Nanomaterials Nanotechnology Nano chemistry Characterization techniques Thermal gravimetric Analysis for Nanomaterials TGA

1. GROUP 3
HAMMAD SAJJAD
BSE-C-19-65
Thermogravimetric analysis for the characterization of
Nanomaterials

2. Introduction to Nanomaterials and Nanochemistry
 Chemical and physical properties of solid materials strongly
depend on both the size and the shape of the microscopic
constituent particles.
 This is particularly true for materials with morphological
features smaller than a micron in at least one dimension
which are commonly called nano-scale materials, or simply
nanomaterials.

3. Nanomaterials and Nanochemistry
 Nanoscale materials are defined as a set of substances
where at least one dimension is less than approximately
100 nanometers.
 Nanochemistry is defined as the synthesis, analysis, and
characterization of chemical compounds at the nanoscale.

4. Characterizaton of Nanomaterials by TGA
 The post processing of the prepared products involved
characterization and investigation of certain features about
them.
 After synthesis the prepared product is subjected to
instrumentation.
 These instruments deal with the elemental analysis of the
products, structural features investigation and
determination of size distributions mainly.

5. Can TGA analyze Nanomaterials?
 TGA is widely used as a QA/QC tool in the manufacture
and use of Carbon Nano Tubes (CNT). TGA is used in
CNT manufacturing process to characterize the amount
of metallic catalytic residue that remains on the CNT.
This is done because CNT are classified by percent
purity; in other words 100% less the percent of catalytic
residue (carbon to metal content). TGA is used to
characterize end products that contain Nanoparticles
(NP) or CNTs as in their usual end product
characterizations.
 Characterization of coatings on NPs and CNTs by evolved
gas analysis can be achieved using TGA-EGA techniques.
Both NP manufacturers and manufacturers of end
products that contain NPs and CNTs use these
techniques. And with TGA Hyphenated systems, the TGA
can always be used alone as a simple TGA.

6. Thermogravimertic Analysis
 Thermogravimertic analysis (TGA) is a straight forwad
analytical technique that typically requires no sample
preparation beyond drying of the sample.
 Post research has shown that TGA can be reliably used to
evaluate the purity of a substance and to characterize
nanomaterials.
 For thermogravimetric analysis, materials are heated to
elevated temperature while monitoring the mass of the
sample, which yields the decomposition curve.
 Analysis of decomposition curve yields the oxidation
temperature and residual mass of the sample.

7. Continue…..
 The oxidation temperature here is defined as the
temperature at which bulk of the material decomposes.
 For Carbon-based materials, the residual mass, or ash
content is the remaining mass of the sample after
decomposition.
 For nanomaterials, residual mass could be due to inorganic
nanomaterials, residual metal catalysts from synthesis or
impurities within the sample.

8. Procedure
 In TGA a quartz crystal microbalance (QCM) is used to detect
the mass of nanomaterials via piezoelectricity, which is
sensitive to mass changes on the order of nanograms.
 When nanomaterials are deposited on the active area of the
QCM electrode, the resonant frequency is dampened.
 The shift in resonant frequency can be related to a shift of
mass by using the equation developed by Sauerbery.
 Once the nanoparticle sample is deposited, the QCMs are
heated in a box-furnace at increasing intervals with the
frequency of the QCM being read at the end of the interval,
thus stimulating the effect of TGA and yielding a
decomposition curve from which materials can be evaluated.

9. A block diagram of the quartz crystal microbalance
measurement system.

10. Decomposition of ammonium perchlorate by using
nanomaterial as catalyst (Example 1)
 Ammonium perchlorate (AP) is the most frequently utilized
oxidizer in composite solid propellants (CSPs). Thermal
decomposition properties of AP significantly influence the
combustion activities of the propellants.
 Due to all these reasons the catalytic thermal
decomposition of AP has garnered great attention.
 Co3O4 has been considered as an exceptional material for
catalyzing thermal decomposition of AP because it is an
important p-type semi-conductor.
 The thermal decomposition is powered by many other
factors namely size of the particles used as catalyst, their
shapes and porosity are most parameters affecting the
catalyst process.

11. Continue….
 Figure illustrates the TG curves for pure AP and the
mixtures of AP and Co3O4 porous cuboids.
 Clearly, the decomposition temperature of AP reduces to a
large extent as a result of adding the Co3O4 particles
significantly. The initial thermal decomposition of AP is
300°C and for sample containg 2 percent porous cuboids
Co3O4 particles and 98 percent AP is 253.8°C. The final
thermal decomposition temperatures are 450.6°C and
297.6°C respectively.
 This data shows a decrease of 153°C in thermal
decomposition temperatur of AP that endroses a significant
catalytic activity of porous cuboids Co3O4.

12. Graph of Example 1

13. Example 2
 The TGA curve of two differently cured epoxy resin is shown in figure
and we can get information about thermal stability of these systems.

14. Investigating Carbon-Based Nanomaterials with
Thermogravimetric Analysis
 Thermogravimetric analysis is one of the quickest
techniques for determining the relative proportions of
amorphous carbon, adsorbed hydrocarbon, structured
carbon, and metal catalyst particles in a CNT powder
sample.
 The observed temperatures of oxidation for amorphous
carbons are around 200 °C, 400 °C for single-wall carbon
nanotubes, 600 °C for multi-wall carbon nanotubes, and
anything above 650 °C is credited to a metal catalyst and its
oxidation products.

15. Continue….
 Thermogravimetric analysis can provide a measure of
purity for CNT materials by calculating the percentage of
the sample that degrades at the desired temperature
range. Thermogravimetric analysis is also useful for
studying carbon nanotubes' thermal behavior in an
oxidative environment.
 Similarly, thermogravimetric analysis is a reliable
analytical tool for characterizing and controlling the
quality of powdered few-layer graphene (FLG) and non-
graphene impurities. The derivative TGA curves of
graphene oxide, FLG, and graphite powders have distinct
peaks with a temperature of maximum mass
decomposition rates (Tmax) in specific ranges, which can
aid in distinguishing few-layer graphene from fake
graphene

16. Thermogravimetric Analysis for Nanoparticles
 Nanocalorimetry is a microchip-based system that can
measure the thermal properties of samples in nanolitres or
nanograms at very fast rates. Due to the small sample
volumes, it is possible to measure interactions between
nanomaterials and cells, which is important in
nanomedicine.
 Using nanocalorimetry has aided in the understanding of
binding reactions between biological systems and
nanoparticles, melting behavior and particle crystallization,
and sizedependent thermodynamics and kinetics.

17. Thermal Characteristics of Nanofluids
 A nanofluid is a fluid that contains nanoparticles that have
been dispersed evenly throughout the fluid. Nanoparticles,
generally smaller than 100 nanometers, are combined with
a base fluid (such as water) to create nanofluids
 These nanoparticles can have a significant impact on the
thermal properties of the fluid. The thermal conductivity of
the base fluid can be significantly increased by the inclusion
of these nanoparticles, making nanofluids an appealing
option for heat transfer applications.

18. Thermal Analysis to Characterize the Thermal
Properties of Nanofluids
 Thermal analysis is required to characterize the thermal
properties of nanofluids, such as thermal conductivity,
thermal diffusivity, and specific heat capacity, to
comprehend their behavior completely. The design and
functionality of heat transfer systems based on nanofluids
may be optimized using these features as a result
 The degree to which different working fluids in thermal
systems can transmit heat from one another is one of the
most important aspects determining how well thermal
systems function. To improve the heat transfer properties
of the base fluids, nanoparticles are incorporated into the
fluids in very small concentrations. If an increase in heat
transmission is desired, the thermal conductivity of the
nanofluids is thought to be the most critical parameter
among its many other hermos-physical features.

19. Applications of Thermogravimetric Analysis
 Thermogravimetric analysis and DSC can be used to assess
crystallization behaviors and the interaction of drug
nanoparticle-based delivery systems. For example, to assess
the interactions of indomethacin, a lipophilic drug, and
solid lipid nanoparticles designed for pharmaceutical drug
delivery
 Proteins or lipid layers are now being coated onto
nanoparticles such as carbon nanotubes (CNTs) for
biomedical applications. Microscale thermogravimetric
analysis is frequently used to assess the purity and amount
of surface coating.

20. Continue….
 Catalytic properties of zeolites are determined by the
distribution of acid sites. Thermogravimetric analysis is
used to determine the relative strength of a catalyst.
 Nanocomposites are materials in which nanoparticles are
infused with a matrix material to enhance their electrical,
optical, or magnetic properties. Thermal analysis methods
are frequently used to investigate the differences between
the matrix and the matrix with nanoparticles incorporated.

21. Advantages
 Here TGA is used to analyze a variety of nanoparticles to
demostrates how this technique could be applied to
evaluate the decomposition of nanomaterials and their
coatings.
 TGA technique can be used to address concers that arise in
nanoparticle samples, such as small volume can validate
the results against other analytical instrumentation.
 Carbon nanotubes are measured by microscale TGA to give
oxidation temperature of the material, as well as residual
mass (which is due to catalyst after the decomposition of
carbon is complete).

22. Continue…
 These results are compared to conventional TGA
measurements to establish accuracy of this technique.
 Reproducibility of the TGA technique is established and
limitations are also identified, from the analysis of SiO2
nanoparticles with and without poly (ethylene glycol)
coatings.
 The advantage of TGA is that micrograms, instead of
milligrams, of mass are required to obtain results.

23. Future Prospectives and Limitations of
Thermogravimetric Analysis (TGA)
 Thermogravimetric analysis techniques and the
determination of thermophysical properties through
thermal analysis provide a wealth of information on
nanoparticle-containing materials
 The primary limitation of thermogravimetric analysis
methods is that mass loss of volatiles does not equal
degradant formation. As a result, mass loss should only be
regarded as an indicator of degradation. Nevertheless,
thermogravimetric analysis is an extremely useful tool for
interpreting the thermal events associated with
nanomaterials.

24. C A R A V A N N A N O M A T E R I A L S A N D
N A N O C H E M I S T R Y
H T T P S : / / W W W . A Z O N A N O . C O M / A R T I C L E . A S P
X ? A R T I C L E I D = 6 3 8 1
H T T P : / / W W W . P E R K I N E L M E R . C O M / A P P L I C A T
I O N S C E N T R A L
References