there is a temperature gradient within a body while undergoing heat

treatment due to heat transfer process…….the sample temperature is seen to
have higher temperature than its actual temperature.

Heat is transferred by the following process:

 conduction Thermal lag becomes
 convection larger when the rate of
 radiation heating gets higher
Correction of thermal lag effects:

Te = Te,0 + α .β + c Where:
Te = uncorrected temperature observed
at a heating rate β
α = a constant
Example: determination of the Te,0 = corrected temperature at β = 0
melting point of Gallium β = heating rate (K/min)
c = correction factor, determined by
Te = 303.56 + 0.074 . β - 0.2 calibration
= 304.10 K
Lecture 2 4-Nov-04 11
 Thermal Analysis
Factors that Influence
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the Thermal Analysis
The Effect of Heating Rate Results

High heating rate

 Some portions of the sample melt before the sample begins to
decompose.

Low heating rate

 All reactions have taken place before the sample begins to melt.
 Low heating rate gives better resolution for two adjacent
changes.

Nearly equilibrium condition

 Where heating rate is very low, less than 1 K/min mostly used.

Lecture 2 4-Nov-04 12
 Thermal Analysis
Factors that Influence
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The Effect of Heating Rate the Thermal Analysis
Results

Heating rate effects the initial

temperature, final temperature Tf
and the temperature range
where the changes occur during
heat treatment. Ti

Ti,fast > Ti,slow

Tf,fast > Tf,slow
(Tf - Ti)fast > (Tf - Ti)slow

Signal
Tp
See an Example

Rate of heating can either:

Temperature, oC
 Linear, OR
 Complex with certain pattern
Example: isothermal at 25 oC for 2 min., followed by 50 K/min up to 300 oC;
isothermal at 300 oC for 10 min., and then cooled at a rate of 5 K/min to room
temperature.

Lecture 2 4-Nov-04 13
 Thermal Analysis
Factors that Influence
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the Thermal Analysis
The Effect of Atmosphere Results

The gas used to provide atmosphere strongly influences

 The heat transfer Figure 3.20 shows the
 Chemical process of the sample effect of temperature
 The reaction products on the thermal
Although the atmosphere is inert towards the sample, the rate conductivity of helium,
of heat transfer is influenced by the type of the atmosphere
used
nitrogen and argon
Four types of gasses that are normally used as the
atmosphere in thermal analysis are as follows:

Gas at 1 atm Thermal conductivity

(10-2 J/(cmK) at 373 K
Helium 17.77
Nitrogen 3.09
Air 3.17
Carbon monoxide 2.23

The table shows that heat transfer by conduction in helium is almost eight
times higher than that in carbon monoxide.

Exercise ?
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 Fa Thermal Analysis
c
th tor SSK 4242
The Effect of Atmospheric Partial Pressure Re
eT st
h
su herm at I
lt s al nflu
An e
aly nce
s is
CaCO3 CaO + CO2

Remember Le Chatelier Principle ? The effect of carbon monoxide partial

pressure on the TG curve of calcium
carbonate AR. 110 mg heated at 100
K/min in
1. 1.0 atm N2,
2. 0.1 atm CO2,
1 – reaction fraction (1 - α )

3. 0.3 atm CO2,

4. 0.5 atm CO2,
5. 0.7 atm CO2,
6. 1.0 atm CO2.
In experiment (2) – (5), N2 was
added to maintain the total pressure
of 1 atm.

Original Ref.: F.W. Wilburn, J.H. Sharp,

J. Thermal Anal., 1993, 40, 133

Temperature
Exercise ? Lecture 2 4-Nov-04 15
 Thermal Analysis
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The Effect of Atmosphere

If the heat treatment is accompanied If the reaction involves an

by chemical reactions, the thermal equilibrium, according to the Le
events may change completely. Chatelier Principle, high
Example, metal is stable when heated concentration of the reaction
in nitrogen but will be oxidized when products will force the reaction to
heated in air. shift backwards.

Calcium Carbonate CaCO3 CaO + CO2

 Begins to decompose at temperature
< 700 oC in the atmosphere that If the sample reaction produces
contains low concentration of CO2 gas, its own atmosphere will be
 The compound does not decompose formed on its surface that may
until the temperature reaches > 900 change the equilibrium, kinetics and
o
C in the CO2 at a pressure of 1 atm heat transfer processes.
(See Figure)

The rate of gas flow is important since static atmosphere will not remove the
released gas during the heat treatment and does not remove heat from the
sample.

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 Thermal Analysis
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The Effect of Sample Mass

The following will affect the If the sample size is too small (1 µ g), the
thermal analysis: signal will become very small, individual
 Physical properties crystals may independently react that leads
 Sample size to the formation of multiple responses/peaks.
 Sample packing
 Sample density On the other hand, if the sample size is too
 Particle size large, the signal will be large but resolution/
separation of adjacent multiple consecutive
Very large sample size will only be reactions will difficult.
needed if the when the sample
consists of several components and
the component of interest
constitutes a small fraction. Comparison between thermal
analysis curves can only be made if
the sample size are the same.

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 Thermal Analysis
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SCRAM: the five important parameters

in thermal analysis

S = Sample
C = Crucible or sample holder
R = Rate of heating
A = Atmosphere
M = Mass of sample

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 Thermal Analysis
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Simultaneous Thermal Analysis

 A single thermal analysis technique does not give sufficient

information for scientists to decide conclusively about the
processes taken place during the sample heat treatment. For
example, DTA with an endothermic peaks does not indicate
whether the process is a chemical reaction or a physical change
such as melting, whether a gas has been released or not.

 TG thermogram on the same sample will indicate whether or not

there is a mass loss within the temperature range to ensure that
the process is not melting. Conversely, no mass lost indicates
that there is melting process.

 The use of combined simultaneous techniques produce more

complete information although this means that the optimum
conditions of a single method will have to be sacrificed.

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 Thermal Analysis
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Complementary Methods

 Two different techniques are used towards different sample or different

time. For example, the TG method is used for first sample of a polymer
and the DTA method is used for the second sample of the same polymer.

 Hyphenated techniques, e.g. TG-DTA, or DSC-optometry are simultaneous

techniques in which two methods are used at the same time for the
analysis of a sample. Simultaneous techniques are preferred to avoid
difficulties arise from the use of single techniques
 Almost any analytical methods can be used as the complementary for
thermal analysis. For example, released gas can be separated using
chromatographic techniques, dissolved and titrate, measured using
electrochemical or spectroscopic techniques such as IR or atomic
spectroscopy.

 Solid reaction products may be studied by surface characterization, study

their catalytic activities and analysed using AAS etc.

 All the analytical methods are important in providing full understanding

towards the process taken place during the heat treatment of thermal
analysis.
Lecture 2 4-Nov-04 20