Thermal Analysis

Introduction
Thermal analysis is a branch of materials science where the properties of materials are
studied as they change with temperature. Several methods are commonly used - these are
distinguished from one another by the property which is measured.

Thermal analysis is defined as a series of technique for measuring the temperature

dependency of a physical property of a certain substance while varying the temperature
of a substance according to specific program.

Physical properties
 Mass
 Temperature
 Dimensions
 Enthalpy
 Dynamic characteristics

Objectives
 Introduce thermal analysis and its application at entry level at pharmaceutical
industry.
 Studying the behavior of pharmaceuticals by different thermal analysis instruments
under different conditions.
 Compare result was another objective

Principle
In thermal analysis the temperature of a substance under investigation is compared with the
temperature of thermally inert material such an alpha-alumina and is recorded with furnace
temperature as the substance is heated or cooled at predetermined uniform rate.
The principle of method consist in a measuring the change in temperature associated with
physical or chemical changes during the gradual heating of substance.

Instumentation
 Sample holder with build in thermocouple assembly
 Flow control system
 Furnace assembly
 Preamplifier and recorder
 Furnace power programmer and controller
Sample holder with build in thermocouple assembly
 Both metallic as well as non-metallic materials are employed for the fabrication of
sample holder.
 Metallic material include nickel , stainless steel , platinum and its alloys.
 Non-metallic material include glass , vitreous silica or sintered alumina.
 Metallic holders give rise to sharp endotherms and flat endotherms.
 Non-metallic holders give rise to sharp endotherms and flat exotherms.

Flow control system

A design of a Flow control Valve is required to maintain the flow rate without the onset of
cavitation or maintaining the flow without exceeding the pressure limit. The device should
have the ability to achieve all product specifications without exceeding the cost to maintain
the market leadership and brand recognition. Understanding the flow and thermal
characteristics inside the flow control valve is imperative in maintaining the higher quality
product

Furnace assembly
 It must be design in such a fashion so as to incorporate an appropriate smooth input
thereby maintaining either a fixed temperature or predetermined linear heating
program
 Temperature control is achieved via a thermocouple mounted very close to the
furnace-winding.
Preamplifier and recorder
The purpose of a preamplifier may be twofold. First of all it should increase the energy in the
detector signal to such a level that it can drive a reasonable length of low impedance coaxial
cable properly terminated at the other end with only a small loss in pulse amplitude. When
the detector produces a very weak signal it may be advantageous to amplify that signal to a
level where external noise becomes negligible.
In thermo analytical studies the signal obtained from sensors is recorded in which the signal
trace is produced on paper or film by ink , heating stylus , electric writing or optical beam.

Two types of recorder are used in thermal analysis:

 Detection type
 Null type

Furnace power programmer and controller

 These are the controller which can provide gradual rise of temperature at fixed rate.
 This device has a coarse and fine control knobs through which desired temperature
with respect to time can be obtained.
 This controlling is done by increasing voltage through the heated elements by motor
driven variable transformer by different thermocouples.
Techniques of thermal analysis
 Differential thermal analysis
 Dynamic mechanical analysis
 Dielectric thermal analysis
 Thermal optical analysis
 Differential scanning calorimetry
 Thermogravimetric analysis
 Evolved gas analysis

Differential thermal analysis

 Differential thermal analysis (DTA), in analytical chemistry, a technique for
identifying and quantitatively analyzing the chemical composition of substances by
observing the thermal behaviour of a sample as it is heated.
 The technique is based on the fact that as a substance is heated, it undergoes reactions
and phase changes that involve absorption or emission of heat.
 In DTA the temperature of the test material is measured relative to that of an adjacent
inert material.
 A thermocouple imbedded in the test piece and another in the inert material are
connected so that any differential temperatures generated during the heating cycle are
graphically recorded as a series of peaks on a moving chart.
 The amount of heat involved and temperature at which these changes take place are
characteristic of individual elements or compounds; identification of a substance,
therefore, is accomplished by comparing DTA curves obtained from the unknown
with those of known elements or compounds.

Differential scanning calorimetry

 The technique was developed by E. S. Watson and M. J. O'Neill in 1962,[1] and
introduced commercially at the 1963 Pittsburgh Conference on Analytical Chemistry
and Applied Spectroscopy.
 Differential scanning calorimetry, or DSC is a thermoanalytical technique in which
the difference in the amount of heat required to increase the temperature of a sample
and reference is measured as a function of temperature.
 Both the sample and reference are maintained at nearly the same temperature
throughout the experiment. Generally, the temperature program for a DSC analysis is
designed such that the sample holder temperature increases linearly as a function of
time.
 The reference sample should have a well-defined heat capacity over the range of
temperatures to be scanned.
Example: The technique is widely used across a range of applications, both as a routine
quality test and as a research tool. The equipment is easy to calibrate, using low melting
indium at 156.5985 °C for example, and is a rapid and reliable method of thermal analysis.

Dynamic mechanical analysis

 A technique in which the sample's kinetic properties are analyzed by measuring the
strain or stress that is generated as a result of strain or stress, varies (oscillate) with
time, applied to the sample.
 DMA is used for measurement of various types of polymer materials using different
deformation modes. There are tension, compression, dual cantilever bending, 3-point
bending and shear modes, and the most suitable type should be selected depending on
the sample shape, modulus and measurement purpose.

 Viscoelastic properties such as:

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

Dielectric thermal analysis

 Dielectric thermal analysis (DETA) is a materials science technique in which an
oscillating electric field is used to analyze changes in the physical properties of a
number of polar materials.
 This thermal analysis technique can be used with materials in a range of forms, from
thin films and sheet materials to powders or liquids.
 Another similar technique is dynamic mechanical analysis (DMA), in which a
mechanical force is used instead of an electrical field.

Thermal optical analysis

 Thermal-optical analysis (TOA) is a principal method for measuring elemental carbon
(EC) associated with atmospheric soot.
 It relies on changes in the optical behavior of carbon in particulate matter (PM) to
indicate when carbon measured as EC separates thermally from organic carbon (OC)
in the sample.
  We cannot assume that char produced by the instrument during pyrolysis of OC
separates physically from native EC during analysis because, as both are products of
incomplete combustion, they are chemically and physically similar substances.
 For the thermal-optical transmission method (TOT), an emphasis on optical behavior
presents it as a method for the accurate measurement of light-absorbing particulate
carbon and thus allows EC to be defined as black carbon (BC) as in the aethelometer.
 To achieve accuracy in EC as BC, three assumptions concerning the TOT s optical
behavior are necessary.
 First, the absorptivity of carbonaceous PM remains constant prior to OC pyrolysis,
i.e., no substantive change to particle refractive index occurs that would affect
absorptivity.
 Second, the absorptivity of pyrolyzed OC remains constant after its formation within
a high-temperature step in the non-oxidizing (He) phase.
 Third, pyrolyzed OC has the same absorptivity as native EC. Tests of these
assumptions using three types of samples (indoor air particles, urban (outdoor) PM,
and smoldering forest fire emissions) showed that all three assumptions are invalid.

Thermogravimetric analysis
 The technique in which the mass of a sample is monitored against time or
temperature, is performed with a ThermoGravimetric Analyser (TGA) or ther the
technique in which the mass of a sample is monitored against time or temperature, is
performed with a ThermoGravimetric Analyser (TGA) or thermobalance. Recently, a
survey of this technique and the available commercial equipment was given by
Wunderlich. Important differences between the balances are:
 The type of balance, vertical or horizontal furnace systems (the horizontal furnace
TGA needs a correction for the influence of the thermal expansion on the length of
the balance-arm),
 The sensitivity in combination with the maximum sample weight (a typical example is
the Perkin Elmer TGA-7 with a sensitivity of 0.0001 mg and a maximum sample
weight of 200 milligramme.
 The temperature range and the temperature accuracy. The sample mass determination
and the sample temperature measurement of the TGA has to be calibrated using
calibrated weights and the ferromagnetic transition (Curie) temperatures of calibration
metals.mobalance. Recently, a survey of this technique and the available commercial
equipment was given by Wunderlich . Important differences between the balances are:
 The type of balance, vertical or horizontal furnace systems (the horizontal furnace
TGA needs a correction for the influence of the thermal expansion on the length of
the balance-arm),
 The sensitivity in combination with the maximum sample weight (a typical example is
the Perkin Elmer TGA-7 with a sensitivity of 0.0001 mg and a maximum sample
weight of 200 milligramme.
  The temperature range and the temperature accuracy. The sample mass determination
and the sample temperature measurement of the TGA has to be calibrated using
calibrated weights and the ferromagnetic transition (Curie) temperatures of calibration
metals.

Evolved gas analysis

 Evolved Gas Analysis (EGA) is the analysis of the effluent of analytical equipment
and chemical processes.
 Understanding the dynamic composition of the gases released by thermal analysis or
continuous flow systems can provide insight into the mechanisms at work within the
experiment.
 When energy or a reagent is added to a reaction, changes to the off-gas can occur
instantaneously.
 The MAX300-EGA has the speed and sensitivity to detect even small shifts in the
evolved fraction as they occur. Characterize unknown samples, quantify solvent
compositions, pin point reaction kinetics.
 The heated transfer line can interface with a wide array of equipment, and signals and
data can be imported into the mass spectrometer for trending and calculation, or
exported for manipulation on another platform.

Applications of thermal analysis

 Thermal analysis is used to study:
 Liquid crystals
 Oxidative stability
 Metals
 Thermal instabilities of compounds
 It is used in:
 drug analysis
 Food science
 General chemical analysis
 Examining polymers
 Pharmaceutical industries
 Identification of polymers
 It is used in rapid identificaion of composition of mixtures of clays.
 Used in carbohydrates and other salt decomposition.
 Used in analysis of magnetic materials