Thermal Analysis: Principles, Techniques, and Applications

Introduction to Thermal Analysis

Thermal Analysis (TA) is a branch of materials science that studies how the physical
and chemical properties of a material change as a function of temperature or time
under a controlled atmosphere. It provides valuable information about a material's
behavior under thermal conditions, aiding in material characterization, quality control,
and research and development.

Basic Principle
The fundamental principle of thermal analysis involves subjecting a material to a
controlled temperature program (heating, cooling, or isothermal) and monitoring its
response. This response can be a change in:
● Mass: Thermogravimetric Analysis (TGA)
● Heat Flow: Differential Scanning Calorimetry (DSC)
● Temperature Difference: Differential Thermal Analysis (DTA)
● Dimension: Thermomechanical Analysis (TMA)
● Mechanical Properties: Dynamic Mechanical Analysis (DMA)
Types of Thermal Analysis Techniques
Here's a brief overview of the common thermal analysis techniques:
● Thermogravimetric Analysis (TGA): Measures changes in the mass of a sample
as a function of temperature or time.
● Differential Thermal Analysis (DTA): Measures the temperature difference
between a sample and a reference material as a function of temperature or time.
● Differential Scanning Calorimetry (DSC): Measures the heat flow into or out of
a sample as a function of temperature or time.
● Thermomechanical Analysis (TMA): Measures the dimensional changes of a
material as a function of temperature or time.
● Dynamic Mechanical Analysis (DMA): Measures the mechanical properties of a
material as a function of temperature, time, and frequency of an oscillating force.
Thermogravimetric Analysis (TGA)
Principle
TGA measures the change in the mass of a sample as it is heated, cooled, or held at a
constant temperature. The mass loss or gain is recorded as a function of temperature
or time. This change in mass provides information about the thermal stability,
composition, and decomposition behavior of the material.

Graphical Representation
TGA data is typically plotted as a thermogram, with mass (or percentage mass) on the
y-axis and temperature or time on the x-axis.

Image of TGA curve

● Mass Loss Steps: Indicate decomposition, volatilization, or sublimation.

● Plateaus: Represent regions of thermal stability.
● The derivative of the TGA curve (DTG) can help pinpoint the exact temperatures
of mass change.
Instrumentation
A TGA instrument consists of the following key components:
● Microbalance: A highly sensitive balance to measure minute changes in sample
mass.
● Furnace: A controlled heating chamber to subject the sample to the desired
temperature program.
● Sample Holder (Crucible): A small container, usually made of platinum or
ceramic, to hold the sample.
● Temperature Programmer: Controls the heating/cooling rate and isothermal
conditions.
● Gas Flow System: Controls the atmosphere (inert or reactive) around the
sample.
● Data Acquisition System: Records the mass and temperature data.
Process Chemistry
TGA can be used to study various chemical processes, including:
● Decomposition: Breakdown of a compound into simpler substances.
○ CaCO3(s)ΔCaO(s)+CO2(g)
● Oxidation: Reaction with oxygen, leading to a change in mass.
○ 2Mg(s)+O2(g)Δ2MgO(s)
● Dehydration: Removal of water from a material.
○ CuSO4⋅5H2O(s)ΔCuSO4(s)+5H2O(g)
● Sublimation: Transition from solid to gas phase.
○ I2(s)ΔI2(g)
Factors Affecting TGA Results
● Heating Rate: Faster heating rates may shift decomposition temperatures to
higher values.
● Sample Size and Morphology: Larger sample sizes and particle size can affect
heat transfer and gas diffusion, influencing the results.
● Atmosphere: The surrounding gas (inert, oxidizing, reducing) can significantly
affect the decomposition process.
● Crucible Material: The material of the sample holder should be inert and not
react with the sample.
● Gas Flow Rate: The flow rate of the purge gas can affect the removal of volatile
products.
Phenomena Occurring During TGA
● Decomposition: Chemical breakdown of the sample.
● Volatilization: Evaporation of volatile components.
● Oxidation/Reduction: Chemical reactions with the surrounding atmosphere.
● Adsorption/Desorption: Uptake or release of gases.

Applications of TGA
● Determination of Thermal Stability: Assessing the temperature at which a
material begins to decompose.
● Compositional Analysis: Determining the amount of each component in a
mixture.
● Moisture and Volatile Content Analysis: Measuring the amount of water or
other volatile substances in a sample.
● Study of Decomposition Kinetics: Investigating the rate and mechanism of
decomposition reactions.
● Polymer Characterization: Determining the thermal stability and composition of
polymers.
● Pharmaceutical Analysis: Analyzing the thermal behavior of drugs and
excipients.
● Food Science: Studying the thermal properties of food products.
Differential Thermal Analysis (DTA)
Principle
DTA measures the temperature difference between a sample and an inert reference
material as they are heated or cooled under identical conditions. The temperature
difference is plotted against time or temperature. Peaks in the DTA curve indicate
thermal transitions in the sample.

Graphical Representation
DTA curves plot the temperature difference (ΔT) between the sample and reference
against temperature or time.

Image of DTA curve

● Endothermic Peaks: Indicate processes that absorb heat (e.g., melting,

dehydration).
● Exothermic Peaks: Indicate processes that release heat (e.g., crystallization,
combustion).
Instrumentation
A DTA instrument consists of:
● Furnace: Heats the sample and reference.
● Sample and Reference Holders: These hold the sample and reference material,
and are designed to ensure good thermal contact with the thermocouples.
● Thermocouples: Measure the temperature of the sample and reference.
● Differential Amplifier: Measures the difference in temperature between the
sample and reference.
● Temperature Programmer: Controls the heating/cooling rate.
● Data Acquisition System: Records the temperature difference and temperature.
● Gas Flow System: Provides a controlled atmosphere.
Process Chemistry
DTA can detect:
● Phase Transitions: Melting, boiling, and sublimation.
● Chemical Reactions: Oxidation, decomposition, and polymerization.
● Crystallization: Formation of a crystalline structure.
● Glass Transitions: The temperature at which a glassy material transitions from a
rigid to a rubbery state.
Factors Affecting DTA Results
● Heating Rate: Affects peak sharpness and position.
● Sample Holder: Material and geometry influence heat transfer.
● Sample Size: Larger samples may show broader peaks.
● Reference Material: Should be thermally inert over the temperature range of
interest (e.g., alumina).
● Atmosphere: Can affect reaction temperatures and types of transitions.

Phenomena Occurring During DTA

● Melting: Endothermic peak.
● Crystallization: Exothermic peak.
● Glass Transition: A change in baseline.
● Chemical Reactions: Exothermic or endothermic peaks.
● Boiling/Sublimation: Endothermic peak
Applications of DTA
● Identification of Thermal Transitions: Determining melting points, boiling
points, glass transition temperatures, and crystallization temperatures.
● Study of Phase Transitions: Investigating solid-solid phase transitions.
● Analysis of Chemical Reactions: Detecting exothermic and endothermic
reactions.
● Characterization of Materials: Identifying and comparing different materials.
● Purity Determination: Assessing the purity of a substance.
● Construction Materials: Cement hydration, ceramic sintering.
● Geology and Mineralogy: Clay mineralogy, carbonate decomposition.
Differential Scanning Calorimetry (DSC)
Principle
DSC measures the difference in heat flow between a sample and a reference as a
function of temperature or time. The sample and reference are maintained at the
same temperature throughout the experiment. DSC measures the amount of energy
absorbed or released by a sample during thermal transitions.

Graphical Representation
DSC curves plot the heat flow rate (mW or J/s) against temperature or time.

Image of DSC curve

● Endothermic Peaks: Represent heat absorption (e.g., melting).

● Exothermic Peaks: Represent heat release (e.g., crystallization).
● The area under the peak is proportional to the enthalpy change (ΔH) of the
transition.
Instrumentation
A DSC instrument consists of:
● Furnace: Provides controlled heating or cooling.
● Sample and Reference Pans: Small containers, often aluminum, that hold the
sample and reference.
● Calorimetric System: Measures the heat flow difference between the sample
and reference. There are two main types:
○ Heat Flux DSC: Measures the temperature difference between the sample
and reference and converts it to heat flow.
○ Power Compensation DSC: Adds power to the sample or reference to keep
them at the same temperature.
● Temperature Programmer: Controls the temperature program.
● Data Acquisition System: Records heat flow and temperature data.
● Gas Flow System: Controls the atmosphere.
Process Chemistry
DSC is used to study:
● Phase Transitions: Melting, crystallization, glass transitions.
● Chemical Reactions: Curing, decomposition, oxidation.
● Heat Capacity: The amount of heat required to change the temperature of a
substance.
● Purity Analysis: Determining the purity of a material.

Factors Affecting DSC Results

● Heating Rate: Affects peak shape and position; slower rates improve resolution.
● Sample Size and Preparation: Smaller, well-prepared samples improve thermal
contact and results.
● Pan Material: влияет на теплопередачу и возможность реакции (e.g.,
aluminum, platinum).
● Atmosphere: Oxidizing, inert, or reducing atmospheres can influence transitions.
● Instrument Calibration: Accurate temperature and enthalpy calibration is
crucial.
Phenomena Occurring During DSC
● Melting: Endothermic peak. The peak area is proportional to the heat of fusion.
● Crystallization: Exothermic peak. The peak area is proportional to the heat of
crystallization.
● Glass Transition: A step change in the baseline.
● Curing: Exothermic peak (e.g., polymerization of resins).
● Decomposition: Endothermic or exothermic, depending on the reaction.
● Oxidation: Exothermic peak.

Applications of DSC
● Polymer Science: Determining glass transition temperatures, melting points,
crystallinity, and curing behavior.
● Pharmaceuticals: Characterizing drug polymorphs, determining purity, and
studying drug-excipient compatibility.
● Food Science: Analyzing melting and crystallization behavior of fats, starches,
and proteins.
● Materials Science: Studying phase transitions in metals, ceramics, and
composites.
● Chemical Industry: Investigating reaction kinetics and thermal stability of
chemicals.
● Purity Determination: Measuring the melting point depression to determine
sample purity.
● Enthalpy and Heat Capacity Measurements: Determining the amount of heat
absorbed or released during transitions.