THERMAL ANALYSIS

INTRODUCTION

 Thermal analysis is a group of techniques in which a physical property of a

substance and/or its reaction products is measured as a function of
temperature while the substance is subjected to a linear increase in temperature
@ 5 or 10 C.

 In this course, you will study three methods

➢Thermo Gravimetric Analysis (TGA)
➢Differential Thermal Analysis (DTA)
➢Differential Scanning Calorimetry (DSC)
 Thermo Gravimetric analysis (TGA)
 Thermogravimetric analysis (TGA) is the most widely used thermal method. It is based on the measurement of mass loss
of material as a function of temperature.
 In thermogravimetry a continuous graph of mass change against temperature is obtained when a substance is heated
at a uniform rate or kept at constant temperature.
 A plot of mass change versus temperature (T) is referred to as the thermogravimetric curve (TG curve).
 For the TG curve, we generally plot mass (m) decreasing downwards on the y axis (ordinate), and temperature (T)
increasing to the right on the x axis (abscissa) as illustrated in Fig below. Sometime we may plot time (t) in place of T.
 TG curve helps in revealing the extent of purity of analytical samples and in determining the mode of their
transformations within specified range of temperature.

A Typical TG Curve
 In thermogravimetry, the term ‘decomposition temperature’ is a complete misnomer.
 In a TG curve of a single stage decomposition, there are two characteristic temperatures; the initial Ti and
the final temperature Tf (see Fig below).
 Ti is defined as the lowest temperature at which the onset of a mass change can be detected by thermo
balance operating under particular conditions and Tf as the final temperature at which the particular
decomposition appear to be complete.
 The difference Tf – Ti is termed as reaction interval. In a dynamic thermogravimetry a sample is subjected
to continuous increase in temperature usually linear with time whereas in isothermal or static
thermogravimetry the sample is maintained at a constant temperature for a period of time during which any
change in mass is noted.

A Typical TG Curve
 Objectives

After studying this unit, you should be able to:

 explain the principle of TGA
 describe the experimental setup of TGA
 interpret the analytical information from TGA curves, and
 describe the applications of TGA in qualitative and quantitative analysis of inorganic,
organic and polymer material.
 INSTRUMENTATION
The instrument used in thermogravimetry (TG) is called a Thermobalance. It consists of several basic
components in order to provide the flexibility necessary for the production of useful analytical data in the
form of TGA Curve.
Basic components of a typical thermobalance are listed below:
1. Balance
2. Furnace: heating device
3. Unit for temperature measurement and control (Programmer)
4. Recorder: automatic recording unit for the mass and temperature changes These components may be
represented by simple block diagram as shown in Fig below.

Block Diagram of Thermobalance

1. Balance
The basic requirement of an automatic recording balance are includes accuracy, sensitivity, reproducibility, and capacity. The different
balances used in TG instruments are having measuring range from 0.0001 mg to 1g depending on sample containers used.

2. Furnace
 The furnace and control system must be designed to produce linear heating at over the whole working temperature range of the
furnace and provision must be made to maintain any fixed temperature.
 A wide temperature range generally -150 °C to 2000 °C of furnaces is used in different instruments.

3. Temperature Measurement and Control

 Temperature measurement are commonly done using thermocouples , chromal – alumel thermocouple are often used for temperature
up to 1100 °C whereas Thermogravimetric Analysis Pt/(Pt–10% Rh) is employed for temperature up to 1750 °C.
 Temperature may be controlled or varied using a program controller with two thermocouple arrangement, the signal from one actuates
the control system whilst the second thermocouple is used to record the temperature.

4. Recorder
Graphic recorders are preferred for meter type recorders. X-Y recorders are commonly used as they plot weight directly against
temperature. The present instrument facilitate microprocessor controlled operation and digital data acquisition and processing using
personal computer with different types recorder and plotter for better presentation of data.
 Factors Affecting Thermogravimetric Results
1. Furnace heating rate
 At a given temperature, the degree of decomposition is greater the slower the
heating rate, and thus it follows that the shape of the TG curve can be influenced by
the heating rate.
 For a single stage endothermic reaction it has been found that:
i) (Ti )F > (Ti )S
ii) (Tf)F > (Tf)
iii) (Tf –Ti )F > ( Tf –Ti )S
where subscripts F and S indicate fast and slow heating rate respectively.
 For example, calcium carbonate would not show any mass loss below 600 °C, when
heated in a thermobalance at heating rate of 3 °C per min., and yet it is known that
CO2 is evolved at 250 °C.
 Similarly, polystyrene decomposes 10% by mass when heating rate is 1 °C per min
by 357 °C and 10% by mass when heating rate is 5 °C per min by 394 °C.
 More specifically, it is observed that the procedural decomposition temperature Ti, and
also Tf (the procedural final temperature) will decrease with decrease in heating rate
and the TG curve will be shifted to the left.
 This effect is illustrated in Fig. shown. The appearance of an inflection in a TG curve
at a fast heating rate may well be resolved into a plateau at a slower heating rate.
Therefore, in TGA there is neither optimum no standard heating rate, but a heating
rate of 3 °C per min. gives a TG curve with maximum meaningful resolution.
2. Furnace Atmosphere
The effect of atmosphere on the TG curve depends on
(i) the types of the reaction
(ii) the nature of the decomposition products and
(iii) type of the atmosphere employed.
The effect of the atmosphere on TG curve may be illustrated by taking the example of
thermodecomposition of a sample of monohydrates of calcium oxalate in dry O2 and dry
N2 as shown in Fig.
The first step, which is dehydration is reversible reaction.
Ca C2O4.H2O(s) Ca C2O4(s) + H2O (g )
This is unaffected because both gases are equally effective in sweeping the evolved water
vapours away from the sample surface. For the second step,
Ca C2O4(s)(s) CaCO3 (s) + CO (g)
The curve diverges in O2 atmosphere because the oxygen reacts with evolved CO, giving a
second oxidation reaction which is highly exothermic and so raises the temperature of the un- TG Curve of Calcium Oxalate in O2 and N2
reacted sample. The temperature accelerates the decomposition of the compound more atmosphere: [ __________N2 ,----------------- O2]
rapidly and completely at a lower temperature as shown in the above diagram in dry O2 then in
N2 atmosphere . The third step in decomposition reaction is also reversible reaction.
CaCO3 (s) CaO (s) + CO2 (g)
This step should not be influenced by O2 or N2. However there is a slight difference in curves
for the two gases as shown in diagram. The small difference was due to the difference in the
nature/composition of CaCO3 formed in the two atmospheres. This is due to the particle size,
surface area, lattice defects or due to the other physical characteristics of CaCO3 formed.
3. Sample Holder
 The sample holders range from flat plates to deep crucible of various capacities. The shape of the TG curve will vary as the sample will not be heated in identical
condition.
 Generally, it is preconditioning that the thermocouple is placed on near the sample as possible and is not dipped into the sample because it might be spoiled due to
sticking of the sample to the thermocouple on heating. So actual sample temperature is not recorded, it is the temperature at some point in the furnace near the sample.
 Thus it leads to source of error due to the thermal lag and partly due to the finite time taken to cause detectable mass change. If the sensitivity of recording mechanism is
not enough to record the mass change of the sample then this will also cause error in recording the weight change of the sample.
 If the composition of the sample contains is such that it reacts either with the sample, or product formed or the evolved gases then this will cause error in recording the
mass change of the sample.

3. Effect of Sample Mass

The sample mass affects the TG curve in following
i. The endothermic and exothermic reactions of the sample will cause sample temperature to deviate from a linear temperature change
ii. The degree of diffusion of evolved gases through the void space around the solid particles
iii. The existence of large thermal gradients throughout the sample particularly, if it has a low thermal conductivity. Thus, it is preferable to use as small a sample as
possible depending on the sensitivity of the balance.

4. Effect of Sample Particle Size

 The particle size will cause a change in the diffusion of the evolved gases which will alter the reaction rate and hence the curve shape.

 The smaller the particle size, greater the extent of decomposition at any given temperature. The use of large crystal may result in apparent vary rapid mass loss
during heating. This may be due to the mechanical loss of part of the sample by forcible ejection from the sample container, when the accumulated evolved gases within
the coarse grains are suddenly released.
 APPLICATIONS OF TERMOGRAVIMETRIC
ANALYSIS
1. Determination Of purity and chemical stability of both primary and secondary standards:

 Thermogravimetry is a valuable technique for assessing the purity of materials. Analytical reagents especially those used in
titrimetric analysis as primary standards (e.g., sodium carbonate, sodium tetraborate and potassium hydrogen phthalate), have
been examined. Many primary standards absorb appreciable amounts of water, when exposed to moist atmospheres. TG data can
show the extent of this absorption, hence the most suitable drying temperature for a given reagent may be determined.
 From TG studies, the thermal stability of EDTA as the free acid and also as the more widely used disodium salt Na2EDTA. 2 H20
have shown that the dehydration of the disodium salt commences at between 110 and 125°C, so Na2EDTA. 2 H20 could be safely
heated to constant weight at 80°C.

2. Investigating the correct drying temperatures and the suitability of various forms gravimetric analysis:

Initially, the most widespread application of thermogravimetry in analytical chemistry has been in the study of the recommended drying
temperatures of gravimetric precipitates. Duval studied over a thousand gravimetric precipitates by this method and gave the
recommended drying temperatures.
3. In qualitative analysis:

 A TG curve indicates the “horizontal portions” (which represent no

weight change) and slinting downwards curves (which represent weight
loss, due to dehydration/ rupture/ formation of volatile products).
 Thus, a TG thermogram is a characteristic for a given compound, since
the unique sequence of physico-chemical reactions occurring over
definite temperature ranges are a function of the molecular structure.
 Fig. below shows the thermogram for decomposition of pure calcium
oxalate (CaC2O4 . H20) obtained by increasing the temperature at a rate
of 5°C/min.
 It is thermally stable upto 100°C and water is evolved slightly above
100°C. At about 226°C, a break is obtained in the downward curve at the
stoichiometry corresponding to anhydrous salt (CaC2O4). TG curve for decomposition of CaC2O4 . H2O
 The horizontal portion between 226 — 346°C indicates that anhydrous
salt is thermally stable in this range. At slightly above 346°C, it again
starts losing CO is yield CaCO3. Process is complete at about 420°C.
 Beyond 420°C, CaCO3 is stable upto about 660°C. Beyond 660°C,
there is evolution of CO2 to give CaO. At 840°C, this decomposition is
complete. At 840°0 and above, the horizontal portion represents the
stable CaO.
4. Determination of composition of alloys and mixtures:
 Thermogravimetry may be used to determine the composition of binary mixtures. If each
component possesses a unique pyrolysis curve then resultant curve for the mixture will afford a basis
for determining its composition.

 In such an automatic gravimetric determination, the initial weight of the sample need not be known. A
simple example is automatic determination of a mixture of calcium and strontium as their
carbonates. Both carbonates decompose to their oxides with the evolution of carbon dioxide.

 The decomposition temperature for calcium carbonate is in the temperature range 650 — 850°C
whereas strontium carbonate decomposes in the range 950 — 1150°C.

 Hence. the amount of calcium and strontium present in a mixture may be calculated from the weight
losses due to the evolution of carbon dioxide at the lower and higher temperature ranges respectively.

 This method can be extended to the analysis of a three-component mixture, as barium carbonate is
reported to decompose at an even higher temperature (-1300°C) than strontium carbonate.
 Fig. below illustrates the application of TG to the analysis of a mixture of
Ca2+, Sr2+ and Ba2+ ions.

 These are first precipitated as monohydrated oxalates (MC2O4.H2O) and

then subjected to heating at a rate of 5°C/min.

 The mass loss between 320°C and 400°C corresponds to the combined ions
of water by three anhydrous salts forming MC2O4.

 Mass between 580°C and 620°C corresponds to the combined mass of the
three carbonates (MCO3). The mass loss in the next two steps represents
loss of C02 by CaC03 (to form CaO) and SrC03 (to form SrO) respectively.

 From this data, we can easily calculate the mass of each clement present
in the sample. Fig. b is the derivative of thermogram shown in Fig. a.

 Thus, in the differential thermogram of Fig. b, the three peaks at 140°C,

180°C and 205°C suggest that the three hydrates lose moisture at
different temperature, but a single sharp peak at about 450°C shows that
three oxalates lose CO simultaneously.
❖ A further example is the automatic determination of a mixture of calcium and magnesium and their oxalates.
Calcium oxalate monohydrate has three distinct regions Of decomposition; magnesium oxalate dihydrate has only two :

 A pyrolysis curve for a mixture of these two oxalates would thus show three decomposition steps.
 The final step would be due entirely to the loss of carbon dioxide from calcium carbonate hence the amount of
calcium present in the mixture may be calculated.
 The amount of magnesium in the oxalate mixture may be calculated from the second step. where stages (b) and (e)
occur.
 This is because the amount of carbon monoxide due to calcium carbonate may be subtracted from the total observed
weight loss, giving the loss of carbon dioxide and carbon monoxide from anhydrous magnesium oxalate.
 Since stages (a) and (d) do not feature in the calculation, the mixture of Calcium and magnesium oxalates does not
require drying before the automatic determination.
5. In study of polymers:
 The most important application of TG is found in the study of
polymers.

 TG thermogram provides valuable information about their

decomposition mechanisms.

 Moreover, each kind of polymer follows a particular characteristic

pattern and hence, TG thermogram can be used for identification
purposes. Fig. below shows the TG thermogram of some common
polymers.

 One of the most important applications of thermogravimetry is in

TG Thermogram Of PVC (polyvinyl chloride),
examining the thermal stability of polymers.
PPMA (polymethyl methacrylate), LDDE (low-
density polythene) and PTEE (polytetra
 Thermogravimetry is also capable of giving information concerning fluoroethene)
polymer identity.

 Since derivative thermogravimetry (DTG) is able to show the

temperature where the maximum weight change appears to take
place, it is a valuable method for distinguishing polymers.
6. Studying the oxidation of alloys
 The oxidation of the cobalt-samarium alloy Co5Sm
was examined by thermogravimetry using an air
atmosphere. The results are shown in Fig below.

 The weight increase AB resulted from the oxidation

of Sm to Sm2O3. The increase BC was due to the
oxidation of Co to Co3O4 and to the formation of the
mixed oxide CoSmO3.

 The final weight loss DE was obtained from the

conversion of Co3O4 to CoO. The formation of Sm2O3
and the mixture of Co3O4 and CoSmO3 were
Oxidation of Co5Sm by thermogravimetry in an air
confirmed by X-ray diffraction studies. atmosphere. AB shows oxidation of Sm to Sm2O3 :
BC shows oxidation of Co to Co3O4 and formation of
the mixed oxide CoSmO4 : DE shows the conversion
of Co3O4 to CoO
DIFFERENTIAL THERMAL
ANALYSIS (DTA)
 INTRODUCTION
 DTA may be defined formally as a technique for recording the difference in temperature between a substance and a
reference material against either time or temperature as the two specimens are subjected to identical temperature
regimes in an environment heated or cooled at a controlled rate.

 In differential thermal analysis (DTA), both the test sample and an inert reference material (usually ά-alumina) undergo a
controlled heating or cooling programme which is usually linear with respect to time.

 There is a zero-temperature difference between the sample and the reference material, when the sample does not
undergo any chemical or physical change.

 But if any reaction takes place, then a temperature difference (⧍T) will occur between the sample and the reference
material.

 Thus, in an endothermic change (when the sample melts or is dehydrated), the sample is at a lower temperature than
the reference material. This condition is only transitory because, on completion of the reaction, the sample will again
show zero temperature difference compared with the reference.
Principle:
The basic principle involved is: the difference of temperature (∆T) between the test sample(TS) and an inert
reference sample(TR) under controlled and identical conditions of heating or cooling is recorded continuously as
a function of temperature or time.
 The heat absorbed and emitted by a chemical system can be estimated or determined.
 The changes are two types- exothermic and endothermic
 If endothermic- ∆T = TR – TS = +ve or TS – TR = -ve
 If exothermic- ∆T = TR – TS = -ve or TS – TR = +ve
 INSTRUMENTATION
1. Sample Holder
Sample and reference crucible are generally metallic or ceramic(silica) and may
or may not have a lid, for good results area of contacts b/w sample and crucible is
maximized. Typically 1-10 mg of sample is required for analytical applications.

2. Furnace
Reference and sample should be thermally matched and symmetrically arranged
with the furnace so that both of them are identically cooled or heated, metal block
around the wall acts as a heat sink and by using internal heater temperature of the
heat sink is slowly increased sink in turn heat the sample and reference material.
Schematic Diagram of DTA Apparatus

3. Sensors and recording system

 Pair of matched thermocouple is used; one pair is in contact with the sample
while the other pair is in contact with the reference.
 The output of the differential thermocouple Ts-Tr is sent to the data acquisition
system after amplification.
 Operating temperature for DTA instruments is generally from room
temperature to around 1600 °C.
 Liquid nitrogen cooling accessories is needed for very low sub ambient
temperature. Figure 5 shows instrumentation of DTA.

Block Diagram of DTA apparatus

 Representation of DTA Data:
 In DTA, a plot is made of ∆T against temperature or time, if the heating or cooling
programme is linear with respect to time.
 An idealised DTA curve shown in Fig. Peak I is an exothermic peak and peak 2 is an
endothermic peak.
 The Shape and size of the peaks can give a large amount of information about the nature
of the test sample.
 The sharp endothermic peaks often signify changes in crystallinity or fusion processes
while broad endotherms arise from dehydration reactions.
 Physical Changes usually result as endothermic curves whereas chemical reactions,
particularly those of an oxidative nature, are predominantly exothermic.

Idealised DTA curve : (1) exothermic

Note : peak. (2) endothermic peak
 The shape of a DTA peak does depend on sample weight and the heating rate used.

 Lowering the heating rate is roughly equivalent to reducing the sample weight; both lead
to sharper peaks with improved resolution.

 The influence of heating rate on the peak shape and disposition can be used to advantage
in the study of decomposition reactions, but for kinetic analysis it is important to
minimise thermal gradients by reducing specimen size or heating rate.
 Factors Affecting Thermogravimetric Results

 Since DTA is a dynamic technique, a large number of factors can affect the resulting experimental curves.
 If the DTA curve is used for quantitative purposes, the shape, position, the area enclosed by the curve are of
great interest.
 For specific heat measurements the baseline deviations become important and such conditions as particle size,
system symmetry, sample packing must be taken into account if accurate results are to be obtained.
 As with the technique of thermogravimetry, the DTA curve is dependent on two general categories of variables:
instruments factor and sample characteristics.

2. Instrumental parameters
It includes furnace atmosphere, size and shape of furnace, sample holder materials, sample holder geometry,
heating rate, and location of thermocouple in sample chamber, speed and response of recording device.
2. Characteristics of sample

 It includes particle size of sample, amount of

sample, packing density, swelling or shrinkage
characteristic of sample, degree of crystallinity,
presence of diluents, thermal conductivity and heat
capacity.
 The effect of furnace atmosphere is similar to that
discussed in the thermogravimetry section and is
significant for equilibrium reactions.
 An increase of the heating rate would cause the
spreading of the DTA curve.
 Since the return of the signal to the baseline is a
time function, this will happen at a higher actual
temperature with more rapid heating as shown in
figure.
DTA provides information about:

(1) phase transformations

(2) structure inversions
(3) dehydration
(4) decomposition or dissociation
(5) oxidation or reduction
(6) destruction
(7) formation of crystalline lattice structure
(8) multiple transitions in crystalline structure
(9) recrystallization of quenched samples
(10) stress release
(11) reactions due to the presence Of impurities
(12) volatilization of liquids, etc.
 where m mass of the sample; ∆H = enthalpy of involved reaction; ⧍T = differential temperature; dt = differential operation, g=
geometrical factor of the apparatus; k = thermal conductivity of the sample. The enthalpy ⧍H is given a negative sign for an exothermic
reaction and a positive sign for an endothermic reaction.
For a given species, k' remains constant, provided the variables like heating rate, particle size of the sample and placement of the
thermocouples are closely controlled.
Under these circumstances it is possible to calculate :
i. mass of the analyte from peak areas by determining k' and ⧍H value by calibration
ii. ⧍H for species, when k' and m have been measured.

 It is possible to measure the heat capacity Cp at constant pressure using DTA:

where Tl and T2 are the differential temperatures generated when the apparatus is first run without any sample at all and then with the test
sample in position. H is the heating rate and the constant K" is determined by calibration against standard substances.
APPLICATIONS
1. Qualitative Analysis of materials
 A rapid method for the fingerprinting of minerals, clays and polymeric materials was provided by
DTA measurements.
 For example, using DTA with a nitrogen atmosphere, chrysolite (white asbestos) was shown to
give a dihydroxylation endotherm at 650ºC and a characteristic crystallisation exotherm at 845ºC.
 A sample containing 1% w/ w chrysolite in talc was detected by DTA.
 This fast technique does not involve the extensive sample preparation required by competitive
methods.
 Polymers can exhibit their own characteristic melting point endotherms. Thus, in a blend containing
seven commercial polymers, each component was readily identified by the endotherm of melting
using DTA.
2. Fig. shows the differential thermogram of calcium oxalate monohydrate in a flowing air (O2), obtained by increasing
temperature at a rate of 8ºC/min.

 It contains two minima (for endothermic processes), equations for these decomposition reactions are shown below the
maxima. The single maxima indicate that oxidation of CaC2O4 to CaCO3 and CO2 is exothermic.

Note:

 If the differential thermogram of calcium oxalate monohydrate is obtained in an inert atmosphere.

 Then maxima changes to minima, since the decomposition reaction under inert condition would be

CaC2O4 CaCO3 + CO

which is an endothermic process. Hence, there will be three maxima.

Fig: Differential thermogram Of CaC 2O4. H2O

in a flowing stream of air
3. DTA provide information regarding processes like fusion, 4. DTA provides an accurate way of determining the
dehydration, dissolution, oxidation, reduction, adsorption, melting and boiling points for organic compounds. Fig.
degradation and solid-state reactions. shows the DTA for benzoic acid at:
 One of the applications of DTA is the generation of phase
(a) atmospheric.
diagrams and the study of phase transitions.
 Fig. shows the DTA thermogram for pure sulphur. (b) 200 lb/m2 (psi).
 Peaks at 113ºC, 124ºC, 179ºC and 446ºC corresponds
 The first peak corresponds to the melting point; while
respectively to the solid-phase change from the rhombic to the
the second to the boiling point.
monoclinic form, melting point of sulphur, a transition among
three forms of sulphur and the boiling point of sulphur.

DTA Curve for Benzoic Acid

DTA Curve of Sulphur
5. DTA has been widely used to study and characterization of polymers. Fig. is an idealized DTA curve
that illustrate the various type of transitions that may be encountered during heating of a polymer.

Note:

 Glass transition temperature (Tg) may be defined as the temperature at which the constituent
particles begins to have translatory motion.

 Alternatively, it is the temperature at which the expansion coefficient of solid exhibits a sharp change.

 In terms of configurational entropy model, it is the temperature at which the configurational entropy of
the material is zero.

Fig: Schematic DTA Thermogram of

a polymer
6. DTA can be used for qualitative analysis of polymer mixture.
 Fig shows a DTA thermogram of a mixture containing of polymers.
 Each peak gives the characteristic melting point of one of the polymers.
 PTFE, however, has an additional low temperature peak, due to a crystalline transition.

Thermogram for a mixture containing PTFE (polytetrafluoroethylene); HIPPE [(high-

pressure low-density polyethylene]; LPPE [low pressure (high density polyethylene);
PP (polypropylene): POM (polyoxymethylene); Nylon 6 and Nylon-66.
DIFFERENTIAL SCANNING
CALORIMETRY (DSC)
 INTRODUCTION
 Differential scanning calorimetry (DSC) is a technique for measuring the energy
necessary to establish a nearly zero temperature difference between a substance and an
inert reference material, as the two specimens are subjected to identical temperature
regimes in an environment heated or cooled at a controlled rate.
 There are two types of DSC systems in common use.
a) In power–compensation DSC the temperatures of the sample and reference are controlled
independently using separate, identical furnaces.
▪ The temperatures of the sample and reference are made identical by varying the power
input to the two furnaces; the energy required to do this is a measure of the enthalpy or
heat capacity changes in the sample relative to the reference.
b) In heat–flux DSC, the sample and reference are connected by a low–resistance heat–flow
path (a metal disc).
▪ The assembly is enclosed in a single furnace. Fig: Heat Flux DSC

▪ Enthalpy or heat capacity changes in the sample cause a difference in its temperature
relative to the reference; the resulting heat flow is small compared with that in differential
thermal analysis (DTA) because the sample and reference are in good thermal contact.
▪ The temperature difference is recorded and related to enthalpy change in the sample using
calibration experiments.
 INSTRUMENTATION
A DSC apparatus consists of identical components to that of
DTA, except that it contains individual heaters, located as close
as possible to the sample and reference vessels. Modern form of
heat flux DSC is shown in Fig.
 A metallic disc (made of constantan alloy) is the primary
means of heat transfer to and from the sample and reference.
 The sample, contained in a metal pan, and the reference, an
empty pan, sit on raised platforms in the constantan disc.
 As heat is transferred through the disc, the differential heat flow Fig: Heat Flux DSC
to sample and reference is measured by thermocouples formed
by the junction of the constantan disc and chromel wafers,
which cover the underside of the platforms.
 These thermocouples, are connected in series and measure the
differential heat flow.
 Chromel and alumel wires attached to the chromel wafers
form thermocouples which directly measure the sample
temperature.
 Purge gas is admitted to the sample character through an orifice
in the heating block.
 With this equipment, it is possible to achieve heating or cooling
rates of 100ºC min-1 down to rates Of 0ºC min-1 (Isothermal).
Fig: Block Diagram of DSC Apparatus
 Representation of Data

 The result of calorimetric measurements is a DSC curve shown as

the temperature/time dependence on the heat flux (per time
unit).
 An endo- and exothermic peaks are recorded on these curves
(Fig.), which result from the temperature differences between a
tested sample and a reference sample, showing negative or
positive deviations from the so called “baseline”, which is
recorded at the time when no transformations/reactions occurs in
the sample.
 The differences are caused by phase transformations and
chemical reactions occurring in the material.
 If the temperature of a tested sample during the phase DSC curves of heating and cooling cycles for pure
transformation/chemical reaction is lower than the reference metal:
temperature, the heat is absorbed. The situation is registered as the (a) onset temperatures (the melting point for this
endothermic peak. example, TM)
(b) peak signals
 Conversely, when the sample temperature is higher and there is (c) peak temperatures
separation of the heat, then this is marked as the exothermic
effect on the DSC curve.
 Factors Affecting DSC Results

1. ranges of temperature and pressure range

 High temperature/pressure and low temperature/pressure;

2. type of the test process

 to measure the heat of mixing, heat capacity;

3. thermodynamic conditions
 adiabatic, non-adiabatic;

4. sample weight change during the measurement

 open (with the exchange of mass), closed (no mass
transfer).
 APPLICATIONS

1. DSC analysis on a blend of synthetic fibres was an early 2. Polymer blends difficult to evaluate by conventional DSC
application. Using an analysis of differential scanning calorimeter, have been successfully analysed by modulated DSC.
a blend, containing Nylon 66, orlon and polyester was determined.
 For example, a polymer blend containing poly-ethyl
 The ⧍H values per gram of sample were compared with the terephthalate (PET) and acrylonitrile-butadiene-styrene
corresponding ⧍H per-gram of each pure component. (ABS) has been separated and evaluated using DSC.
 Hence, the ⧍H values for the crystallisation peaks of nylon and
the polyester were measured together with a cross-linking
exotherm for orlon. 3. Differential scanning calorimetry can be used to study the
number and temperature range of polymorphs, since each
 A quantitative analysis was then made on the fibre blend. For
polymorphic transition causes an energy change that may be
example, the ratio of the ⧍H value for the nylon crystallisation
peak in the fibre blend over the ⧍H value for the pure nylon detected by DSC.
multiplied by 100 gave the percentage nylon in the fibre
blend.  Various forms of digoxin have been investigated.

 The total time for the analysis, performed without sample

treatment or any separatory procedure, was less than 30 min.
4. DSC finds widespread use in calculating enthalpy of transition such as
enthalpy of melting, enthalpy of crystallization, enthalpy of fusion, etc. of
polymeric materials.

 DSC also provides a simple and accurate way of determining melting, boiling
and decomposition points for organic compounds.

 Moreover, DSC curves can be used to determine the purity of drug samples.

 For example, Fig. shows the DSC curves for phenacetin having different
purities. Generally, the curves provide purity data within 1% error.

Note:
 The weight changes monitored by thermogravimetry invariably involve the
absorption or release of energy, hence they can be measured by either DSC
or DTA.
Fig: DSC curves for samples of
phenacetin of different purities.
 But there are many changes in energy that are not accompanied by a gain or
loss in weight.

 For Example: melting, crystallisation, fusion and solid-state transitions do

not involve weight changes.

 Thus, TG is often used in conjunction with either DTA or DSC.

Difference between TGA, DTA and DSC: