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Thermogravimetric Analysis For Characterization of Nanomaterials
Thermogravimetric Analysis For Characterization of Nanomaterials
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
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
4.2 Instrumental Setup for Thermogravimetric Analysis 69
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.
n FIGURE 4.2 Different types of microbalance. (A) Deflection- and (B) null-point-type balances [1e5].
n FIGURE 4.3 Different types of crucibles used in thermogravimetric analysis based on shape [1e5].
n FIGURE 4.4 Thermal decomposition profiles for poly(methyl methacrylate) analyzed with different
types of crucibles.
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
74 CHAPTER 4 Thermogravimetric Analysis for Characterization of Nanomaterials
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
Fig. 4.6C is the widely preferred and generally employed design for accurate
measurement of temperature changes.
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.
n FIGURE 4.9 Simultaneous differential scanning calorimetry and thermogravimetry curves for a
pharmaceutical sample analyzed by an STA 6000/STA 8000 thermal analyzer.
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.
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
FePOH, iron hydroxyl phosphate; PMMA, poly(methyl methacrylate); TGA, thermogravimetric analysis.
84 CHAPTER 4 Thermogravimetric Analysis for Characterization of Nanomaterials
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].
4.6 Case Studies for Applications of Thermogravimetric Analysis 85
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].
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].
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
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-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.
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
4.6 Case Studies for Applications of Thermogravimetric Analysis 89
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.
90 CHAPTER 4 Thermogravimetric Analysis for Characterization of Nanomaterials
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].
4.6 Case Studies for Applications of Thermogravimetric Analysis 91
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.
92 CHAPTER 4 Thermogravimetric Analysis for Characterization of Nanomaterials
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 Case Studies for Applications of Thermogravimetric Analysis 93
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].
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].
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
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.
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
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.
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].
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.
102 CHAPTER 4 Thermogravimetric Analysis for Characterization of Nanomaterials
n FIGURE 4.25 CoatseRedfern plots for (A) polystyrene, (B) polystyrene/organoclay nanocomposite (PSNC)-3, (C) PSNC-7, and (D) PSNC-20 [17].
4.6 Case Studies for Applications of Thermogravimetric Analysis 103
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)
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
106 CHAPTER 4 Thermogravimetric Analysis for Characterization of Nanomaterials
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].
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108 CHAPTER 4 Thermogravimetric Analysis for Characterization of Nanomaterials