Thermal Analysis

Prof. Nizam M. El-Ashgar

1
 Introduction
❖ Thermal Analysis is the term applied to a group of methods
and techniques in which chemical or physical properties of a
substance, a mixture of substances or a reaction mixture are
measured as a function of temperature or time, while the
substances are subjected to a controlled temperature
programme.
❖ Over a dozen thermal methods can be recognized, which
differ in the properties measured and the temperature
programs.
❖ Find widespread use for both quality control and research
applications on industrial products such as polymers,
pharmaceuticals, clays and minerals, metals and alloys.
What TGA Can Tell You

• Thermal Stability of Materials.

• Oxidative Stability of Materials.
• Composition of Multi-component Systems.
• Estimated Lifetime of a Product.
• Decomposition Kinetics of Materials.
• The Effect of Reactive or Corrosive Atmospheres
on Materials.
• Moisture and Volatiles Content of Materials.
The following table is a list of the main thermal
analysis methods:
While carrying out these measurements, the
furnace atmosphere can either be static air or a
continuous flow of gas (purging).
Examples are: inert conditions (nitrogen) to inhibit
oxidation, or reducing condition (e.g. purging
hydrogen), etc.
 General thermodynamic relationships
Thermal analyses are usually run under conditions of constant
pressure, the underlying thermodynamic equation is the Gibbs-
Helmholtz expression:
G0 = H0 - TS0
where G=free energy of the system, H=enthalpy of the system,
S=entropy of the system, T=temperature in kelvins

The general chemical reaction

aA + bB → cC + dD
Is spontaneous as written if G<0, is a t equilibrium if G=0, and
does not proceed if G >0.

Thermal analysis involves the monitoring of spontaneous

reaction.
Differentiating the Gibbs-Helmholtz equation with respect to
temperature (assuming S and H not vary with temperature):

d (G )
= −S
dT
Show how to move from a stable situation (G>>0) to one
where reaction will occur.
S > 0, an increase in temperature cause G<0,
S < 0, decreasing the temperature will achieve the desired
spontaneous reaction.

Once the reaction is made to occur, thermal analysis may be

used to detect the process, yielding different and
complementary information.
 Thermal methods
Generalized instrument:
• Temperature programmer

• Sample in furnace with controlled atmosphere

 x axis  y axis
• temperature property

• Output: Plot of the property (y axis) versus T.

Types of thermal event
- Phase transition.
- Sublimation.
- Radiolytic decomposition.
- Oxidation/ combustion.
- Double decomposition.
- Melting (fusion).
- Adsorption, desorption.
- Thermal decomposition.
- Glass transition.
- Heterogeneous catalysis.
- Desolvation.
 Thermogravimetry (TG)
❖ Thermogravimetric analysis (TG): is the study of weight changes of
a specimen as a function of temperature or time. The
temperature is increased at a constant rate for a known initial
weight of the substance and the changes in weights are
recorded as a function of temperature at different time interval.
❖ The technique is useful strictly for transformations involving the
absorption or evolution of gases from a specimen consisting of a
condensed phase.
❖ A plot of mass versus temperature (thermogravimetric curves or
thermogram or TG curves) permits evaluation of thermal stabilities,
rate of reaction, reaction processes, and sample composition.
Measurements of changes in sample mass with temperature are
made using thermobalance. The balance should be in a suitably
enclosed system so that the atmosphere can be controlled.
General considerations

Suitable samples for TG are solids that undergo one of

the two general types of reaction:

Reactant(s) → Product(s) + Gas (a mass loss)

Gas + Reactant(s) → Product(s) (a mass gain)

Processes occurring without change in mass (e.g., the

melting of a sample) obviously cannot be studied by
TG.
 Mechanisms of Weight Change in TGA
• Weight Loss:
– Decomposition: The breaking apart of chemical bonds.
– Evaporation: The loss of volatiles with elevated
temperature.
– Reduction: Interaction of sample to a reducing
atmosphere (hydrogen, ammonia, etc).
– Desorption: a substance is released from a surface.
• Weight Gain:
– Oxidation: Interaction of the sample with an oxidizing
atmosphere.
– Absorption: absorbing something or of being absorbed.

All of these are kinetic processes (i.e. there is a rate at

which they occur).
 Factors affecting the TG curve

The factors which may affect the TG curves are

classified into two main groups.
(1) Instrumental factors (2) Sample Characteristics
(1) Instrumental factors
(a) Furnace heating rate
(b) Furnace atmosphere
(2) Sample characteristics includes
(a) Weight of the sample
(b) Sample particle size
 Instrumental factors
• Furnace Heating rate: The temperature at which the
compound (or sample) decompose depends upon
the heating rate. When the heating rate is high, the
decomposition temperature is also high. A heating
rate of 3.5°C per minute is usually recommended for
reliable and reproducible TGA.
• Furnace atmosphere: The atmosphere inside the
furnace surrounding the sample has a profound
effect on the decomposition temperature of the
sample. A pure N2 gas from a cylinder passed
through the furnace which provides an inert
atmosphere.
 Sample characteristics

(a)Weight of the sample: A small weight of the

sample is recommended using a small weight
eliminates the existence of temperature gradient
throught the sample.
(b) Particle size of the sample: The particle size of
the sample should be small and uniform. The use of
large particle or crystal may result in apparent, very
rapid weight loss during heating
 Applications of TGA
• From TGA, we can determine the purity and thermal
stability of both primary and secondary standard.
• Determination of the composition of complex mixture and
decomposition of complex.
• For studying the sublimation behaviour of various
substances.
• TGA is used to study the kinetics of the reaction rate
constant.
• Used in the study of catalyst: The change in the chemical
states of the catalyst may be studied by TGA techniques.
(Zn-ZnCrO4) Zinc-Zinc chromate is used as the catalyst in
the synthesis of methanol.
 Optimum conditions
i) Few mg sample.
ii) Thin layer of sample.
iii) Open sample container.
iv) Inert gas flow.
v) Slow heating rate.
Instrumentation
Modern commercial instruments for thermogravimetry
consists of:
1- A sensitive analytical balance.
2- A furnace.
3- A purge gas system for providing an inert (or
sometimes reactive atmosphere).
4- A microcomputer/microprocessor for instrument
control and data acquisition and display.
5- A purge gas switching system is a common option for
applications in which the purge gas must be changed
during an experiment.
 Instrumentation

LINSEIS L81
 The balance
• A number of different thermobalance designs are available
commercially.
• Capable of providing quantitative information about samples ranging in
mass from 1 mg to 100 mg.
• Common type balance: has a range of 5 to 20 mg.
• Sample holder of balance must be housed in the furnace. But the rest
of the balance must be isolated from the furnace.
• A change in sample mass causes a deflection of the beam which
interposes a light shutter between a lamp and one of two photodiodes.
• The resulting imbalance in the photodiode current is amplified and fed
into coil which is situated between the poles of a permanent magnet.
• The magnetic field generated by the current in the coil restores
the beam to its original position.
• The amplified photodiode current is monitored and transformed into
mass or mass loss information by the data acquisition system.
Balances must remain precise and accurate continuously under
extreme temperature and atmosphere conditions, and should
deliver a signal suitable for continuous recording.
❖ Null-deflection weighing mechanisms are favoured
in TG as they ensure that the sample remains in the
same zone of the furnace irrespective of changes in
mass.
❖ Sensitivity of balance  1g for a 1g maximum load
balance.
❖ The output weight signal may be differentiated
electronically to give a derivative
thermogravimetric curve (DTG)
TGA Apparatus
 The Furnace
❖For TGA ,T range is from ambient to 1500 oC.
❖The heating and cooling rate of the furnace can be
selected from >0 to 200 oC/min.
❖Insulation and cooling to the exterior of the furnace is
required to avoid heat transfer to the balance.
❖Nitrogen or argon are usually used to purge the
furnace and prevent oxidation of the sample.
❖For some analysis it is desirable to switch purge
gases as the analysis proceeds (different gases used
(N2, O2, air, CO2, He, Ar, etc. at controlled rate).

❖The furnace is normally an electrical resistive heater.

Some basic requirements of the heating chamber are:
➢ be non-inductively wound ‫ال تعمل توصيل حثي‬.
➢ be capable of reaching 100 to 200°C above the maximum desired
working temperature.
➢ have a uniform hot-zone of reasonable length.
➢ reach the required starting temperature as quickly as possible.
➢ not affect the balance mechanism through radiation or convection ‫ الحمل الحراري‬.

❖In order to overcome the problem of possible temperature gradient,

infrared or microwave radiation have been used in some equipment.
Infrared heating: use halogen lamp, temperature up to 1400°C, heating
rate can be as high as 1000°C/min, accuracy is about ±0.5°C.
Microwave heating: large sample can be used because uniform heating
generated within sample but temperature measurement and power control
are difficult.
Constant heating rate
 Constant heating rate: lag behind of the sample temperature

During heating a temperature difference Measurement of the melting

between the furnace and the sample point of Di-tert.-biphenyle at
temperature appears which means that the
sample temperature lags always behind the
different heating rates.
furnace temperature.
 Gradual raise of temperature

Thermal equilibrium is better reached by gradual raise of the

temperature.
 The atmosphere
Sort, pressure and flow rate of the gas in the sample chamber
influence the following parameters:
•Sample reaction
Sample reactions with the gas (oxidation in the presence of oxygen).

•Heat transitions
Different heat conductivity of the gases used in an experiment.

•Buoyancy ‫ طفو‬and current effects

Different density and flow rate of the gases used in an experiment.
For all thermoanalytical investigations it is very important to report
the sort, the pressure and the flow rate of the gases used in the
experiment.
Thermal decomposition temperatures for CaCO3 in different gas
atmospheres
 SOURCES OF ERRORS IN TGA
There are a number of sources of error in TGA, and they can lead to
inaccuracies in
• The recorded temperature and mass data.
Some of the errors may be corrected by:
• Placing the thermobalance at proper place and handling it with great
care.
• For understanding we are discussing some common source of errors
during operation of a thermobalance.
• i) Buoyance effect ‫تأثير الطفو‬: If a thermally inert crucible is heated
when empty there is usually an apparent weight change as
temperature increases. This is due to effect of change in buoyancy of
the gas in the sample environment with the temperature, the
increase convection )‫ (الحمل الحراري‬and possible effect of heat from the
furnace in the balance itself.
• Now, in most modern thermobalances, this effect is negligible.
However, if necessary, a blank run with empty crucible can be
performed over the appropriate temperature range. The
resultant record can be used as a correction curve for
subsequent experiment performed in the same condition.
• ii) Condensation on balance suspension: Condensation of the
sample will also affect the mass of the sample and consequently
the shape of TG curve .
• This can be avoided by maintaining a dynamic atmosphere
around the sample in the furnace so that all the condensable
product may be driven by the flowing gases.
• iii) Random fluctuation of balance mechanism
• iv) Reaction between sample and container
• v) Convection effect from furnace
• vi) Turbulence effect from gas flow
• vii) Induction ‫ الحث‬effect from furnace
• Errors of type (iii) can be avoided by proper placing of balance in the
laboratory.
• Error (v) can be avoided by sensible choice of sample container.
• Last three errors (v-vii) have to be considered in the design of the
furnace, the balance and its suspension system. By avoiding excessive
heating rate and proper gas flow rate some of above mentioned errors
may be avoided.
In the light of above discussion it is necessary to calibrate thermobalance
before to use.
• Calibration of thermobalance for the measurement of mass: It can be
done by adding known mass of the sample container and noting the
reading of the chart.
• Temperature calibration: ferromagnetic standards are used for this
purpose. In a magnetic field there substances shown detectable mass
changes. The ferromagnetic standards are quite suitable for the
temperature range from 242 to 771° C.
❖ Thermbalance are normally housed in glass or metal system to
allow for operation at pressures ranging from high vacuum (< 10-
4 Pa) to high pressure (>3000 kPa) of inert, oxidizing, reducing or

corrosive gases.
❖ Care must be taken to correct for buoyancy arising from the lack
of symmetry in the weighing system
❖ Thermal convection ‫ الحمل الحراري‬is
responsible for noise in the signal of
TG.
❖ The use of dense carrier gases at high
pressures in hot zones with large
temperature gradients give the most
noise.
❖ Fitting of convoluted baffles ‫حواجز ملتوية‬
was found to be most successful in
reducing thermal convection.
 Instrument control/data handling
• The T recorded in a thermogram is ideally the actual T of the sample.
• This T can be obtained by immersing a small thermocouple directly in
the sample.
Problems:
This procedure is seldom followed because of catalytic decomposition of
samples, potential contamination of samples and weighing errors
resulting from the thermocouple leads.
Another method:
Problems reduced by measuring T with a small thermocouple located as
close as possible to the sample container.
Modern thermobalances:
Usually use a computerized T control routine that automatically
compares the voltage output of the thermocouple with a voltage versus
T table that is stored read only memory ROM. The voltage difference is
used to adjust the voltage of the heater. (achieving agreement between
specified T program and T of sample).
 The sample

❖ Sample form, defect content, porosity and surface

properties has influence to the behaviour on heating,
e.g. single crystal sample give different response from
powdered sample
❖ Large sample size cause problems like heat transfer, and
gas exchange with the surrounding is reduced; in
general, the use of small (~ 20 mg) specimen is
preferable if sensitivity of balance permits
❖ Sample should be powdered and spread thinly and
uniformly in the container
Crucibles
Decomposition temperatures of CaCO3 as function of crucibles
 Temperature measurement and calibration
❖Platinum resistance thermometers
or thermocouples are used for
temperature measurement.
❖Large difference between sample
temperature (Ts) and furnace
temperature (Tf) can exist,
sometime as high as 30°C.
Calibration is thus needed.
❖The difference or lag is more
marked when operating in vacuum
or in fast flowing atmosphere and
with high heating rate.
Temperature calibration for small furnace can be done by making use
of the melting point or Curie points of a range of metals and alloys.
❖A series of high purity wires may be
suspend in the region where the
specimen crucible would normally be
located. If the furnace temperature is hanger of sample pan
slowly raised through the melting furnace
point of a particular wire, a significant
weight loss will be recorded when the
wire melts.
different
❖A series of fusible wire, such as : metal wires
indium (156.63°C), lead (327.5°C),
zinc (419.58°C), aluminium thermocouple
(660.37°C), silver (961.93°C), and
gold (1064.42°C) should give a
reasonable calibration curve.
Calibration can also be done by placing a series of ferromagnetic
materials in the specimen basket and a magnet below or above it,
external to the furnace. When each material goes through its Curie
temperature (ferro- to paramagnetic transition), a sharp ‘weight’
change will be indicated.
Using mixtures, a multi-point temperature calibration can be
performed.
e.g. Curie points (in oC) of alumel 163; Ni 354; perkalloy 596; Fe 780;
Hisat 1000.
 Interpretation of TG and DTG curves
i.The sample undergoes no decomposition with loss of
volatile products over the temperature range shown
but solid phase transformation, melting ,etc can not
be detected by TG,
ii. The rapid initial mass loss is characteristic of
desorption or drying. If it is true, then re-run the
sample should result in type (i) curves,
iii. Single stage decomposition,
iv.Multi-stage decomposition with relatively stable
intermediates : provide information on the
temperature limit of stability of reactants and
intermediate products and also stoichiometry,
v.Multi-stage decomposition with no stable
intermediate product. However heating-rate effect
must be considered. At low heating rate, type (v)
resemble type (iv). At high heating rate, type (iv) and
(v) resemble type (iii) and lose all the details,
Resolution of stages can be vi.Gain in mass due to reaction with atmosphere, e.g.
improved by recording DTG or by oxidation of metals,
digital differentiation of TG data. vii.Oxidation product decompose again at higher
temperature; this is not often encountered.
 Preparing the measurement
General advices:

• Exact characterization of the starting materials (purity, grain

size)!.
• Large amount of the starting material for repeated and further
measurements.
• Removal of absorbed water by drying (m must be constant).
• Use samples with narrow grain size distribution (Sieving).
• For measurement in vacuum no sample with a grain size below
60 mesh (0.25 mm) (a part of the sample can be lost).
 Applications of TG
❖Only for studying thermal events accompanied by mass change
❖Provide valuable information for desorption, decomposition and
oxidation. e.g. dehydration of CuSO4·5H2O

TG curve for CaSO42H2O at different

TG curve for CuSO45H2O water-vapour pressure
❖ knowledge of thermal stability can give information on problems
like the hazards of storing explosives, shelf life of drugs, etc.
❖ The thermal balance in a TG equipment can also be used to
measure vapour pressure of a sample and magnetic susceptibility,
etc.

ATTN:
Three factors should be noted when you get a TG curve:
1. General shape,
2. The particular temperatures at which changes in mass occur
(severely affected by many experimental conditions),
3. The magnitudes of the mass changes can be used for precise
quantitative analysis.
 Analytical calculations
Under controlled and reproducible conditions, quantitative data can be
extracted from the relevant TG curves. Most commonly, the mass change
is related to sample purity or composition.
Example: A pure compound may be either MgO, MgCO3, or MgC2O4. A
thermogram of the substance shows a loss of 91.0 mg from a total of 175.0
mg used for analysis. What is the formula of the compound? The relevant
possible reactions are
MgO → No reaction
MgCO3 → MgO+CO2
MgC2O4 → MgO+CO2+CO
Solution: % Mass loss Sample=(91.0/175.0)(100%)=52.0
% Mass loss if MgCO3=(44/84.3)(100%)=52.2
% Mass loss if MgC2O4=((44+28)/112.3)(100%)=64.1
If the preparation was pure, the compound present is MgCO3.
 Applications
• Information provided by TGA methods is more limited than
that obtained with DTA and DSC.
• Because here T variation must bring about a change in mass
of the analyte.
• TGA are largely limited to decomposition and oxidation
reactions and some physical processes such as vaporization,
sublimation and desorption.
Most important applications:
• Studying of polymers: Provides information about
decomposition mechanisms for various polymeric
preparations.
• Decomposition patterns are characteristic for each kind of
polymer and identification purposes.
 Some Applications: TGA Curve for AgNO3
• The horizontal portion of the curve indicates
that, there is no change in weight (AB &CD) and
the portion BC indicates that there is weight
change.
• The weight of the substance (AgNO3) remains
constant up to a temperature of 473°C
indicating that AgNO3 is thermally stable up to a
temperature of 473°C.
• At this temperature it starts losing its weight
and this indicates that the decomposition starts
at this temperature. It decomposes to NO2, O2
and Ag.
• The loss in weight continues upto 608°C and The diagram indicates the
beyond this temperature the weight of the TGA curve for AgNO3.
sample remains constant, this is shown by the
portion of the curve CD.
AgNO3 → Ag + NO2 + O2
• The portion between BC, represents the
decomposition of silver nitrate, the
decomposition is complete at 608°C leaving
metallic silver as the stable residue
 Some Applications
TGA for :
PVC = polyviny chloride.
PMMA = polymethyl methacrylate.
LDPE = low density polyehylene.
PTFE = polytetrafluoroethylene.
PI = aromatic polypyromellitimide.

Conditions:
10 mg, 5oC/min in N2
 Thermogravimetric determination of Carbon black in
polyethylene

• TGA Used for quant.

Analysis of polyethylene
(formulated with fine
carbon-black particles to
inhibit degradation from
exposure to sunlight).

• The analysis is difficult by

most other substances.
 TGA for decomposition of CaC2O4.H2O in an inert
atmosphere.
Rate: 5oC/min.
The clearly defined horizontal regions corresponds to temperature
ranges in which the indicated calcium compounds are stable.
Importance: Defining thermal conditions for the gravimetric
determination of pure species.
 Quantitative determination of a mixture of Ca, Sr and Ba
ions
The three are first precipitated as
monohydrated oxalates.
The mass in the temperature
range:
320oC- 400oC: for the anhydrous
compounds (CaC2O4, SrC2O4 and
BaC2O4).
580oC- 620oC:
Corresponds to the weight of the
three carbonates.
next two steps:
The weight changes results from
the loss of CO2 as first CaO and
then SrO are formed.
The TGA data sufficient to
calculate Wt of each element
presents in the sample.
 Derivative of thermogram
Plots change in mass with temperature, dm/dt, and resolves
changes more clearly.
Modern instruments are capable
of providing both TG as well as its
derivative.
The derivative curve may reveal
information that is not detectable
in the ordinary thermogram.
Example:
The three peaks at 140oC, 180oC
and 205oC suggest that the three
hydrates lose moisture at different
temperatures.
However all appear to lose CO2
simultaneously in a single sharp
peak at 450oC.
 Calcium Oxalate Example
Sample: calcium oxalate
Size: 6.9610 mg
Method: Ramp
TGA
File: 111301.001
Operator: cgs
Run Date: 13-Nov-01 10:16
Instrument: TGA Q50 V2.34 Build 127
120 6

12.57% Water
(0.8753mg)
19.47% Carbon Monoxide
100 (1.355mg)
4

Deriv. Weight (%/min)

30.07% Carbon Dioxide
80
(2.093mg)
Weight (%)

60

0
40

20 -2
0 200 400 600 800 1000
Temperature (°C) Universal V3.4A TA Instruments
Derivative thermogravimetry (DTG)
 Differential Thermal analysis (DTA)
Measure sample temperature relative to a reference, for the
same heat transferred

Thermal events: Exothermic event and endothermic event

Reaction/decomposition, Melting, Crystallization, Change in crystal
structure Glass transition
DTA Instrumentation
Instrumentation
Handling :
• A few mg of the sample (S) and an inert substance R are
contained in a small aluminum dishes that are located above
sample and reference thermocouples in an electrically heated
furnace.
• The reference material is an inert substance such as
alumina, silicon carbide or glass beads.
• The output potential Es from the sample thermocouple passes
into a microcomputer where it is made to control the current
input to the furnace in such a way that the sample
temperature increases linearly and at a predetermined rate.
• The sample thermocouple signal is also converted to
temperature Ts and is then recorded as abscissa of the
differential thermogram.
• The output across the sample and reference
thermocouples E is amplified and converted to
temperature difference T = (Tr-Ts) which serves as
the ordinate of thermogram.
• Circulation of inert gas such as N2 or a reactive gas
such as O2 within sample and reference.

• There is a constant temperature difference T between s

and r since they have different heat capacities. But when
the sample undergoes an endo (exo) thermic change T
becomes different.
Example
 General principles
• From Figure 31-7
• The initial decrease in T is due to glass transition.
• The glass transition temperature Tg is the characteristic temperature at
which glassy amorphous polymers become flexible.
• Upon being heated to a certain temperature Tg the polymer changes
from a glass to a rubber .
• Such a transition involves no absorption or evolution of heat (no change
in enthalpy H = 0).
• The heat capacity of rubber is however different from that of the glass
(lowering of the baseline) No peak results during this transition (because
no change in enthalpy H = 0).
• The two maxima are the result of exothermic processes in which heat
evolved from sample ( T rise).
• The minimum labeled melting is the consequence of endothermic
process in which heat is adsorbed by the analyte. Crystallization of
amorphous polymers is an exothermic process (first exothermic peak).
• The second peak in the figure is endothermic and evolves melting of the
microcrystals formed in the initial exothermic process.
• The third peak is exothermic and is encountered only if the heating is
performed in presence of air or oxygen. (results from the exothermic
oxidation of the polymer).
• The final –ve change in T results from the endothermic decomposition of
the polymer to produce a variety of products.
As suggested in the figure differential thermal analysis peaks result
from both physical changes and chemical reactions induced by T
changes in the sample.
Physical processes:
Endothermic: include fusion, vaporization, sublimation, absorption and
desorption.
Exothermic: Adsorption and crystallization (generally).
Chemical reactions:
Endothermic: include dehydration, reduction in a gaseous atmosphere
and decomposition.
Exothermic: oxidation in air or oxygen, polymerization and catalytic
reactions.
Peak areas in DTA depend upon:
- Mass of the sample (m)
- The enthalpy H of the chemical or physical process.
- Geometry and conductivity factors.
A = -kGm H = -K’m H
Where A is the peak area, G is calibration factor that depends upon
the sample geometry, and k is a constant related to the thermal
conductivity of the sample.
-ve for exothermic enthalpy change.
If K’ is remains constant: variables can be controlled such as heating
rate, particle size and placement of the sample relative to the
sample thermocouple.
So mass of analyte can be determined by knowing of H and K’ by
calibration.
H determined if K’ and m are known.
Applications of DTA finds widespread use in:
DTA 1) Determining the thermal behavior and
composition of naturally occurring and
manufactured products.
Examples:
Studying and characterization of polymers.
The figure illustrates the type of physical and
chemical changes in polymeric materials.
Thermal transition occurs for a polymer at
extended range because a pure polymer is a
mixture of homologs.
2) Quantitative identification and purity
assessment of materials are accomplished by
comparing the DTA curve of sample to that to
reference curve
Impurities may be detected by depression of the
M.P.
 Key points in DTA thermogram
• Sharp endotherm: crystalline rearrangemets,
fusion, solid state transition.
• Broader endotherm: dehydration, melting of
polymers, slow reactions
• Narrow exotherm: crystallization
• Sharp exotherm: phase change
The figure is a DTA of a
physical mixture of 7
commercial polymers.
Each peak corresponds to
the melting point of one of
the components.
PTFE has an additional low
T peak that arises from
crystallization transition.
DTA can identify the
polymers.
DTA used for studies the thermal behavior of
pure inorganic compounds or inorganic
substances:
Silicates, ferrites, clays, oxides, ceramics,
catalysts and glasses.
Processes occurs:
Fusion desolvation, dehydration, oxidation,
reduction adsorption and solid-state
reactions.
Figure: DTA of calcium oxalate.
Two minima (sample cooler than ref) for two
endothermic reaction (endo).
The single maxima: oxidation of calcium
oxalate to give carbon dioxide and calcium
carbonate (exo).
By using inert gas (N2) three minima are
encountered (endothermic decomposition of
oxalate to give carbonate and carbon
monoxide.
Generation of phase diagrams
and study of phase transitions.
• The Figure is DTA of sulfur.
• The peak at 1130C
corresponds to solid-phase
change (rhombic →
monoclinic) form
• The peak at 1240C
corresponds to the melting
point of the element.
• (Three forms of liquid sulfur is
known) The peak at 1790C
apparently involves these
transitions).
• The peak at 446 0C

corresponds to the boiling

point of sulfaur.
Simple and accurate
determination the melting,
boiling and decomposition
points of organic compounds.

The Figure shows

thermograms of benzoic acid
at atmospheric pressure (A)
and at 200 psi (B).
The first peak corresponds for
the melting point and the
second to boiling point of the
acid.
 To fingerprint substances
A DTA curve can be used as a fingerprint for identification
purposes.

T a

temp →
DTA of (a) butter and (b) margarine
 Advantages
• Instruments can be used at very high temperatures.
• Instruments are highly sensitive.
•Characteristic transition or reaction temperatures can
be accurately determined.
Factors affect results in DTA
• Sample weight
• Particle size
• Heating rate
• Atmospheric conditions
• Conditions of sample packing into dishes.
 Differential Scanning Calorimetry

In power-compensated DSC, the sample and a reference

material are maintained at the same temperature throughout
the controlled temperature programme. The difference in the
independent energy supplies to the sample and the reference is
then recorded against the programme temperature

DSC can be used to study heats of reaction, kinetics, heat

capacities, phase transitions, thermal stabilities, sample
composition and purity, critical points, and phase diagrams.
Comparison between DTA and DSC
DTA DSC
Differential Scanning Calorimetry (DSC)
DSC is a thermal technique in which differences in heat
flow into a substance and a reference are measured as
a function of sample temperature while the two are
subjected to a controlled temperature program.
Basic differences between DSC and DTA.
➢ DSC is a calorimetric method in which differences in
energy are measured.
➢ DTA differences in T are recorded.
➢ Temperature program of the two are similar.
➢ DSC has by now become the most widely used of all
thermal methods.
 Instrumentation
Two types of methods:
Power compensated DSC:
The sample and reference material are heated by
separate heaters in such away that their temperatures are
kept equal while these temperatures are increased (or
decreased) linearly.
Heat flux DSC:
The difference in heat flow into the sample and reference
is measured as the sample temperature is increased (or
decreased) linearly.
The two methods provide the same information but the
instrumentation is fundamentally different.
 Power compensated DSC:
The instrument has two independent furnaces:
• One for heating the sample.
• The other for heating the reference.
• Commercial design: The furnaces are small weighing about a
gram each, a feature that leads to rapid rates of heating, cooling
and equilibration.
• The furnaces are imbedded in a large temperature-controlled heat
sink.
• Above the furnaces are the sample and reference holders, which
have platinum resistance thermometers imbedded in them to
monitor the temperatures of the materials continuously.
• Two control circuits are employed in obtaining differential
thermograms with the instrument one for average-temperature
control and one for differential-temperature control.
In the average temperature control circuit:
❖ A programmer provides an electrical signal that is
proportional to the desired average temperature of the
sample and reference holders as a function of time.
❖ This signal is compared in a computer with the average of
the signals from the sample and reference detectors
imbedded in the sample and reference holders.
❖ Any differences between the programmer signal and the
average platinum sensor signal is used to adjust the
average temperature of the sample and reference.
❖ The average temperature then serves as abscissa for the
thermogram.
In the differential temperature circuit:
❖ Sample and reference signals from the platinum resistance
sensors are fed into a differential amplifier via a comparator
circuit that determines which is greater.
❖ The amplifier output then adjusts the power input to the two
furnaces in such a way that their temperatures are kept
identical.
❖ During the exp the sample and reference are isothermal.
❖ A signal that is proportional to the difference in power input
to the two furnaces is also transmitted to the data
acquisition system.
❖ This difference in power usually in milliwatts is the
information most frequently plotted as a function of sample
tempearute.
Heat flux DSC
An electrically heated constantan disc (60% Cu, 40% Ni) thermoelectric disc
enables the heat to flow into S and R, which are in small Al pans in a raised
platform. The differential heat flow to S and R is monitored by the difference
in output at the two chromel/constantan area thermocouples. Temperature of S
is obtained from the chromel/alumel junction under the S disc.
 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
Heat Capacity Measurement Using DSC
Baseline change h occurs for substances with different Cp, or
for same substance after phase change.
h  Cp where Cp is thermal capacity (= mass in g  specific
heat capacity in J g-1 oC-1);

h = B  Cp
B = calibration factor, found by using standard e.g. sapphire; m is
sample mass g;  is heating rate oC s-1; unit of y axis (h) is J s-1.
To measure Cp for a substance, obtain DSC results for:
Empty pans in both holders, sample in one pan and reference in other pan. S,
R in crimped Al pans (T<500 oC)
standard in one pan and reference in other.
Other uses of DSC
•kinetics of curing araldite;
•determination of polymer
oxidation temperatures as a guide
to stability;
•determination of phase diagrams
of liquid crystals;
•determination of thermal
conductivity;
•determination of purity of
pharmaceutical products, e.g.
phenacetin (Right)
 Sample containers and sampling
* T<500°C : usually contained in aluminium sample pans which
can be sealed either by crimping or by cold-welding for holding
volatile samples
* T>500°C : use quartz, alumina (Al2O3), gold or graphite pans
* the reference material in most DSC applications is simply
an empty sample pan
* purging of gas into the DSC sample holder is possible, e.g. N2,
O2, etc.
* the mass of (sample+pan+lid) should be recorded before and
after a run so that further information about the processes can be
deduced.
 The reference sample
For all difference methods (DTA, DSC) reference samples like Al2O3
are needed to ensure that the heat flow from the furnace to the sample
and from the furnace to the reference sample is identical!
The thermal behavior of the reference sample is included in the
measured signal.
Requirements for the reference sample:
•Known temperature behavior
•No discontinuity in the temperature curve
•If possible a similar thermal behavior as the sample (similar heat
capacity)
For small weights of the sample and when no precise measurements
are required an experiment without a reference sample is possible.
In such case an empty crucible can be used as reference.
 Interpretation of DSC curves

* aim at correlating the features recorded with the thermal

events taking place in the sample
* after baseline correction, the peak area is proportional to
enthalpy change,

AK
H =
m
where K is a constant and m is the mass of the sample
K can be obtained by melting a known amount of a pure metal
❖ reversibility can be monitored by cooling and reheating

Heating and cooling curves for a partially

crystallized polymer.
* Melting point of pure components are easily determined
* DSC curves for slow cooling of mixture
General Applications
* Temperature and enthalpy changes for the thermal events
enthalpy  area of peak after baseline correction

Corresponding TG curve
* Detection of solid-solid phase transition and the
measurement of H for these transitions

DSC curve of carbon tetrachloride

❖ Tracing the ferromagnetic to paramagnetic transformation.
❖Most rewarding applications is in study of polymer

•Most solid polymers are formed by rapid cooling to low temperatures

(quenching) are thus in glassy state; by heating above Tg, glass transition,
with change in cp but no change in enthalpy, is observed, therefore no
peak is observed, only discontinuity results
•degradation or oxidation of polymers can be study with DSC in isothermal
mode
•for recycling plastics, identification is important and DSC curves provide
'fingerprint'of the materials.
 References:

* Introdcution to Thermal Analysis, M.E. Brown -- Chapman and

Hall
* Thermal Analysis - Techniques and Applications, ed. E.L.
Charsley and S.B. Warrington -- Royal Society of Chemistry
* Thermal Analysis of Materials, Robert F. Speyer –Marcel
Dekker, Inc.