Unit I - Thermal Analysis

Theory, methodology and applications of thermogravimetric analysis (TGA), differential thermal analysis (DTA),
and differential scanning calorimetry (DSC). Principles, techniques and applications of thermometric titration
methods.

Thermogravimetric Analysis

• In a thermogravimetric analysis (TGA) the mass of a sample in a controlled atmosphere is recorded continuously as a
function of temperature or time as the temperature of the sample is increased (usually linearly with time).
• A plot of mass or mass percentage as a function of time is called a thermogram or a thermal decomposition curve.
Instrumentation
• Commercial instruments for TGA consist of
1. a sensitive microbalance, called a
thermobalance;
2. a furnace;
3. a purge-gas system for providing an inert, or
sometimes reactive, atmosphere;
4. a computer system for instrument control, data
acquisition, and data processing
The Thermobalance
• A number of different thermobalance designs
available commercially are capable of providing
quantitative information about samples ranging
in mass from less than 1 mg to 100 g.
• The usual range of thermobalances, however, is
from 1 to 100 mg.
• Many of the balances can detect changes in mass as small as 0.1 μg.
• Although the sample holder must be housed in the furnace, the rest of the balance must be thermally 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 E, which is situated between the poles
• of a permanent magnet F.
• 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-processing system.
The Furnace
• Furnaces for TGA typically cover the range from ambient temperature to 1000°C, although some can be used for
temperatures up to 1600°C.
• Heating rates can often be selected from 0.1°C/ min to 100°C/min.
• Insulation and cooling of the exterior of the furnace is required to avoid heat transfer to the balance. Nitrogen or argon is
usually used to purge the furnace and prevent oxidation of the sample
• The temperature axis is usually calibrated by using a material of known Curie point or sometimes a melting point standard.
• When thesample is heated through its Curie point, the magnetic mass is lost, and the balance indicates an apparent loss in
mass
 • Furnaces are usually cooled by forced air. Many furnaces can be cooled from 1000°C to 50°C in less than 15 minutes.
Sample Holders
• Samples are typically contained in sample pans made of platinum, aluminum, or a ceramic such as alumina
• Platinum is most often used because of its inertness and ease of cleaning
• Ceramic pans are best for high-volume, low-density samples (e.g., foams) and for materials that react with platinum
• Aluminum pans are inexpensive substitutes, but cannot be used for temperatures exceeding 600°C
Temperature Control and Data Processing
• The temperature recorded in a thermogram is ideally the actual temperature of the sample. This temperature can, in
principle, be obtained by immersing a small thermocouple directly in the sample.
• Such a procedure is seldom followed, however, because of possible catalytic decomposition of samples, potential
contamination of samples, and mass measurement errors resulting from the thermocouple leads.
• Because of these problems, recorded temperatures are generally measured with a small thermocouple located as close as
possible to the sample container.
• The recorded temperatures then generally lag or lead the actual sample temperature. In some cases, dual thermocouples are
used in a control/feedback mode.
• Modern TGA systems use a computerized temperature control routine that automatically compares the voltage output of
the thermocouple with a voltage-versus-temperature table stored in computer memory
TGA/MS and TGA/FTIR
• TGA is used to determine the loss in mass at particular temperatures, but TGA cannot identify the species responsible. To
obtain this type of information, the output of a thermogravimetric analyzer is often connected to a Fourier transform infrared
(FTIR) or a mass spectrometer (MS). Several instrument companies offer devices to interface the TGA unit to a
spectrometer. Some even claim true integration of the software and hardware of the TGA/MS or TGA/FTIR systems
Applications
• Because TGA monitors the mass of the analyte with temperature, the information provided is quantitative, but limited to
decomposition and oxidation reactions and to such physical processes as vaporization, sublimation, and desorption.
• In polymer studies, thermograms provide information about decomposition mechanisms for various polymeric preparations

• Above is a recorded thermogram obtained by increasing the temperature of pure CaC2O4 .H2O at a rate of 5°C/min.
• The clearly defined horizontal regions correspond to temperature ranges in which the indicated calcium compounds are
stable. This figure illustrates the use of TGA in defining the thermal conditions needed to produce a pure species.
Differential Thermal Analysis
• Differential thermal analysis (DTA) is a technique in which the
difference in temperature between a substance and a reference
material is measured as a function of temperature while the
substance and reference material are subjected to a controlled
temperature program
• Usually, the temperature program consists of heating the sample
and reference material in such a way that the temperature of the
sample Ts increases linearly with time.
• The difference in temperature ΔT between the sample temperature
and the reference temperature Tr (ΔT = Ts – Tr) is then monitored
and plotted against sample temperature to give a differential thermogram
Instrumentation
• A few milligrams of the sample (S) and an inert reference substance
(R) are contained in small aluminum dishes 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 digitized output voltage Es from the sample thermocouple is the
input to a computer. The computer controls 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,
which is used as the x-axis of the differential thermogram.
• The output across the sample and reference thermocouples ΔE is
amplified and converted to a temperature difference ΔT, which
serves as the y-axis of the thermogram.

General Principles
• The initial decrease in ΔT is due to the glass transition, a phenomenon observed in the initial segments of many differential
thermograms of polymers.
• The glass transition temperature Tg is the characteristic temperature at which glassy amorphous polymers become flexible
or rubber-like because of the onset of the concerted motion of large segments of the polymer molecules.
• When heated to the glass transition temperature Tg, the polymer changes from a glass to a rubber. Such a transition involves
no absorption or evolution of heat so that no change in enthalpy results—that is, ΔH = 0.
• The heat capacity of the rubber is, however, different from that of the glass, which results in the lowering of the baseline,
as shown in the figure. No peak appears during this transition, however, because of the zero enthalpy change.
• Two maxima and a minimum are observed in the thermogram
• The two maxima are the result of exothermic processes in which heat is evolved from the sample, thus causing its
temperature to rise.
 • When heated to a characteristic temperature, many amorphous polymers begin to crystallize as microcrystals, giving off
heat in the process. The second peak in the figure is endothermic and involves melting of the microcrystals formed in the
initial exothermic process.
• The minimum labeled “melting” is the result of an endothermic process in which heat is absorbed by the analyte.
• DTA peaks result from both physical changes and chemical reactions induced by temperature changes in the sample.
Applications
• DTA is considered a qualitative technique. Although able to measure the temperatures at which various changes occur,
DTA is unable to measure the energy associated with each event
• DTA is a widely used tool for studying and characterizing polymers
• DTA is also widely used in the ceramics and metals industry.
• An important use of DTA is for the generation of phase diagrams and the study of phase transitions
• The DTA method also provides a simple and accurate way of determining the melting, boiling, and decomposition points
of organic compounds.
Differential Scanning Calorimetry
• Differential scanning calorimetry (DSC) is the most often used thermal analysis method, primarily because of its speed,
simplicity, and availability.
• In DSC a sample and a reference are placed in holders in the instrument. Heaters either ramp the temperature at a specified
rate (e.g., 5°C/min) or hold the DSC at a given temperature.
• The instrument measures the difference in the heat flow between the sample and the reference
• The basic difference between DSC and DTA is that DSC is a calorimetric method in which differences in energy are
measured. In contrast, in DTA, differences in temperature are recorded
Instrumentation
• There are three different types of DSC instruments: power-compensated DSC, heat-flux DSC, and modulated DSC.
• Each produces a plot of power or heat flow versus temperature, called a thermogram
Power-Compensated DSC Instruments
• In power-compensated DSC, the temperatures of the sample and
reference are kept equal to each other while both temperatures are
increased or decreased linearly.
• The power needed to maintain the sample temperature equal to
the reference temperature is measured.
• Two independent heating units are employed. These heating units
are quite small, allowing for rapid rates of heating, cooling, and
equilibration
• The heating units are embedded in a large temperature-controlled heat sink. The sample and reference holders have
platinum resistance thermometers to continuously monitor the temperature of the materials.
• Both sample and reference are maintained at the programmed temperature by applying power to the sample and
• reference heaters. The instrument records the power difference needed to maintain the sample and reference at the same
temperature as a function of the programmed temperature
• Power-compensated DSC has lower sensitivity than heatflux DSC, but its response time is more rapid. This makes power-
compensated DSC well suited for kinetics studies in which fast equilibrations to new temperature settings are needed.
• Power-compensated DSC is also capable of higher resolution than heat-flux DSC.
Heat-Flux DSC Instruments
 • In heat-flux DSC, the difference in heat flow into the
sample and reference is measured while the sample
temperature is changed at a constant rate
• Both sample and reference are heated by a single
heating unit. Heat flows into both the sample and
reference material via an electrically heated constantan
thermoelectric disk,
• Small aluminum samples and reference pans sit on
raised platforms on the constantan disk. Heat is
transferred through the disks and up into the material
via the two pans
• The differential heat flow to the sample and reference is monitored by Chromel-constantan area thermocouples formed by
the junction between the constantan platform and Chromel disks attached to the underside of the platforms
• The differential heat flow into the two pans is directly proportional to the difference in the outputs of the two thermocouple
• junctions. The sample temperature is estimated by the Chromel-alumel junction under the sample disk.
• In heat-flux DSC, we can write the total heat flow dH/dt as

•
•

Modulated DSC Instruments

• Modulated DSC (MDSC) uses the same heating and cell arrangement as the heat-flux DSC method. In MDSC, a sinusoidal
function is superimposed on the overall temperature program to produce a micro heating and cooling cycle as the overall
temperature is steadily increased or decreased
• Using Fourier transform methods, the overall signal is mathematically deconvoluted into two parts, a reversing heat flow
signal and a nonreversing heat flow signal. The reversing heat flow signal is associated with the heat capacity component
of the thermogram, and the nonreversing heat flow is related to kinetic processes.
Applications
• Determination of the glass transition temperature Tg is one of the most important applications of DSC
• In most cases DSC is one of the easiest methods for determining levels of crystallinity.
• Many chemical reactions, such as polymer formation reactions, are exothermic and readily monitored by DSC methods
• The characterization of proteins is another important application of DSC
Thermometric Titrations
• In the thermometric titration, titrant is added at a known
constant rate to a titrand until the completion of the reaction
is indicated by a change in temperature. The endpoint is
determined by an inflection in the curve generated by the
output of a temperature measuring device
• At completion, the reaction produces a molar heat of
reaction ΔHr which is shown as a measurable temperature
change ΔT.