Thermogravimetric Analysis For Characterization of Nanomaterials

Thermogravimetric Analysis for
Chapter
4
Characterization of Nanomaterials
Sravanthi Loganathan1,
Ravi Babu Valapa , Raghvendra Kumar Mishra , G. Pugazhenthi3 and Sabu Thomas1
2 1
1
Mahatma Gandhi University, Kottayam, India; 2Centre for Biopolymer Science and Technology, A Unit of Central
Institute of Plastics Engineering and Technology (CIPET), Kochi, India; 3Indian Institute of Technology Guwahati,
Guwahati, India
CHAPTER OUTLINE
4.1 Introduction 68
4.1.1 Definition and Principle of Thermogravimetry Analysis 68
4.2 Instrumental Setup for Thermogravimetric Analysis 69
4.2.1 Electronic Microbalance 69
4.2.1.1 Types of Microbalance 70
4.2.2 Sample Holder 71
4.2.2.1 Types of Crucibles 73
4.2.3 Furnace 73
4.2.4 Thermocouple 75
4.2.5 Temperature Programmer 76
4.2.6 Data Recording Unit 76
4.3 Classification of Thermogravimetric Analysis 76
4.3.1 Dynamic Thermogravimetric Analysis 76
4.3.2 Static or Isothermal Thermogravimetric Analysis 76
4.3.3 Quasistatic Thermogravimetric Analysis 76
4.4 Thermogravimetry Curve 77
4.4.1 Interpretation of TG Curve 77
4.4.1.1 Types of Thermogravimetry Curve 77
4.4.1.2 Plateau 78
4.4.1.3 Initial Decomposition Temperature 78
4.4.1.4 Final Decomposition Temperature 78
4.4.1.5 Reaction Interval 79
4.4.1.6 Determination of Isobaric Mass Change 79
4.4.1.7 Evolved Gas Analysis 79
Thermal and Rheological Measurement Techniques for Nanomaterials Characterization. http://dx.doi.org/10.1016/B978-0-323-46139-9.00004-9

Copyright © 2017 Elsevier Inc. All rights reserved. 67
68 CHAPTER 4 Thermogravimetric Analysis for Characterization of Nanomaterials
4.4.1.8 Information From Thermograms 79

4.5 Advanced Thermogravimetric Analysis Instruments 80
4.5.1 Simultaneous Determination of Thermogravimetry and Heat Flow
Curves 80
4.5.2 Evolved Gas Analysis 80
4.5.2.1 Thermogravimetric AnalysiseCoupled Fourier Transform Infrared
Spectrometry 81
4.5.2.2 Thermogravimetric AnalysiseMass Spectrometry 81
4.5.2.3 Thermogravimetric AnalysiseGas Chromatography Mass
Spectrometry 82
4.6 Case Studies for Applications of Thermogravimetric Analysis 82
4.6.1 Determination of Thermal Stability Under Modified Atmosphere 82
4.6.2 Prediction of Thermal Decomposition Mechanism 87
4.6.3 Determination of Nanoparticle Purity and Amount of Surface
Coatings 93
4.6.4 Evaluation of Loading of Drug or Functional Moieties 95
4.6.5 Gas Adsorption Studies 97
4.6.6 Determination of Relative Strength for Catalysts 98
4.6.7 Kinetic Analysis 99
4.7 Conclusions 105
References 107
4.1 INTRODUCTION
4.1.1 Definition and Principle of Thermogravimetry
Analysis
Thermogravimetry deals with the branch of thermal analysis that investi-
gates the change in weight of a substance as a function of time or temper-
ature. The weight change profile is recorded when the sample is subjected to
a heating or cooling environment in a controlled manner. When the weight
change is recorded as a function of time, then it is termed as “isothermal
mode.” In case of scanning mode, the weight change is recorded as a func-
tion of temperature.
The main principle of thermogravimetric analysis (TGA) is that mass
change of a sample can be studied under programmed conditions. There-
fore, TGA is mainly used for understanding certain thermal events such
as absorption, adsorption, desorption, vaporization, sublimation, decompo-
sition, oxidation, and reduction. In addition to this, TGA can be utilized for
the evaluation of volatile or gaseous products lost during such chemical re-
actions for samples such as nanomaterials, polymers, polymer nanocompo-
sites, fibers, paints, coatings, and films. Along with the prediction of thermal
stability for samples, it is also possible to study the kinetics of chemical re-
actions under various conditions using TGA. To investigate the kinetics, it
becomes essential to optimize the factors or conditions that influence the

mass change of samples throughout the experimental period. The factors
that are found to influence mass change include (1) weight and volume
of the sample taken for analysis, (2) physical form of the sample, (3) shape
as well as nature of the sample holder, (4) nature of the atmosphere under
which the analysis is performed, (5) pressure of the atmosphere maintained
in the sample chamber during the analysis, and (6) rate of heating or cool-
ing. It is well known that temperature conditions can bring changes in the
sample mass. However, it is important to understand the fact that not all
types of thermal changes can influence the weight change of samples.
For example, melting and crystallization behavior of samples cannot be
studied using TGA.
4.2 INSTRUMENTAL SETUP FOR

THERMOGRAVIMETRIC ANALYSIS
The thermobalance is regarded as the heart of a TGA unit. A schematic rep-
resentation of a thermobalance can be seen in Fig. 4.1. It comprises several
subunits, such as (1) electronic microbalance, (2) sample holder, (3) furnace,
(4) temperature programmer, and (5) recorder. The thermobalance consists
of a clamp that is utilized to hold the arm of a microbalance. Once the clamp
is released, it should be noted whether the balance is returned to zero posi-
tion. The thermobalance should not be transported while it holds the arm of
the microbalance using clamps. The zero point will be affected if such trans-
portation is attempted. It is generally preferred to allow the microbalance to
stabilize for w15e20 min after placement of the sample is ensured [1e5].
4.2.1 Electronic Microbalance

The microbalance serves as the most significant component of a thermoba-
lance. The main purpose of a microbalance is to record the changes
n FIGURE 4.1 Schematic representation of a thermobalance.

associated with sample mass. The important characteristics that an ideal mi-
crobalance should possess are as follows:
1. Mass change of a sample should be recorded accurately and in a repro-
ducible manner under various atmospheric conditions as well as
temperatures.
2. Electronic signals should be appropriately provided by the microbal-
ance to precisely record the mass change.
3. An immediate and ultimately fast response to mass change must be
provided by electronic signals.
4. An arrangement for automatic mass regulation should be enabled by
the microbalance.
5. A high range of mechanical as well as electrical stability must be
ensured by the microbalance.
6. The microbalance should not be affected by vibrations.
7. The operation of the microbalance should be user friendly.
4.2.1.1 Types of Microbalance

Microbalances are divided into two types: (1) deflection type and (2) null-
point type [1e5].
4.2.1.1.1 Deflection-Type Balance

Deflection-type balances are further subdivided into four types as shown in
Fig. 4.2A.
1. Beam type: In beam-type balances, conversion of deflected beams
occurs along with the mass change. The thermogravimetry (TG) curves
thus formed are then identified using photographic trace and signals
that are generated by displacement-measuring transducers.
2. Helical type: In helical-type balances, a spring may undergo contraction
or elongation with respect to the mass change of a sample, which in
turn is recorded using transducers.
3. Cantilevered beam type: In cantilevered-beam-type balances, the
sample is present on one end and the other end of the beam is fixed.
During mass change, deflections are produced, which are then recorded
using photographic trace and signals generated with the help of
displacement-measuring transducers or electromechanically.
4. Torsion wire type: In torsion-wire-type balances, a hard torsion wire
is present and it acts as a fulcrum. Here, the beam is attached to the
hard torsion wire. The wire is then attached to one or both ends of
the balance. This is done to make the beam deflection proportional to
the mass change. The deflections are recorded in the usual manner,
which is similar to other deflection-type balances discussed earlier.
n FIGURE 4.2 Different types of microbalance. (A) Deflection- and (B) null-point-type balances [1e5].
4.2.1.1.2 Null-Point-Type Balance

A schematic representation of a null-point-type balance is shown in
Fig. 4.2B. It usually comprises a sensor through which deviations from
the null point are detected. The restoration of balance to its original or
null-point position is made through restoration force.
4.2.2 Sample Holder

The sample holder is also called a crucible. The sample to be subjected to
investigation or characterization is placed in the crucible, which is attached
to the weighing arm of the microbalance. Images of various types of cruci-
bles used in TGA based on shape are shown in Fig. 4.3. In general, the
crucibles used for TGA vary in shape, size, and material. The main materials
employed for making crucibles include aluminum, platinum, and quartz. In
addition to this, a few other materials are utilized occasionally, such as stain-
less steel, glass, and graphite. The utilization of crucibles made of different
materials in TGA depends on the temperature range required for performing
n FIGURE 4.3 Different types of crucibles used in thermogravimetric analysis based on shape [1e5].
experiments. It is necessary that the crucible should possess at least 100 C

higher thermal stability compared to experimental temperature conditions.
Also, the crucible selected for a certain experiment should efficiently and
uniformly transfer heat to the sample. Therefore, it becomes appropriate
that the thermal conductivity, shape, and thermal mass of the crucible are
the significant parameters that should be taken into consideration before
the usage of any crucible under predetermined experimental conditions.
All the aforementioned parameters are in turn dependent on the nature and
mass of the samples as well as the fixed experimental temperature regime.
In the case of powdered samples, generally flat crucibles are used whereas
liquid samples are analyzed using walled crucibles. The temperature
gradient present in the sample is determined by the type of crucible used
for analysis. Fig. 4.4 shows the TGA profile for the poly(methyl methacry-
late) (PMMA) polymer analyzed using different types of crucibles. In
Fig. 4.4, the TGA profile presented with a continuous line indicates the
PMMA sample analyzed by a normal aluminum crucible. The dashed line
in Fig. 4.4 represents the PMMA sample analyzed by a special type of
aluminum crucible fitted with an aluminum disk at the bottom position to
enhance the thermal mass. It can be carefully analyzed from the figure
that the two TG curves obtained for the same PMMA sample present differs
in terms of shape as well as residue rate. This variation is due to the different
types of crucible used for analysis despite the sample being the same. The
temperature at which the maximum rate of weight loss occurs (Tmax) is
enhanced by 5 C owing to the greater thermal mass exhibited by the
aluminum crucible with a disk fitted at its bottom. In general, crucibles
must be cleaned regularly using methanol, and preheating of the crucible
to its maximum temperature must be ensured before analysis to get a precise
decomposition profile.
n FIGURE 4.4 Thermal decomposition profiles for poly(methyl methacrylate) analyzed with different
types of crucibles.
4.2.2.1 Types of Crucibles

The different types of crucibles used in TGA are as follows [1e5]:
1. Shallow pan: Such type of crucible is used for analyzing samples in
which the diffusion of volatile substances plays the role as rate-limiting
factor. The gaseous substances released as decomposition products of
samples such as polymers should be able to escape so that the weight
loss of the sample can be evaluated. For such circumstances, a sample
in the form of a thin layer is made and placed in the shallow pan
crucible such that the volatile decomposition products escape easily and
the weight loss profile for the sample can be determined accurately.
2. Deep crucible: This type of crucible is utilized in certain studies, such
as industrial-scale calcinations, in which side reactions become
mandatory.
3. Loosely covered crucible: Such type of crucible is used in isothermal
studies in which the rate at which the temperature proceeds during
analysis or the weight loss of samples is neglected.
4. Retort cup: This type of crucible is used in determination of the
boiling point of samples. The utilization of such crucibles helps in
providing a single plait of reflux for a boiling-point evaluation.
4.2.3 Furnace
The furnace should be designed so that a linear heating rate can be
achieved. The furnace consists of a hot zone in which both crucible and
sample are placed. It should be considered here that the temperature of
crucible as well as the sample corresponds to the furnace temperature. It is

known that the internal atmosphere of a furnace can be affected by the tem-
perature regime maintained in the furnace. Hence, it becomes adequate to
select a furnace specifically suitable for the temperature regime to be
used. Various types of materials used for making heating coils according
to temperature range are presented in Table 4.1. It should be ensured that
there exists no magnetic interaction among the sample and the heating
coil present in the furnace. This is because the presence of magnetic interac-
tions can lead to changes in the weight of the sample.
In addition, the size of the furnace also plays an important role in accurate
measurement. A furnace with high mass may withstand an enhanced tem-
perature regime and ensure a uniform hot zone. However, an increased
timescale is required for achieving the targeted temperature. On the other
hand, low-weight furnaces can be able to provide quick heating with great
difficulty in controlling the rate of increase in temperature. Therefore, light-
weight furnaces do not allow for proper maintenance of the hot zone.
Another significant parameter that affects the quality of analysis is the
position of the furnace with respect to balance. Fig. 4.5 presents the position
of the furnace with respect to different types of microbalance. It can be seen
from Fig. 4.5A that the weighing balance is below the furnace in the case of a
quartz spring-type balance. In the case of a beam-type balance, shown in
Fig. 4.5B, it can be noticed that the weighing balance is above the furnace
position. Also, the presence of the weighing balance in different positions
with respect to the same furnace position can be interpreted from Fig. 4.5B.
Table 4.1 Materials Used for Heating Coils and Their

Corresponding Temperature Range [1e5]
S. No: Material Used Temperature ( C)
1 Nichrome wire <1300

2 Ribbon <1300
3 Platinum >1300
4 Platinum (90%)/rhodium <1800
(10%) alloy
5 Silicon carbide <1600
6 Silver <650
7 Steel <1000
8 Rhodium <1700
9 Graphite <2000
10 Tungsten <2400
n FIGURE 4.5 Position of the furnace with respect to (A) spring-type and (B) beam-type balances
[1e5].
4.2.4 Thermocouple
A thermocouple is used for measuring temperature. Similar to heating coils,
various types of material are used for the fabrication of thermocouples,
which include tungsten or platinum alloys. Aluminum alloys, namely
chromal and alumel, are used as thermocouples for measuring temperature
conditions below 1100 C. For temperature conditions above 1100 C, tung-
sten materials are used for making thermocouples. The position at which the
thermocouple is placed plays a governing role in precise measurement
during analysis. The various thermocouple positions that are possible in a
microbalance are presented in Fig. 4.6. The thermocouple positioned near
the crucible can be seen in Fig. 4.6A. In such a design, it can be noticed
that there is no contact between the thermocouple and the sample container.
This type of setup is not usually preferred under low pressure conditions.
Fig. 4.6B shows the thermocouple positioned below the sample container
and in contact with the sample holder in the bottom position. This type of
arrangement may correspond to only small changes in temperature condi-
tions. In Fig. 4.6C, it can be noticed that the thermocouple is placed inside
the sample container. In this type of design, the thermocouple is in contact
with both sample holder and sample. Therefore, the arrangement shown in
n FIGURE 4.6 Possible positions for the thermocouple in a thermobalance [1e5].

Fig. 4.6C is the widely preferred and generally employed design for accurate
measurement of temperature changes.
4.2.5 Temperature Programmer

The temperature programmer is basically used to control the heating rate
when the temperature tends to increase during the analysis. The heating
rate is customized to be recorded in degrees per minute in terms of the
Kelvin or Celsius scale. The rate of heating or cooling can be considered
constant when the temperature versus time curve appears to be linear.
4.2.6 Data Recording Unit

The data recording unit is basically a chart recorder or microcomputer that
is used for recording the output provided by balance and furnace. A micro-
computer enables one to both save and plot the temperature versus weight
loss curve using preinstalled software while performing mathematical prob-
lems, whereas this feature is not present in a chart recorder. Also, a micro-
computer helps in plotting the multiple weight loss curves in a simultaneous
manner as a function of temperature or time. In addition to chart recorder
and microcomputer, some other types of data recorder unit include xey
recorder and time-base potentiometric strip chart recorder.
4.3 CLASSIFICATION OF THERMOGRAVIMETRIC

ANALYSIS
TGA is classified into three types as follows.
4.3.1 Dynamic Thermogravimetric Analysis

In this method, the temperature of the sample will be increasing continu-
ously at a specific heating rate. Therefore, the temperature of the sample
varies linearly with time.
4.3.2 Static or Isothermal Thermogravimetric

Analysis
In this method, the sample is kept at a constant temperature condition for a
fixed interval of time. During this time period, the mass change that occurs
in the sample will be recorded.
4.3.3 Quasistatic Thermogravimetric Analysis

In this method, the sample is heated to a constant weight at each in a series
of increasing temperatures.
4.4 THERMOGRAVIMETRY CURVE

The TG curve usually represents a plot of weight change as a function of
temperature or time. An example of a typical TG curve is shown in
Fig. 4.7. The TG curve shown in Fig. 4.7 exhibits a single stage of decom-
position. In the curve, “Ti” represents the temperature at which the onset of
decomposition is initiated, whereas “Tf” represents the temperature at which
the decomposition reaction is terminated or completed. It should be
understood that the values of Ti and Tf depend on the thermal stability of
the sample being analyzed.
4.4.1 Interpretation of TG Curve

Interpretation of the TG curve can be done in several ways as follows.
4.4.1.1 Types of Thermogravimetry Curve

The TG curve is classified into seven types on the basis of shape as shown
in Fig. 4.8.
1. Type 1: This type of curve exhibits no weight change throughout the
entire temperature range used for analysis. The possible reason for this
phenomenon may be the fact that the thermal stability of the sample is
higher than the temperature range.
2. Type 2: This type of curve exhibits a mass loss region, which is then
followed by a constant line. TG curves of type 2 result from certain
processes such as drying in which volatile compounds are evaporated
and desorption occurs.
3. Type 3: TG curves that demonstrate a single stage of weight loss or
decomposition correspond to type 3.
n FIGURE 4.7 A typical thermogravimetry curve.

n FIGURE 4.8 Classification of thermogravimetry curve based on shape [1e5].
4. Type 4: This type of curve can be exhibited by samples that undergo a

multistage decomposition process.
5. Type 5: This type of curve can result when there is an increment in
sample weight due to surface oxidation reactions that take place in a
reacting atmosphere.
6. Type 6: This type of curve can be possible if there are multiple
reactions with respect to a rise in temperature. The increase in weight is
due to the surface oxidation reaction, whereas the decrement in weight
with further rise in temperature corresponds to the decomposition
process of the reaction products.
4.4.1.2 Plateau
The plateau is the region present in the TG curve that corresponds to a
constant line that follows after the weight loss portion. In this region, the
mass of the sample is constant or else no weight change can be found. In
Fig. 4.8, the plateau region can be visualized in type 2 and type 3 curves.
4.4.1.3 Initial Decomposition Temperature

The initial decomposition temperature (Tinitial) corresponds to the tempera-
ture point at which the cumulative weight change attains a magnitude that
can be detectable by a thermobalance.
4.4.1.4 Final Decomposition Temperature

The final decomposition temperature (Tfinal) corresponds to the temperature
point at which the cumulative weight change attains a maximum and cannot
change further.
4.4.1.5 Reaction Interval

The temperature difference that occurs among the initial and final decompo-
sition temperatures corresponds to the reaction interval. In the case of a sin-
gle stage of decomposition, there exists only a single reaction interval. For a
multistage decomposition profile, several reaction intervals may be present,
according to the decomposition stages revealed by the sample with respect
to heating.
4.4.1.6 Determination of Isobaric Mass Change

The isobaric mass change curve can be recorded at constant partial pressure
of the volatile products released during decomposition. The isobaric mass
change curve refers to the equilibrium mass measured as a function of tem-
perature when the sample undergoes heating in a controlled temperature
program.
4.4.1.7 Evolved Gas Analysis

It is well known that the evolution of gaseous compounds takes place when
the sample undergoes decomposition under a controlled temperature pro-
gram. When TGA is coupled to Fourier transform infrared (FTIR) spectros-
copy or gas chromatographyemass spectrometry instruments, it is possible
to analyze the functional composition of gaseous compounds released from
a sample subjected to a controlled temperature program.
4.4.1.8 Information From Thermograms

The term “thermogram” refers to a plot obtained by TGA that comprises
weight loss versus temperature data. The following information can be
derived from a typical thermogram as shown in Fig. 4.7.
1. Thermal stability: Thermal stability is determined for a substance
using TGA based on its ability to maintain its characteristics as almost
unaffected upon exposure to heat. The knowledge of thermal stability
is very important for engineers so that it is possible to predict the
temperature regime of alloys, polymers, and nanomaterials.
2. Composition of sample: Upon increasing the temperature of a sample,
it is certain that the sample undergoes weight loss. The information
about weight loss remains significant for chemists to determine the
composition of a sample so that it is possible to understand the reaction
steps involved in the decomposition process. Through the weight loss
profile, it is also possible to identify an unknown compound present in
the sample or evaluate the amount or percentage of a specific compound
present among a mixture of different compounds in the sample.
3. Procedural decomposition temperature: With the help of a thermo-

gram, the procedural decomposition temperature, which indicates
evaporation or decomposition processes of a substance, can be
evaluated.
4.5 ADVANCED THERMOGRAVIMETRIC ANALYSIS

INSTRUMENTS
4.5.1 Simultaneous Determination of
Thermogravimetry and Heat Flow Curves
At present, advanced instruments are available on the market for simulta-
neous determination of TG and heat flow curves. For example, PerkinElmer
Co. introduced product Nos. STA 6000 and STA 8000 with advanced
analytical technique to simultaneously determine TG and heat flow curves.
Both STA 6000 and STA 8000 instruments measure heat flow data using
differential scanning calorimetry (DSC) and weight loss data via TGA,
simultaneously. The DSC heat flow data are usually measured in milliwatts
or joules per gram. The STA 6000/STA 8000 simultaneous thermal
analyzer instruments are designed with leading-edge sensor technology to
yield great accuracy as well as quality results. Also, STA 6000/STA
8000 instruments encompass a patent pending “SaTurn A” sensor and high-
ly compact furnace ensuring better temperature control, consistent measure-
ments, as well as the fastest cool-down timing compared to other
simultaneous TGA-DSC analyzers.
Fig. 4.9 shows the TG curve for a pharmaceutical sample analyzed by STA
6000/STA 8000 instruments. In Fig. 4.9, blue and red lines show TG and
DSC heat flow curves, respectively. The pharmaceutical sample corresponds
to a free base and small-molecule crystalline powder. It can be seen from the
figure that the crystalline melt peak is at 229 C. It is seen that the baseline
returns to a slightly lower position after the melt transition. This is an indi-
cation of lower heat capacity exhibited by the liquid phase compared with
the crystalline phase. Also, it is evident from the heat flow curve that post-
melt baseline changes slope as soon as the sample starts to decompose. It can
be noticed from Fig. 4.9 that the decomposition peak exhibited by the DSC
curve at 287 C is exothermic in nature and this corroborates with the onset
decomposition temperature of 287 C extrapolated from the TG curve.
4.5.2 Evolved Gas Analysis

Several techniques are now available for analysis of gaseous products from
TGA and the approach is termed as “evolved gas analysis” (EGA). The
EGA approach involves a subset of hyphenated techniques in which two
4.5 Advanced Thermogravimetric Analysis Instruments 81
n FIGURE 4.9 Simultaneous differential scanning calorimetry and thermogravimetry curves for a
pharmaceutical sample analyzed by an STA 6000/STA 8000 thermal analyzer.
or more instruments are integrated. The TGA-EGA techniques followed

currently are discussed as follows:
4.5.2.1 Thermogravimetric AnalysiseCoupled Fourier

Transform Infrared Spectrometry
The most general system used for EGA involves the utilization of TGA
coupled with an FTIR spectrometer (TGA-FTIR). When a sample is sub-
jected to heating in TGA, volatile or combustion components are generated
by burning. Such volatile or combustion components released will then be
transferred to an infrared (IR) cell through which identification of released
components is done. This instrumental method of analysis is more useful if
the gases released correspond to simple components such as carbon dioxide
or general solvents that present featured IR spectra. An image of TGA-FTIR
is presented in Fig. 4.10.
4.5.2.2 Thermogravimetric AnalysiseMass Spectrometry

Another type of integrated instrument used for EGA is TGAemass spec-
trometry (MS), which is useful for detection of very low levels of impurities
in real time. Like TGA-FTIR, gases released during heating of the sample
are passed to the mass spectrometer where the compounds can be detected.
TGA-MS serves as a powerful tool for EGA because of its ability to identify
even minute levels of components present in the evolved gas. Hence, this
technique finds great potential for identification of components in quality
control, safety, as well as product development departments. An image of
TGA-MS is presented in Fig. 4.10.
n FIGURE 4.10 Different types of advanced thermogravimetric analysis (TGA) instruments used for
evolved gas analysis. FTIR, Fourier transform infrared; GC, gas chromatography; MS, mass spectrometry.
4.5.2.3 Thermogravimetric AnalysiseGas Chromatography

Mass Spectrometry
In recent years, there has been an increase in the utilization of TGA-coupled
gas chromatography/MS (TGA-GC/MS) for EGA. Similar to TGA-MS, the
gas evolved during the heating of a sample is transferred to a gas chromato-
graph where the components are collected. Thereafter, the collected gas
sample is run using GC to separate the different components and the peaks
are identified by MS. This technique gained popularity because of its ability
to detect even very minute levels of components present in complex
mixtures. Like TGA-MS, TGA-GC/MS also finds potential application in
quality control, safety, as well as product development sections. An image
of TGA-GC/MS is presented in Fig. 4.10.
4.6 CASE STUDIES FOR APPLICATIONS OF

THERMOGRAVIMETRIC ANALYSIS
4.6.1 Determination of Thermal Stability Under
Modified Atmosphere
It is well known that PMMA serves as a very significant thermoplastic
material in the polymer industry. The drawbacks associated with PMMA
include its poor thermal stability as well as its easy flammability. When
PMMA is burned, the methyl methacrylate (MMA) monomer unit, which
is released during burning, further generates bubbles, which in turn help in

the production of a flammable gas phase. Therefore, the rate at which the
mass loss occurs for PMMA is accelerated by the generation of flammable
MMA gas and so no residue is left after pyrolysis takes place, even in an
inert atmosphere. To overcome the aforementioned drawbacks, the fabrica-
tion of PMMA/inorganic hybrid composites has received great attention.
Incorporation of inorganic nanoparticles in the PMMA matrix helped in
improving the flame retardant characteristics for the composites by acting
as catalysts for enhancing the formation of char.
A study based on analyzing the flame retardant characteristics of iron
hydroxyl phosphate (FePOH) nanoparticles incorporated into a PMMA
matrix is reported. In case study 1, the thermal stability of the PMMA/
FePOH composite is analyzed to understand the thermal degradation
behavior of the composite under modified atmosphere conditions. The
TGA data obtained for PMMA and PMMA/FePOH composites under air
and nitrogen atmospheric conditions are presented in Table 4.2. It is inter-
preted that the T10% (temperature at which 10% weight loss occurs)
increased by w19 C for 6 wt% loading of FePOH in the PMMA matrix
under air atmosphere. In the case of the nitrogen atmosphere, the PMMA
composites exhibit a decrement in T10% values compared to neat PMMA.
Under the nitrogen atmosphere, chain end scission and random chain scis-
sion reactions are accelerated, which affects the thermal stability of
PMMA composites. In the air atmosphere, random chain scission reactions
take place in a controlled manner and hence the PMMA/FePOH composites
show improved thermal stability [6].
In case study 2, the effect of amino-group-containing constituents on the
thermal stability of chitosan (CS) and CS/magnetite (Fe3O4) nanocomposites
Table 4.2 Thermogravimetric Analysis Data for Poly(methyl methacrylate) (PMMA) and PMMA/FePOH
Composites Under Different Atmospheric Conditions [6]
TGA Data
Air Atmosphere Nitrogen Atmosphere
Residue % Residue %
Sample T10% ( C) T50% ( C) at 600 C T10% ( C) T50% ( C) at 600 C
PMMA 231 308 0.9 260 355 0.2

PMMA/2 wt% FePOH 232 323 4.5 221 362 3.2
PMMA/6 wt% FePOH 250 342 12.2 249 363 8.1
FePOH, iron hydroxyl phosphate; PMMA, poly(methyl methacrylate); TGA, thermogravimetric analysis.
is investigated [7]. The amino groups are introduced into the polysaccharide
chain of CS, and the derivatives of CS (CS-1, CS-2, and CS-3) thus prepared
are used as a matrix for the incorporation of Fe3O4 nanoparticles to fabricate
modified CS/Fe3O4 nanocomposites (Fe3O4/CS-1, Fe3O4/CS-2, and Fe3O4/
CS-3). Thereafter, TGA is performed to evaluate the thermal stability of
neat CS, modified CS, and Fe3O4/modified CS nanocomposites. The synthe-
sis route and structure for CS and modified CS can be seen in Fig. 4.11.
The TGA curves obtained for neat CS, modified CS, and Fe3O4/modified
CS nanocomposites under a nitrogen atmosphere can be seen in Fig. 4.12.
In the case of CS, the initial weight loss corresponds to the removal of
adsorbed water by hydrophilic groups present in CS. The main stage of
degradation that occurs between 200 C and 500 C is due to chain scission
and ring opening reactions. The carbon residue noticed during thermal
n FIGURE 4.11 Synthesis route and structure for chitosan and modified chitosan [7].
n FIGURE 4.12 Thermogravimetry and differential thermogravimetry curves under nitrogen atmosphere
for (A) neat chitosan (CS) and modified CS and (B) Fe3O4/modified CS nanocomposites [7].
degradation of neat CS under an air atmosphere at 800 C corresponds to

w34%. Similar to CS, the derivatives CS-1 and CS-3 also demonstrate three
stages of weight loss. However, CS-2 shows a complex degradation profile
with a minimum of four steps during degradation. In the case of nanocom-
posites, four stages of degradation are noticed because of the presence of
inorganic filler.
The TGA curves obtained for neat CS, modified CS, and Fe3O4/modified
CS nanocomposites under air atmosphere can be seen in Fig. 4.13. For
neat CS, three stages of degradation are noticed under an air atmosphere.
The first stage corresponds to moisture loss and the second stage presents
weight loss due to decomposition as well as oxidation reactions.
n FIGURE 4.13 Thermogravimetry and differential thermogravimetry curves under air atmosphere for
(A) neat chitosan (CS) and modified CS and (B) Fe3O4/modified CS nanocomposites [7].
Interestingly, complete weight loss due to degradation of intermediates

formed at earlier stages is noticed at the last stage. The carbon residue left
after 800 C corresponds to only 2%, which is associated with the burning
of polysaccharide constituents in the presence of air. The CS-1 and CS-3
samples show similar degradation profiles, but not CS-2, under air atmo-
sphere also.
For precise interpretation of differences in thermal degradation behavior of
all the samples, comparative analysis of thermal parameters derived from
TGA is carried out. The TGA data obtained for CS, modified CS, and
Fe3O4/modified CS nanocomposites under nitrogen and air atmospheric
conditions are presented in Table 4.3. The higher mass loss exhibited by
Table 4.3 Thermogravimetric Analysis Data for Chitosan (CS), Modified CS, and Fe3O4/Modified CS
Nanocomposites Under Nitrogen and Air Atmospheric Conditions [7]
Nitrogen Atmosphere Air Atmosphere
First Second Third First Second Third

Stage Stage Stage Residue Stage Stage Stage Residue
After After
Sample Dm (%) Dm (%) Dm (%) 800 C Dm (%) Dm (%) Dm (%) 800 C
CS 10 44 12 34 9 48 41 2
CS-1 11 43 12 34 10 44 44 2
CS-2 44 5 12 39 19 14 15 52
CS-3 12 40 12 36 12 40 45 3
Fe3O4/CS-1 10 17 18 55 10 17 7 66
Fe3O4/CS-2 35 15 10 40 17 10 10 63
Fe3O4/CS-3 7 28 16 49 9 21 3 67
CS, chitosan; Dm, change in mass.
CS-2 and Fe3O4/CS-2 in the first stage may be due to their ability to bind
higher water content compared to other samples under both atmospheric
conditions. The higher residue content exhibited by Fe3O4/CS-1 and
Fe3O4/CS-3 samples under both atmospheres compared to Fe3O4/CS-2 is
due to the formation of nonvolatile intermediates.
4.6.2 Prediction of Thermal Decomposition

Mechanism
Case study 3 demonstrates the application of a thermal degradation profile
obtained for polymer composites in predicting the thermal decomposition
mechanism. In case study 3, a hypothetical thermal degradation mechanism
for poly(lactic acid)esucrose palmitate (PLA-SP) biocomposites is pro-
posed based on the TG curve obtained for SP [8]. The TG and differential
thermogravimetry curves obtained for SP, PLA, and PLA-SP biocomposites
are presented in Fig. 4.14. In this study, it is noticed that the Tmax values
remain unaffected for PLA-SP biocomposites up to 5 wt% loading. With
further increase in SP loading, the Tmax value is drastically reduced.
The reason for the decrement exhibited in Tmax values for PLA-SP
biocomposites at 10 wt% loading is derived by understanding the thermal
degradation behavior of SP. The initial stage of decomposition in PLA-
SP biocomposites is due to the thermal degradation of the sucrose func-
tional group present in SP. It is reported that the Hþ ions released during
the thermal degradation of SP diffuse into the amorphous phase of PLA
n FIGURE 4.14 (A) Thermogravimetry and (B) differential thermogravimetry curves for sucrose palmitate (SP), poly(lactic acid) (PLA), and PLA-SP bio-
composites [8].
and hydrolyze the ester bonds present in PLA. The hydrolysis of ester
groups leads to the generation of oligomers with carboxylic acid terminals.
This phenomenon further triggers autocatalysis and results in the faster
degradation of PLA composites. A hypothetical mechanism for thermal
degradation for PLA-SP biocomposites is proposed and the same is
depicted in Fig. 4.15. The relatively higher concentration of Hþ released
for higher loadings of SP triggers the hydrolysis of the ester backbone of
PLA. The increased acid terminal groups generated by the fastened random
chain scission process leads to earlier as well as faster decomposition of
PLA composites at higher loadings of SP in comparison with lower SP
concentration in the PLA matrix.
In case studies 4 and 5, advanced instrumental methods that combine TGA
with FTIR, MS, and GC/MS are used to predict the reaction intermediates
released during thermal degradation of nanomaterials and pyrolysis of
biomass. In case study 4, EGA is carried out for b-cyclodextrin using an
integrated TG-MS/FTIR device [9]. The National Institute of Standards
and Technology mass spectral database was utilized to interpret the mass
spectra obtained during EGA. It is interpreted from the TG-MS/FTIR
analysis that a complex volatile mixture is generated during the thermal
degradation of b-cyclodextrin. Fig. 4.16 shows the MS and FTIR spectra
obtained during thermal degradation of b-cyclodextrin at 308 C.
The evolved compounds identified in the MS spectra include methanol
(m/z values: 32 and 29), ethanol (m/z values: 46, 45, and 31), acetic
n FIGURE 4.15 Hypothetical mechanism for the thermal decomposition of poly(lactic acid)esucrose
palmitate (PLA-SP) biocomposites [8].
acid (m/z values: 60, 45, and 43), furfural (m/z values: 96, 95, and 39), and 2-
methylfuran (m/z values: 82 and 81). The FTIR spectra also corroborated the
identification made using MS spectra. The broad absorption band obtained in
the range of 3500e3000 cm1 reveals the presence of alcoholic compounds
evolved during thermal degradation of b-cyclodextrin. The sharp peak iden-
tified at 3239 cm1 corresponds to the stretching vibrations of amine-based
compounds. The absorption band obtained at 2816 cm1 reveals the stretch-
ing vibrations of alkyl groups. The signals found in the range of
2000e1628 cm1 confirm the presence of carboxyl and alkene moieties.
The peak identified at 863 cm1 is due to the CeH stretching vibration of
the furan compound.
Case study 5 deals with the analysis of fast copyrolysis compounds

produced using pyroprobe-coupled GC/MS/FTIR during the degradation
of cellulose and polypropylene (PP) [10]. The vapors generated during
pyrolysis are analyzed using GC/MS, whereas the functional key com-
pounds evolved over time are identified via FTIR. Different temperature
conditions affect the composition of major products formed during fast
copyrolysis of cellulose and PP. The products formed are again found to
be dependent on feed composition. The influence of pyrolysis temperature
n FIGURE 4.16 (A) Mass spectrometry and (B) Fourier transform infrared spectra obtained during thermal degradation of b-cyclodextrin and its derivatives at
308 C [9].
for the cellulose/PP mixtures with different feed compositions on product

distribution is shown in Fig. 4.17. It is reported that long-chain alcohols
are formed by the interactions among cellulose and PP. With the rise in
pyrolysis temperature, the char yield is decreased and generation of aromatic
compounds is increased. For a mixture with higher PP content, pyrolysis at
600 C results in the formation of w36% alcohols and w45% hydrocarbons.
Based on the information obtained from the product distribution profile, it is
predicted that the dominant reactions responsible for transformations are
hydroxyl, hydrogen, and methyl abstraction.
The higher percentage of alcohols as well as hydrocarbon production
noticed when the feed is subjected to a temperature condition of 600 C
confirms the vapor phase interactions. Such interactions are favored by
n FIGURE 4.17 Influence of temperature for cellulose (C)/polypropylene (PP) mixtures with different feed compositions on product distribution [10]. PAHs,
polycyclic aromatic hydrocarbons.
hydroxyl radical generation and b-chain scission reaction products from the
degradation of cellulose and PP, respectively. Fig. 4.18 depicts the possible
intermediate compounds responsible for the formation of major alcohols
during fast copyrolysis of cellulose/PP mixtures at 600 C. It is predicted
that linear alcohols like octanol, dodecanol, and decanol are formed by
methyl abstraction from PP and successive hydrogen transfer reactions.
On the other hand, alcohols with long chain branches are formed through
free hydrocarbon radical recombination.
n FIGURE 4.18 Possible intermediate compounds responsible for formation of major alcohols during fast copyrolysis of cellulose/polypropylene mixture at 600 C [10].
4.6.3 Determination of Nanoparticle Purity and

Amount of Surface Coatings
Case studies 6 and 7 deal with the determination of nanoparticle purity and
measurement of the amount of surface coatings [11]. As of this writing, pro-
teins or lipid layers are coated onto nanoparticles before they are introduced
into complex environments like biological fluids. Several analytical tech-
niques face drawbacks in the determination of nanoparticle purity as well
as the presence of surface coatings. Case study 6 discusses the application
of a microscale TGA, or m-TGA, for evaluation of the purity and composi-
tion of carbon nanotubes (CNTs) by identifying the oxidation temperature
and residual mass remaining after carbon decomposition is completed.
Fig. 4.19 shows the mass (%) versus temperature curve obtained for
CNTs using m-TGA and conventional TGA. In case of m-TGA, a spray
coating process is used for a uniform and thin film coating of CNTs onto
a quartz crystal balance (QCM). Then, the sample is heated to 300 C
initially and thereafter the temperature is raised by only 25 C at regular
intervals until it reaches 525 C. This is done to capture the full oxidation
of the CNTs.
It can be seen from Fig. 4.19A that the m-TGA curve closely follows the
conventional TGA curve. However, there is a fluctuation in the initial stages,
which is due to the presence of water in the CNTs and a limit to the detection
of humidity by the QCM. Decomposition of CNTs is initiated at 425 C,
which is evident from both m-TGA and conventional TG curves. It can be
seen from Fig. 4.19A that m-TGA and conventional TG curves show a resid-
ual mass of w17% and w7%, respectively. The residual mass (%) corre-
sponds to the catalysts left over from the synthesis procedure or oxidation
products released from catalysts remaining after complete decomposition
of carbon. In Fig. 4.19B, it can be seen that w32% residual mass remains
for CNTs with high metal content analyzed by m-TGA. Through this anal-
ysis, it is possible to determine the purity of different types of CNTs accu-
rately by evaluating the residual mass remaining after the oxidation
process. The results clearly indicate that CNTs with high metal content
correspond to an impure sample as they exhibit high residual mass left
over after complete decomposition of the carbon content.
Case study 7 discusses the application of m-TGA to confirm the presence of
ligand coating on gold nanoparticles as well as determining the quantity of
surface-bound coverage of ligand moieties. Fig. 4.20 shows mass (%) versus
temperature curves for layer-by-layer coatings of poly-L-lysine and DNA on
30-nm gold (Au) nanoparticles, which were specially designed for gene
delivery purposes.
n FIGURE 4.19 Mass (%) versus temperature curve obtained for (A) carbon nanotubes (CNTs) with
high purity and (B) CNTs with high metal content using microscale thermogravimetric analysis (TGA)
(red line (Light Gray in print versions)) and conventional TGA (blue line (Gray in print versions)) [11].
Through dynamic light scattering experiments, it is confirmed that the

particle size of coated Au nanoparticles increases with respect to the addi-
tion of layers. The mass (%) left over after decomposition of all layers at
400 C, size, and DNA content for layer-by-layer-coated Au nanoparticles
are presented in Table 4.4. Based on the mass (%) loss information obtained
using m-TGA curves for different layers coated, the content of DNA depos-
ited onto the surface of the Au nanoparticles is determined accurately.
n FIGURE 4.20 Mass (%) versus temperature curves for layer-by-layer coatings of poly-L-lysine and
DNA on 30-nm Au nanoparticles [11].
4.6.4 Evaluation of Loading of Drug or Functional

Moieties
Case study 8 deals with the application of TGA in the determination of
anticancer drug curcumin loading in amine-functionalized mesoporous
silica particles [12]. In case study 8, three different types of mesoporous
silica particles are selected, namely, KIT-6, MSU-2, and MCM-41.
The selected mesoporous silica particles are functionalized with a
3-aminopropyltriethoxysilane coupling agent and the samples are designated
as KIT-6-AP or S1, MSU-2-AP or S3, and MCM-41-AP or S5. Further,
curcumin loading is carried out on amine-functionalized mesoporous silica
supports S1, S3, and S5, after which the samples are designated as KIT-6-
AP-CUR or S2, MSU-2-AP-CUR or S4, and MCM-41-AP-CUR or S6.
Table 4.4 Mass (%) Left Over After Decomposition of All Layers at 400 C, Size, and DNA Content for
Layer-by-Layer-Coated Gold Nanoparticles [11]
Mass Left Over After Size Measured by DNA Content
Sample 400 C DLS (nm) Estimated (ng/mL)
Au þ PLL 86 34 e
Au þ PLL þ DNA 70 53 72
Au þ PLL þ DNA þ PLL þ DNA 43 61 104
DLS, dynamic light scattering; PLL, poly-L-lysine.

The weight loss that occurs in the temperature range of 100e600 C is

considered for all the samples to determine the organic loading as well as
the curcumin loading. The weight (%) of organic groups that are attached
to the porous surface of the mesoporous silica particles, as well as curcumin
loading (%), is calculated from the TGA profile obtained for the respective
samples and presented in Table 4.5. It can be seen from Table 4.5 that the
weight loss (%) that occurs between 100 C and 600 C differs for samples
S1 (without curcumin) and S2 (with curcumin). For sample S1, the entire
weight loss (%) noticed in the aforementioned temperature regime corre-
sponds to organic loading (%). In the case of sample S2, the entire weight
loss of w11.76% that occurs between 100 C and 600 C does not corre-
spond to organic loading (%) alone. Rather, 11.76% of weight loss is due
to the combined decomposition of organic groups as well as curcumin.
Because the weight loss that occurs because of organic loading is already
known for sample S1 (9.08%), curcumin loading can be calculated by
subtracting 9.058% from the entire weight loss (11.76%). Therefore, the
total amount of curcumin loaded in the KIT-6-AP support is estimated to
be 2.68%.
Case study 9 deals with the application of TGA in the evaluation of
organic and amine loadings on pore-expanded MCM-41 silica (PE-
MCM-41) [13]. In case study 9, two different amino silane coupling
agents, namely, 3-aminopropyltriethoxysilane or monoamine (AP) and
N-(3-trimethoxysilylpropyl)diethylenetriamine or triamine (TP), are used
for tethering on PE-MCM-41. In case study 9, organic and amine loadings
are calculated considering both bidentate (mono- and triamino ligands teth-
ered with two surface silanol groups of PE-MCM-41 with one dangling
alkoxyl group) and tridentate (mono- and triamino ligands tethered with
three surface silanol groups of PE-MCM-41) grafting phenomena. The
Table 4.5 Organic and Curcumin Content (%) Evaluated Using

Thermogravimetric Analysis Measurements [12]
% Weight Loss % Weight Loss %
Sample (20e100 C) (100e600 C) Curcumin
S1 (KIT-6-AP) 3.62 9.08 e

S2 (KIT-6-AP-CUR) 3.28 11.76 2.68
S3 (MSU-2-AP) 2.93 8.46 e
S4 (MSU-2-AP-CUR) 2.32 14.34 3.56
S5 (MCM-41-AP) 5.31 11.00 e
S6 (MCM-41-AP-CUR) 3.75 14.58 3.58
organic and amine loadings estimated for AP- and TP-grafted PE-MCM-41
based on the weight loss information obtained from TGA are presented in
Table 4.6. The weight loss that occurs between 200 C and 550 C is consid-
ered for the calculation of organic and amine loadings. This is because
decomposition of organic groups functionalized in PE-MCM-41 takes
place in the aforementioned temperature regime. It can be seen from Ta-
ble 4.6 that organic loading as well as amine loading remains the same
in the case of AP-functionalized PE-MCM-41. However, this is not appli-
cable for TP-functionalized PE-MCM-41 because of the presence of three
nitrogen groups per organic chain.
4.6.5 Gas Adsorption Studies

Case study 10 deals with the application of a modified TGA instrument
used for gas adsorption measurements on zeolite 13X and TP-tethered mes-
oporous PE-MCM-41 (TP-PE-MCM-41) silica material [14]. Fig. 4.21
shows the modified TGA instrument utilized for carbon dioxide adsorption
measurements.
In case study 10, the TGA instrument is coupled with a mass spectrometer
for determination of carbon dioxide (CO2) capacity and analysis of the
decomposition products released during degradation studies carried out on
zeolite 13X and TP-PE-MCM-41. For both CO2 measurements and decom-
position studies, a specific amount of sample is loaded into a platinum
crucible. Initially, activation of the sample is carried out under N2 atmo-
sphere and at a predetermined activation temperature. Activation is carried
out to remove preadsorbed gases on the sample prior to CO2 adsorption mea-
surements. The activation temperature is predetermined based on the thermal
stability acquired by the sample. Activation is performed until a constant
mass for the sample is reached. Once activation is completed, the balance
is allowed to cool until it reaches the desired temperature required for
Table 4.6 Estimated Organic and Amine Content Present in Pore-Expanded MCM-41 Using
Thermogravimetric Analysis [13]
Organic Loading Amine Loading
2
mmol/g molecules/nm mmol (N)/g Molecules (N)/nm2
Sample BD TD BD TD BD TD BD TD
AP-PE-MCM-41 1.78 3.16 1.02 1.82 1.78 3.16 1.02 1.82

TP-PE-MCM-41 1.75 2.13 1.01 1.22 5.25 6.39 3.03 3.66
AP, monoamine; PE, pore-expanded; TP, triamine.

n FIGURE 4.21 Modified thermogravimetric analysis instrument for CO2 adsorption measurements [14].
MFC, mass flow controller; MS, mass spectrometer.
CO2 adsorption measurements. The feed used for analysis contains 5% CO2
and 95% N2. The feed flow rate is controlled with the help of a mass flow
controller. The effect of moisture on the adsorption capacity is also studied
by passing gas with a relative humidity of 27% to the TGA balance. Fig. 4.22
shows the CO2 adsorption capacities measured for zeolite 13X and TP-PE-
MCM-41 using the modified TGA. It can be seen from Fig. 4.22 that the
adsorption capacity increases initially and almost tends to attain saturation
with respect to time at a specified temperature.
4.6.6 Determination of Relative Strength for

Catalysts
Case study 11 deals with the application of TGA for characterizing
temperature-programmed desorption (TPD) profiles of zeolites [15]. In
general, the distribution of acid sites in zeolites determines their catalytic
property. Initially, zeolite is preheated at 500 C to remove the preadsorbed
gases under an inert atmosphere until a constant mass is reached. Thereafter,
the balance is allowed to cool until it reaches the analysis temperature of
100 C. After equilibrium is attained, the furnace purge is changed to the
analysis gas containing the base. The adsorption of the base on the zeolite
results in a weight gain for the sample. Once a constant mass is reached,
the furnace purge is again switched to inert gas flow. Now, loss of mass
of the sample can be achieved by desorption of the physisorbed base on
the zeolite. After a constant mass is reached, once again the balance
n FIGURE 4.22 CO2 adsorption capacities with respect to time for zeolite 13X and triamine-tethered
pore-expanded MCM-41 (TP-PE-MCM-41) measured using modified thermogravimetric analysis [14].
temperature is increased to 600 C. Fig. 4.23 shows several steps involved in

the TGA-TPD experiment performed for zeolite HZSM-5.
It can be seen from Fig. 4.23 that two weight loss regions are present in the
TGA-TPD profile obtained for zeolite HZSM-5. The weight loss due to
physidesorption corresponds to desorption of the physically bound base
ammonia on weak acidic sites of zeolite HZSM-5. The weight loss due to
chemidesorption corresponds to desorption of the chemically bound base
ammonia on strong acidic sites of zeolite HZSM-5. Through this weight
loss information, the numbers of strong and weak acidic sites for zeolite
HZSM-5 are calculated to be 0.34 and 0.32 mmol/g, respectively.
4.6.7 Kinetic Analysis

Case study 12 deals with the application of TGA in predicting thermal
degradation kinetics for polymer nanocomposites [16,17]. To perform ther-
mal degradation kinetic analysis, PMMA and PMMA/nanoclay composites
are subjected to TGA at three different heating rates, such as 5, 10, and 15 C/
min [16]. The TG data obtained at the three different heating rates are
analyzed by thermal degradation kinetic models such as those of Kissinger
and Friedman. Using these models, a kinetic parameter called “activation
energy (Ea)” is determined for the PMMA/nanoclay composites. This is
n FIGURE 4.23 Steps involved in thermogravimetric analysisetemperature-programmed desorption

experiment performed for zeolite HZSM-5 [15].
because the determination of activation energy for degradation helps us bet-

ter understand the thermal stability of polymer nanocomposites. For PMMA/
nanoclay composites, it is found that the decomposition temperature
increases with respect to the rise in heating rate. This phenomenon is due
to the timeetemperature superposition principle, which states that the time
necessary for a sample to reach the desired temperature will decrease with
a rise in heating rate.
Fig. 4.24 shows Kissinger and Friedman plots obtained for PMMA/nanoclay
composites. The activation energy via the Kissinger method for PMMA/
nanoclay composites is obtained by using the inflection point temperatures
(Tmax) present in the TG curve. The activation energy values calculated using
the Kissinger and Friedman methods are presented in Table 4.7. It is found
that the activation energy calculated by both methods for composites
increases with respect to an increase in clay loading in the PMMA matrix.
It can be seen from Fig. 4.24B that the activation energy values for compos-
ites are higher compared to those of neat PMMA. This reveals that a heat
barrier effect is provided by the incorporation of nanoclay such that the
degradation of PMMA composites slows down.
In case study 13, TGA data obtained at a single heating rate is analyzed by
the CoatseRedfern method to determine the kinetic parameters associated
with thermal degradation of polystyrene/organoclay nanocomposites
(PSNCs) [17]. Fig. 4.25 shows CoatseRedfern plots obtained for PS and
PSNCs at a heating rate of 10 C/min.
n FIGURE 4.24 (A) Kissinger plot and (B) activation energy versus conversion plot obtained by the
Friedman method for poly(methyl methacrylate) (PMMA) and PMMA/nanoclay composites [16].
The kinetic parameters such as activation energy, reaction order, and preex-
ponential factor evaluated using the CoatseRedfern method are presented
in Table 4.8. It can be seen from Table 4.8 that activation energy increases
for PSNCs up to 7 wt% loading compared with neat PS. With further
increase in loading, activation energy tends to decrease for PSNCs. This is
because the large organic surfactant content in the composites generated
charred layers with less stability during degradation.
Table 4.7 Activation Energy (Ea) Values for Poly(methyl

methacrylate) (PMMA) and PMMA/Nanoclay Composites Obtained
by Kissinger and Friedman Kinetic Models [16]
Ea (kJ/mol)
Sample Kissinger Method Friedman Method
Neat PMMA 88 121

PMMA-3 126 167
PMMA-5 161 196
PMMA-7 212 200
Ea, activation energy; PMMA, poly(methyl methacrylate).
n FIGURE 4.25 CoatseRedfern plots for (A) polystyrene, (B) polystyrene/organoclay nanocomposite (PSNC)-3, (C) PSNC-7, and (D) PSNC-20 [17].
Table 4.8 Kinetic Parameters Evaluated Using the CoatseRedfern Method at Optimum Correlation
Coefficient for Polystyrene and Polystyrene/Organoclay Nanocomposites at 10 C/min [17]
Activation Energy Preexponential Correlation
Sample Reaction Order (n) (Ea kJ/mol) Factor (A) Coefficient (R)
Neat PS 0.2 96 4.72 106 0.9996

PSNC-3 0.6 185 2.25 1013 0.9937
PSNC-7 1 186 2.59 1013 0.9943
PSNC-20 0.4 155 9.49 1010 0.9950
PS, polystyrene; PSNC, polystyrene/organoclay nanocomposite.
Case study 14 deals with the application of a modified high-pressure TGA

to study the kinetics of CO2 adsorption on PE-MCM-41 silica under
different pressures as well as temperature conditions [18]. The experimental
data obtained for CO2 adsorption on PE-MCM-41 with respect to time under
four different temperatures (30, 45, 60, and 75 C) and a wide range of pres-
sure conditions (0.2e11 bars) are analyzed by kinetic models. The analysis
of experimental data using pseudo-first-order and pseudo-second-order
models shows that adsorption of CO2 on PE-MCM-41 occurs via physisorp-
tion. The mechanism of CO2 diffusion in PE-MCM-41 is predicted using
interparticle diffusion, intraparticle diffusion, and Boyd’s model. Based on
the information provided by these three models, the rate-controlling step
associated with CO2 diffusion is predicted. The intraparticle diffusion plots
obtained for CO2 adsorption kinetics of PE-MCM-41 are shown in Fig. 4.26.
In this study, it is elucidated that film diffusion becomes rate governing
under a low-pressure and low-temperature regime. On the other hand,
pore diffusion becomes dominating in the case of high-pressure and high-
temperature conditions.
Case study 15 discusses the application of a high-pressure thermogravimet-
ric balance to generate CO2 adsorption isotherm and kinetic data on AP- and
TP-tethered PE-MCM-41 silica [19]. The CO2 adsorption isotherm data are
obtained under four different temperature conditions (30, 45, 60, and 75 C)
and a pressure regime ranging from 0 to 5 bars. On the other hand, kinetic
data are obtained under the pressure condition of 1 bar and the four different
temperature conditions mentioned earlier.
The CO2 adsorption isotherm data are analyzed by two different isotherm
models, the Langmuir and the Langmuir dual-site models, to understand
whether adsorption takes place via physisorption or chemisorption.
Fig. 4.27 shows the CO2 adsorption isotherm data analyzed by the Langmuir
and Langmuir dual-site models. Based on the model fitting, it is predicted
n FIGURE 4.26 Prediction of CO2 adsorption kinetics on pore-expanded MCM-41 using the intraparticle diffusion model. (A) 30 C, (B) 45 C, (C) 60 C, and (D)
75 C [18].
that chemisorption tends to control the initial phases of adsorption and the
later phases of adsorption are governed by physisorption. The kinetic uptake
measurement data analyzed by pseudo-first-order, pseudo-second-order, and
double-exponential models are shown in Fig. 4.28. It is found that the
double-exponential model closely follows the experimental kinetic uptake
data, indicating that both chemisorption and physisorption govern the CO2
uptake kinetics on both AP- and TP-tethered PE-MCM-41.
4.7 Conclusions 105
n FIGURE 4.27 Isotherm model plots for CO2 adsorption on triamine-tethered pore-expanded MCM-41. (A) 30 C, (B) 45 C, (C) 60 C, and (D) 75 C [19].
4.7 CONCLUSIONS
TGA serves as a valuable tool for understanding thermal events associated
with nanomaterials and polymer composites when subjected to heating un-
der predetermined heating rate and temperature conditions. Different types
of microbalances, such as null-point and deflection, are described and dis-
cussed adequately. Several case studies that deal with different applications
of TGA are also addressed. Case studies 1 and 2 explain different
n FIGURE 4.28 Kinetic model plots for CO2 adsorption on triamine-tethered pore-expanded MCM-41.
(A) 30 C and (B) 75 C [19].
degradation patterns for CS composites under modified atmosphere. Case

studies 3e5 describe applications of advanced TGA instruments such as
TGA-FTIR, TGA-MS, and TGA-GC/MS for the prediction of reaction in-
termediates evolved through EGA as well as hypothetical mechanisms for
thermal degradation of polymer nanocomposites and biomass.
Case studies 6 and 7 discuss m-TGA used for the determination of CNT
purity and DNA content in layer-by-layer coating on Au nanoparticles,
respectively. Case studies 8 and 9 explain the method to evaluate the
References 107
amount of drug as well as functional moiety loading in porous silica mate-

rial. A modified TGA instrumental setup used for CO2 adsorption study is
described in case study 10. The experimental method for determination of
acidic strength in zeolites using a TGA-TPD instrument is explained in
case study 11. Case studies 12 and 13 explain the application of several ther-
mal degradation kinetic models to TGA data to derive activation energy
values for polymer nanocomposites. Case studies 14 and 15 describe the
application of a high-pressure TG balance to elucidate the mechanism of
CO2 adsorption and diffusion kinetics on bare PE-MCM-41 and TP-PE-
MCM-41.
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Thermogravimetric Analysis For Characterization of Nanomaterials

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Thermogravimetric Analysis for

Thermal and Rheological Measurement Techniques for Nanomaterials Characterization. http://dx.doi.org/10.1016/B978-0-323-46139-9.00004-9

4.4.1.8 Information From Thermograms 79

becomes essential to optimize the factors or conditions that inﬂuence the

4.2 INSTRUMENTAL SETUP FOR

4.2.1 Electronic Microbalance

n FIGURE 4.1 Schematic representation of a thermobalance.

4.2.1.1 Types of Microbalance

4.2.1.1.1 Deﬂection-Type Balance

4.2.1.1.2 Null-Point-Type Balance

4.2.2 Sample Holder

experiments. It is necessary that the crucible should possess at least 100 C

4.2.2.1 Types of Crucibles

crucible as well as the sample corresponds to the furnace temperature. It is

Table 4.1 Materials Used for Heating Coils and Their

1 Nichrome wire <1300

n FIGURE 4.6 Possible positions for the thermocouple in a thermobalance [1e5].

4.2.5 Temperature Programmer

4.2.6 Data Recording Unit

4.3 CLASSIFICATION OF THERMOGRAVIMETRIC

4.3.1 Dynamic Thermogravimetric Analysis

4.3.2 Static or Isothermal Thermogravimetric

4.3.3 Quasistatic Thermogravimetric Analysis

4.4 THERMOGRAVIMETRY CURVE

4.4.1 Interpretation of TG Curve

4.4.1.1 Types of Thermogravimetry Curve

n FIGURE 4.7 A typical thermogravimetry curve.

n FIGURE 4.8 Classiﬁcation of thermogravimetry curve based on shape [1e5].

4. Type 4: This type of curve can be exhibited by samples that undergo a

4.4.1.3 Initial Decomposition Temperature

4.4.1.4 Final Decomposition Temperature

4.4.1.5 Reaction Interval

4.4.1.6 Determination of Isobaric Mass Change

4.4.1.7 Evolved Gas Analysis

4.4.1.8 Information From Thermograms

3. Procedural decomposition temperature: With the help of a thermo-

4.5 ADVANCED THERMOGRAVIMETRIC ANALYSIS

4.5.2 Evolved Gas Analysis

or more instruments are integrated. The TGA-EGA techniques followed

4.5.2.1 Thermogravimetric AnalysiseCoupled Fourier

4.5.2.2 Thermogravimetric AnalysiseMass Spectrometry

4.5.2.3 Thermogravimetric AnalysiseGas Chromatography

4.6 CASE STUDIES FOR APPLICATIONS OF

is released during burning, further generates bubbles, which in turn help in

PMMA 231 308 0.9 260 355 0.2

degradation of neat CS under an air atmosphere at 800 C corresponds to

Interestingly, complete weight loss due to degradation of intermediates

First Second Third First Second Third

CS, chitosan; Dm, change in mass.

4.6.2 Prediction of Thermal Decomposition

Case study 5 deals with the analysis of fast copyrolysis compounds

for the cellulose/PP mixtures with different feed compositions on product

4.6.3 Determination of Nanoparticle Purity and

Through dynamic light scattering experiments, it is conﬁrmed that the

4.6.4 Evaluation of Loading of Drug or Functional

DLS, dynamic light scattering; PLL, poly-L-lysine.

The weight loss that occurs in the temperature range of 100e600 C is

Table 4.5 Organic and Curcumin Content (%) Evaluated Using

S1 (KIT-6-AP) 3.62 9.08 e

4.6.5 Gas Adsorption Studies

AP-PE-MCM-41 1.78 3.16 1.02 1.82 1.78 3.16 1.02 1.82

AP, monoamine; PE, pore-expanded; TP, triamine.

4.6.6 Determination of Relative Strength for