DIFFERENTIAL THERMAL ANALYSIS &

DIFFERENTIAL SCANNING
CALORIMETRY

Under the esteemed guidance of

Presented by A. MADHU SUDHAN REDDY
S. LAKSHMI SRAVANTHI M.Pharm (Ph.D)
(M. Pharm) Associate Professor
15AB1SO308 Department Of Pharmaceutics

VIGNAN PHARMACY COLLEGE

(Approved by AICTE, PCI & Affiliated to JNTU KAKINADA)
VADLAMUDI, GUNTUR DIST, ANDHRA PRADESH, INDIA,PIN:522 213
2015
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 CONTENTS
1. Introduction
2. Differential thermal analysis
a. Principle
b. Instrumentation
c. Applications
3. Differential scanning calorimetry
a. Principle
b. Instrumentation
c. Applications
4. Conclusion
5. Reference
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 Introduction
 Thermal analysis includes a group of techniques in which specific
physical properties of a materials are measured as a function of
temperature.
Theoretically, almost any substance whether solid, semi-solid or
liquid can be analyzed and characterized with thermal analytical
techniques.
Common materials include foods, pharmaceuticals, electronic
materials, polymers, ceramics, organic and inorganic compounds, even
biological organisms.

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 DIFFERENTIAL THERMAL
ANALYSIS

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 PRINCIPLE

 Differential thermal analysis is a

technique in which the difference in
temperature between a substance
and reference material is measured
as a function of temperature while
the sample and reference are
subjected to controlled temperature
programme.

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  If zero temperature difference b/w sample & reference
material sample does not undergo any chemical or physical
change.
If any reaction takes place temperature difference (∆T) will
occur b/w sample & reference material .
The Difference in temperature is called as Differential
temp(∆t) is plotted against temp. or a function of time.

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 Phenomena causing changes in temperature
Physical changes:
• Adsorption (exothermic)
• Desorption (endothermic)
• A change in crystal structure
(endo – or exothermic)
• Crystallization (exothermic)
• Melting (endothermic)
• Vaporization (endothermic)
• Sublimation (endothermic)
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 Chemical changes:
• Oxidation (exothermic)
• Reduction (endothermic)
• Break down reactions
(endo – or exothermic)
• Chemisorption (exothermic)
• Solid state reactions
(endo – or exothermic)

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 Differential Thermal Analysis (DTA)
Instrument

Endothermic - heat flows into the sample.

Exothermic
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 The various component of a DTA apparatus are as following:

1. Furnace Assembly:
This is device for heating the sample.

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2.Sample and
reference holder
with Temperature
detector

Sample holder- This is used to contain the

sample as well as the reference material.

Differential Temperature Detector- The function of this detector is

to measure differential temperature.
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 3.Temperature programmer
The main function of this is to increase the temperature of the
furnace at a steady rate.

4. Amplifier and recorder

Generally a low level DC amplifier is employed

5. Recorder
6. Control Equipment -Its
function is to maintain a suitable
atmosphere in the furnace & sample
holder.

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Advantages:

• Instruments can be used at very high temperatures.

• Instruments are highly sensitive.

• Characteristic transition or reaction temperatures can be accurately

determined.

Disadvantages:

• Uncertainty of heats of fusion, transition, or reaction estimations is

20-50%.
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 Interpretation of DTA

ΔH = K * Peak area

K - can2016
20 February be determined by measuring ΔH and peak area of know metals
thecollege
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 Factors affecting DTA curves

 DTA is a dynamic temperature technique. Therefore, a large

number of factors can affect. These factors can be divided into
the three groups:

1. Instrumental factors

2. Sample factors

3. Environmental factors

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 Instrumental factors

 Furnace atmosphere

 Furnace size and shape

 Sample holder material

 Sample holder geometry

 Wire and bead size of thermocouple junction

 Heating rate

 Speed and response of recording instrument

 Thermocouple location in sample

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 Sample factors
 Particle size

 Thermal conductivity

 Heat capacity

 Packing density

 Swelling or shrinkage of sample

 Amount of sample

 Effect of diluent

 Degree of crystallinity

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 Heating rate

• Effect of heating rate

on curve peak
resolution,
compound used was
cholesterol
propionate.

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 • Effect of heating rate
on the peak
amplitude, compound
used was cholesterol
propionate.

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 Effect of diluent

• Masking effect of sample peaks caused by diluent

(a) 8-quinolonol diluted

to 6.9% with carborundum

(b) 8-quinolinol diluted

to 5.9% with alumina

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 Environmental factors

• Effect of O2 and N2
atmosphere on the DTA
curve of a mixture of
2.5% lignite in Al2O3.

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 Limitations of Differential Thermal
Analysis (DTA)
 ΔT determined by DTA is not so accurate (2-3 ̊C).

 Small change in ΔT cannot be determined and

quantified.

 Due to heat variation between sample and reference

makes, it less sensitive.

To improve the above limitations change in the methodology is

required.

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 Applications
• Quantitative identification and purity assessment of
materials are accomplished by comparing the DTA curve
of sample to that of a reference curve.

• Impurities may be detected by depression of the M.P.

• Identification of substances.

• Identfication of products.

• Quantitative analysis

DTA peak curve is proportional to the total heat of

reaction and hence weight of the sample.
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 DTA technique has been widely used for the quality control of a
large number substances like cement , glass, soil, catalysts, textiles,
explosives, resins.
DTA has been used to study the oxides of uranium and plutonium.
DTA investigations have been carried to help detection, purity
determination and quantitative analysis including the evaluation of
kinetic parameters of polymers, explosives, pharmaceuticals, oils, fats
and other organic chemicals.

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Differential Scanning
Calorimetry (DSC)

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 Principle
 The sample and reference are maintained at the same

temperature, even during a thermal event in the sample.

• The energy required to maintain zero temperature difference

between the sample and the reference is measured.

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• Conventional DSC

Sample Empty

Metal Metal Metal Metal

1 2 1 2
Sample Reference
Temperature Temperature

Temperature
Difference =
Heat Flow

•A “linear” heating profile even for isothermal methods

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 Diagram of a DSC apparatus
• A DSC apparatus is built Gas
around control Furnace

- a differential detector Sample Reference

Furnace
- a signal amplifier Detectors controller
four
- a furnace
- a temperature controller
Microvolt
- a gas control device amplifier Data
acquisition
- a data acquisition device

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Differential Scanning Calorimeter(DSC)
Heat flux

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Sample and reference holders
• Al or Pt pans placed on constantan disc.
• Sample and reference holders are connected by a low-resistance
heat flow path.

Sensors
• Chromel® (an alloy made of 90% nickel and 10% chromium)-
constantan area thermocouples (differential heat flow).
• Chromel®-alumel (an alloy consisting of approximately 95%
nickel, 2% manganese, 2% aluminium and 1% silicon)
thermocouples (sample temperature).

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 Thermocouple is a junction between two different metals that
produces a voltage due to a temperature difference

Furnace
• One block for both sample and reference cells

Temperature controller
• The temperature difference between the sample and reference is
converted to differential thermal power, which is supplied to the
heaters to maintain the temperature of the sample and reference at
the program value

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 Power Compensation DSC Cell

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Sample holder
• Aluminum or Platinum pans.

Sensors
• Platinum resistance thermocouples.
• Separate sensors and heaters for the sample and reference.

Furnace
• Separate blocks for sample and reference cells.

Temperature controller
• Supply the differential thermal power to the heaters to maintain the
temperature of the sample and reference at the program value.
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 Modulated Temperature – DSC (MT-DSC)

This new technique introduced in 1993 has been thoroughly examined.

Polymer blends difficult to evaluate by conventional DSC have been
successfully analysed by modulated DSC
Main advantages are the separation of overlapping events in the DSC scans.
 In conventional DSC, a constant linear heating or cooling rate is applied.
 In modulated DSC (MDSC), the normally linear heating ramp is overlaid
with a sinusoidal function (MDSC) defined by a frequency and an amplitude to
produce a sinusoidal shaped temperature vs. time function.
Using Fourier mathematics, the DSC signal is split into two components: one
reflecting non-reversible events (kinetic) and the other reversible events.
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 It has been recently applied for the determination of glass transitions
of hydroxypropylmethylcellulose films and for the study of amorphous
lactose, as well as for the study of some glassy drugs

Micro-DSC
 The instruments of conventional DSC allows to measure very
small amounts of material.
 New instrument generation will permit to increase sensitivity
and amount of material to be studied decrease to nanorange.

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 DSC Thermogram
Heat Flow -> exothermic

Oxidation
Crystallisation Cross - Linking
(Cure)

Glass
Transition

Melting

Temperature
6
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 Main Sources of Errors

• Calibration
• Contamination
• Sample preparation – how sample is loaded into a pan
• Residual solvents and moisture.
• Thermal lag
• Heating/Cooling rates
• Sample mass
• Processing errors

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 Sample preparation

Form of sample: bulk solid, powder (pressed), liquid.

Amount of sample: 3-5mg.

DSC Pan: Al, Pt, stainless steel, Ag, Cu, Al2O3

* Small sample masses and low heating rates increase resolution

Al Pt alumina Ni Cu quartz
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Sample Preparation : Shape
• Keep sample as thin as possible (to minimise thermal
gradients)
• Cover as much of the pan bottom as possible
• Samples should be cut rather than crushed to obtain a
thin sample (better and more uniform thermal contact
with pan)

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 Typical TGA and DSC Results for Various Transitions
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 Modern Approach to Research by DSC and its Advancements

MEMS – DSC
It has been applied in manufacturing 3-D silica based structures with
specific geometrical, mechanical and electrical characteristics to operate
certain functions.
Analysing structural transitions of biological molecules in liquid phase
this is not workout with conv.DSC.

IR- heated DSC

It is a heat flux DSC, that comprises of a DSC sensor assembly for
receiving a sample that is installed in a cavity within an elongated cylinder
and an IR lamp assembly that is disposed of circumferentially around the
elongated cylinder with a length approximately similar to that of the cylinder.
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 MTDSC
MTDSC provides the amplitude and phase signals i.e. altering signals and
the total heat-flow signal equivalent to that given by DSC simultaneously in
a single experiment. Highly advanced and fast technique.

GFMDSC
GFMDSC modulates a DSC by setting the properties of a gas in thermal contact
With the sample and the reference in the calorimeter.
High accuracy and high efficient

PNDSC
It is PCDSC that included the plurality of cell structures being used to
define a selective region for calorimetric measurements of nanomaterial. It
provides reproducible results.
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 Food industry Cosmetic industry Polymer
industry
Applications

Pharma industry Research and Ceramic industry

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development
 Stability of the Materials
Sn(OH)Cl - Catalyst

200 ̊ C- Dehydration

200-400 ̊ C-
Dehydroxylation

400-550 ̊C
̊ – Formation
of oxide

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V.S.Marakatti et. al .RSC Adv., 2013,3, 10795-10800
 Application in determination of phase
transition
Sulfur element

113 ̊ C
Rhombohedral to monoclinic

124 ̊C
Melting point

179 ̊C
Liquid phase transistion

446 ̊C
Boiling point

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Polymorphism
DSC has proven to be very useful in the identification of polymorphic
transitions primarily due to the ability to easily study the sample under various
heating and cooling conditions needed to induce the polymorph formation.
DSC also measures • Glass transitions
• Melting and boiling points
•Crystallization time and temperature
•Percent crystallinity
•Heats of fusion and reactions
•Specific heat capacity
•Oxidative/thermal stability
•Rate and degree of cure

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 Conclusion

As formulations become more and more complex and

characterizing them becomes more difficult, manufacturers have
done an excellent job in keeping pace with more precise and
sensitive yet more durable instruments.
The applications discussed in this review represent a tiny fraction
of what is currently being done and with continual advances in the
field.

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 REFERENCES

1) Ashish Chauhan & Bharti Mittu , Modern approaches to research

by DSC and its advancements, Pharmaceutica Analytical Acta,
Vol. 3, Issue 8, 2012.
2) Steven P. Stodghill, Thermal Analysis – A Review of Techniques
and Applications in the pharmaceutical sciences, 2010.
3) Bhupendar kumar*, Monish Sharma, Ramchandra, A Review on
Instrumentation of Thermal analysis method: DTA,DSC.
4) Gurdeep R. Chatwal, Sham K. Anand, Instrumental methods of
Chemical analysis, 5th edition, pg.no:2.719-2.753.
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 THANKS
TO
ALL

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