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tga measurement
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Thermal Analysis
Dr. S. Anandhan,
Asst. Professor,
Dept. of Met. and Mat. Engg., NITK
What is thermal analysis?
"A group of techniques in which a physical property of a substance and/or its reaction products is measured as a function of temperature whilst the substance is subjected to a controlled temperature program"
R.C.Mackenzie, Thermochim. Acta, 1979, 28, 1.
Heat flow into a substance induces many physical and chemical changes which can help to identify and characterize a sample
Thermal Analysis
A group of analytical techniques
Each technique defines a material property
TA Techniques TA Use
Thermal Analysis is widely used
For a wide variety of Applications
Over a dozen thermal methods can be recognized, which differ in the properties measured and the temperature programs
These are used for quality control and research applications on industrial products, such as polymers, pharmaceuticals, clays and minerals, metals and alloys
Thermogravimetric Analysis (TGA) or Thermogravimetry
Thermogravimetry fundamentals
Principle
Changes in the mass of a sample are studied while the sample is subjected to a programme.
The temperature programme is most often a linear increase in temperature, but, also be carried out, when the changes in sample mass with time are followed.
TGA is inherently quantitative, and therefore an extremely powerful thermal technique, but gives no direct chemical information. The ability to analyze the volatile products duvalue
TGA + Mass Spectrometry: TGA
TGA + Infrared Spectroscopy: TGA
Processes that lead to weight gain or loss in TGA experiments
Instrumentation
Thermobalance/microbalance
Balance sensitivity is usually around one microgram, with a total capacity of a few hundred milligrams
Furnace
Temperature programmer
A typical operating range for the furnace is ambient to 1500C, with heating rates up to 200C/min
Thermogravimetric Analysis (TGA) or Thermogravimetry
fundamentals
of a sample are studied while the sample is subjected to a
The temperature programme is most often a linear increase in temperature, but, also be carried out, when the changes in sample mass with time are followed.
TGA is inherently quantitative, and therefore an extremely powerful thermal technique, but gives no direct chemical information. The ability to analyze the volatile products during a weight loss is of great
TGA + Mass Spectrometry: TGA-MS
TGA + Infrared Spectroscopy: TGA-FTIR
Processes that lead to weight gain or loss in TGA experiments
Thermobalance/microbalance
sensitivity is usually around one microgram, with a total capacity of a few hundred
A typical operating range for the furnace is ambient to 1500C, with heating rates up to
of a sample are studied while the sample is subjected to a controlled temperature
The temperature programme is most often a linear increase in temperature, but, isothermal studies can also be carried out, when the changes in sample mass with time are followed.
TGA is inherently quantitative, and therefore an extremely powerful thermal technique, but gives no ring a weight loss is of great
sensitivity is usually around one microgram, with a total capacity of a few hundred
A typical operating range for the furnace is ambient to 1500C, with heating rates up to
Temperature sensor
thermocouple placed close to the sample
Sample holder/pan
An enclosure for establishing the required atmosphere
Reactive or inert
Microcomputer/microprocessor
Instrument control
Data acquisition and display
Balance/furnace configurations
thermocouple placed close to the sample
An enclosure for establishing the required atmosphere
Microcomputer/microprocessor
Data acquisition and display
Pans for TGA
aluminum, platinum, silica, and alumina
Data Analysis
Thermogram is graph of mass versus temperature. Sometimes given as % of original mass.
Draw tangents of the curve to find the onset and the offset points
mi, mf and m are fundamental properties ofthe sampleTi and Tf depend on operating variables
Typical TG curves
Derivative thermogram (DTG)
plots change in mass with temperature, dm/dt, and resolves changes more clearly.
Calibration
MASS - Use standard weights.
Use standard samples to check operation, but unwise to use them as weight standards.
TEMPERATURE -
Four approaches:
Observe deflection on Temperature/time curve
Curie-point standards
Drop-weight methods
In simultaneous-type units, use melting standards
DO NOT use decomposition events to define temperature.
Calibration using curie point
Factors affecting TG Analysis
heating rate and sample size
increase in either of which tends to increase the decomposition temperature, and to decrease the resolution between successive mass losses
particle size and packing of the sample
crucible shape
Gaseous atmosphere
Nature
flow rate
Effect of gaseous atmosphere
Polymers degrade at a lower temperature in presence of O
heating rate and sample size
in either of which tends to increase the decomposition temperature, and to decrease the resolution between successive mass losses
particle size and packing of the sample
Polymers degrade at a lower temperature in presence of O
in either of which tends to increase the decomposition temperature, and to decrease the
Polymers degrade at a lower temperature in presence of O2
Effect of heating rate
10 mg samples of PTFE, heated at 2.5, 5, 10 and 20 C/min in nitrogen
Important note
Careful attention to consistency in experimental details normally results in good repeatability.
On the other hand, studying the effect of deliberate alterations in such factors as the heating rate can give valuable insight into the nature of the observed reactions.
Sources of error
A) MASS
Classical buoyancy
Effect temp. on balance
convection and/or turbulence
viscous drag on suspension
These are lumped together as the buoyancy correction, and if significant, can be allowed for by a blank run
B) TEMPERATURE
Temperature calibration difficult to carry out accurately.
Many methods exist, but none totally satisfactory.
Best accuracy from simultaneous TG-DTA or TG-DSC instrument.
NOISY OR ERRATIC RECORDS CAN ARISE FROM:
static
vibration
pressure pulses in lab.
uneven gas flow
Applications of TGA
Ability of TG to generate fundamental quantitative data from almost any class of materials, has led to its widespread use in every field of science and technology. Key application areas are listed below:
Thermal Stability: related materials can be compared at elevated temperatures under the required atmosphere. The TG curve can help to elucidate decomposition mechanisms.
Material characterization: TG and DTG curves can be used to "fingerprint" materials for identification or quality control.
Compositional analysis: by careful choice of temperature programming and gaseous environment, many complex materials or mixtures may be analyzed by selectively decomposing or removing their components. This approach is regularly used to analyze e.g. filler content in polymers; carbon black in oils; ash and carbon in coals, and the moisture content of many substances.
Simulation of industrial processes: the thermobalance furnace may be thought of as a mini-reactor, with the ability to mimic the conditions in some types of industrial reactor.
Kinetic Studies: a variety of methods exist for analyzing the kinetic features of all types of weight loss or gain, either with a view to predictive studies, or to understanding the controlling chemistry.
Corrosion studies: TG provides an excellent means of studying oxidation, or reaction with other reactive gases or vapors.
Ex.1.Comparison of thermal stability of materials
Ex.2.Quantitative analysis of materials - % composition of a rubber sample
Ex.3.Quantitative analysis of materials - % composition of a composite used in making doors
Ex.4.Mechanism of thermal reactions
Ex.5. Effect of additives on thermal stability of materials
EX.6.Analysis of Chewing Gum with Auto Stepwise TGA
Chewing gum is a complex mixture of a number of components, including: natural elastomers, glycerin, softening agents, and carbonates, flavoring agents, sweeteners and colorants.
The correct combination of the gum formulation proincluding: stickiness, softness and chewability.
Sample is heated at a constant rate until a significant weight loss event is encountered.
Equipment automatically holds the sample under isothermal conditiothat the given component has essentially completed its given degradation.
Ex.5. Effect of additives on thermal stability of materials
EX.6.Analysis of Chewing Gum with Auto Stepwise TGA
Chewing gum is a complex mixture of a number of components, including: natural elastomers, glycerin, softening agents, and carbonates, flavoring agents, sweeteners and
The correct combination of the gum formulation provides the end characteristics to the chewing gum, stickiness, softness and chewability.
Sample is heated at a constant rate until a significant weight loss event is encountered.
Equipment automatically holds the sample under isothermal conditions until becomes small, meaning that the given component has essentially completed its given degradation.
Chewing gum is a complex mixture of a number of components, including: PVAc (poly vinyl acetate), natural elastomers, glycerin, softening agents, and carbonates, flavoring agents, sweeteners and
vides the end characteristics to the chewing gum,
Sample is heated at a constant rate until a significant weight loss event is encountered.
ns until becomes small, meaning
Heating is automatically resumed, at a constant rate, until the next significant weight loss event. By this process, we are able to nicely resolve closely occurring decomposition events and provide better quantitative analysis of a sample.
Standard TGA results for Doublemint chewing gum sample
TGA auto stepwise results for Doublemint chewing gum sample
References
D. A. Skoog et al., Principles of instrumental analysis, fifth edition, Harcourt Publishers, 2001.
http://www.anasys.co.uk/library/macrota.htm