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Thermogravimetry Analysis for Characterization of Nanomaterials

Chapter · May 2017

DOI: 10.1016/B978-0-323-46139-9.12001-8

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 Thermogravimetry Analysis for Characterization of Nanomaterials
a* b* c d
Sravanthi Loganathan , Ravi Babu Valapa , Raghvendra Mishra , G. Pugazhenthi and
a
Sabu Thomas

a
School of Chemical Sciences, Mahatma Gandhi University, Kottayam, Kerala, India.
b
Centre for Biopolymer Science and Technology, A Unit of Central Institute of Plastics Engineering and

Technology (CIPET), Kochi, Kerala, India.

c
International and Interuniversity Centre for Nanoscience and Nanotechnology, Mahatma Gandhi University,

Kottayam, Kerala, India.

d
Department of Chemical Engineering, Indian Institute of Technology Guwahati, Guwahati, Assam, India.

*corresponding author, email id: sravanthi.signup@gmail.com, lsravanthi09@gmail.com

valaparavi@gmail.com

Abstract

The current chapter discusses the basics and principle involved in instrumentation of

thermogravimetry analysis (TGA). Different types of balances, crucibles and furnaces used in

TGA instrument are addressed. The basic information that can be derived from TG thermogram is

also discussed in detail. Advanced TGA instruments utilized for evolved gas analysis and their

application in predicting the thermal decomposition mechanism for polymer nanocomposites.

Further, application of TGA in different fields such as determination of drug and functional

moieties loading, gas adsorption studies, relative strength for catalysts as well as thermal

degradation kinetic analysis for polymer nanocomposites is addressed with appropriate case

studies.

Keywords: Thermogravimetry analysis, thermogram, electronic microbalance, furnace, evolved

gas analysis, thermal degradation kinetics, gas adsorption studies, nanoparticle purity, surface

coatings, drug loading and acidic sites.

1
1. Introduction

1.1. Definition and principle of thermogravimetry analysis

Thermogravimetry deals with the branch of thermal analysis which investigates the change in

weight for a substance as a function of time or temperature. The weight change profile is

recorded when the sample is subjected to 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 function of temperature.

The main principle of thermogravimetry analysis (TGA) includes mass change for a sample can

be studied under programmed condition. Therefore, TGA is mainly used for understanding certain

thermal events such as absorption, adsorption, desorption, vaporization, sublimation,

decomposition, oxidation and reduction. In addition to this, TGA can be utilized for evaluation of

volatile or gaseous products lost during such chemical reactions for samples such as

nanomaterials, polymers, polymer nanocomposites, fibers, paints, coatings and films. Along with

the prediction of thermal stability for samples, it is also possible to study the kinetics of chemical

reactions under various conditions using TGA. In order to investigate the kinetics, it becomes

essential to optimize the factors or conditions which influence the mass change for samples

throughout the experimental period. The factors which are found to influence the mass change

include (i) weight and volume of sample taken for analysis, (ii) physical form of sample, (iii) shape

as well as nature of sample holder, (iv) nature of atmosphere under which the analysis is

performed, (v) pressure of the atmosphere maintained in the sample chamber during the analysis

and (vi) rate of heating or cooling conditions. It is well known that temperature conditions can

bring changes in the sample mass. However, it is important to understand the fact that all types of

thermal changes cannot influence the weight change for samples. For example, melting and

crystallization behavior of samples cannot be studied using TGA.

2
2. Instrumental setup for TGA

Thermo balance is regarded as the heart of a TGA unit. The schematic representation of a

thermo balance can be seen from Figure 1. It is comprised of several sub-units such as (i)

electronic microbalance, (ii) Sample holder, (iii) furnace, (iv) temperature programmer and (v)

recorder. The thermo balance consists of a clamp that is utilized in order to hold the arm of

microbalance. Once the clamp is released, it should be noted whether the balance is returned to

zero position. The thermobalance should not be allowed for transportation while it holds the arm

of microbalance using clamps. Otherwise, zero point will be affected under such transportation is

attempted. It is generally preferred to allow the microbalance to leave for stabilization for ~15-20

min after placement of sample is ensured [1-5].

Figure 1. Schematic representation of a thermo balance

2.1. Electronic microbalance

Microbalance serves as the most significant component of a thermobalance. The main purpose of

a microbalance is to record the changes associated with sample mass. The important

characteristics that an ideal microbalance should possess are as follows:

(i) Mass change for a sample should be recorded accurately and in a reproducible manner

under various atmospheric conditions as well as temperatures.

3
 (ii) Electronic signals should appropriately be provided by the microbalance in order to

precisely record the mass change.

(iii) An immediate and ultimately fast response to mass change must be provided by

electronic signals.

(iv) An arrangement for automatic mass regulation should be enabled by the microbalance.

(v) A high range mechanical as well as electrical stability must be ensured by the

microbalance.

(vi) Microbalance should possess the ability to not get affected due to vibrations.

(vii) The operation of microbalance should be user-friendly.

2.1.1. Types of microbalance

Microbalance is divided into two types (i) deflection type and (ii) null-point type balances [1-5].

2.1.1.1. Deflection type balance

Deflection type balance is further subdivided into four types as shown in Figure 2(a)

(a) Beam type: In beam type balances, conversion of deflected beams occurs along with

the mass change. The TG curves thus formed are then identified using photographic

trace and signals which are generated by displacement measuring transducers.

(b) Helical type: In helical type balances, spring may undergo contraction or elongation with

respect to mass change of a sample which in turn is recorded using the presence of

transducers.

(c) Cantilevered beam type: In cantilevered beam type balances, 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.

(d) Torsion wire type: In torsion wire type balances, hard torsion wire is present and it acts

as a fulcrum. Here, beam is attached to the hard torsion wire. The wire is then attached

to one or both the ends of balance. This is done in order to make the beam deflection to

be proportional to the mass change. The deflections are recorded in a usual manner

which is similar to other deflection type balances discussed earlier.

4
2.1.1.2. Null-point type balance

The schematic representation of a null-point type balance is shown in Figure 2(b). It usually

comprises of a sensor through which detection of deviation from null-point is performed. The

restoration of balance to its original or null-point position is made through restoration force.

Figure 2. Different types of microbalance (a) Deflection and (b) Null type balances [1-5]

5
2.2. Sample holder

Sample holder is otherwise called as crucible. The sample to be subjected for investigation or

characterization is placed in the crucible which is attached to weighing arm of microbalance. The

images for various types of crucibles used in TGA based on shape are shown in Figure 3. In

general, the crucibles used for TGA vary in shape, size and materials. The main materials

employed for making crucibles such include aluminum, platinum and quartz. In addition to this,

few other materials are also being utilized occasionally such as stainless steel, glass and

graphite. The utilization of crucibles made of different materials in TGA depends on the

temperature range required for performing experiments. It is necessary that the crucible should

possess at least 100 °C higher thermal stability as 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 crucibles are the significant parameters which should be taken

into consideration before the usage of any crucible under predetermined experimental conditions.

All the above mentioned parameters are in turn dependent on the nature and mass of samples as

well as fixed experimental temperature regime.

Figure 3. Different types of crucibles used in TGA based on shape [1-5]

6
In case of powdered samples, generally flat crucibles are used whereas liquid type samples are

analyzed using walled crucibles. The temperature gradient present in the sample is determined

by the type of crucible used for analysis. Figure 4 shows the TGA profile for the poly(methyl

methacrylate) (PMMA) polymer analyzed using different type of crucibles. In Figure 4, the TGA

profile presented in continuous line indicates the PMMA sample analyzed by normal aluminum

crucible. The dashed line in Figure 4 represents the PMMA sample analyzed by special type of

aluminum crucible fitted with an aluminum disc at the bottom position in order to enhance the

thermal mass. It can be carefully analyzed from the Figure that both the TG curves obtained for

same PMMA sample present difference in terms of shape as well as residue rate. This variation is

because of the different type of crucible used for analysis in spite of sample being the same. The

temperature at which the maximum rate of weight loss occurs (Tmax) is found to be enhanced by

5 °C due to the greater thermal mass exhibited by aluminum crucible with disc fitted at its bottom.

In general, crucible must be cleaned regularly with using methanol as well as pre-heating of the

crucible till its maximum temperature must be ensured before analysis in order to get precise

decomposition profile.

Figure 4. Thermal decomposition profile for PMMA analyzed with different types of

crucibles

7
2.2.1. Types of crucibles

The different types of crucibles used in TG analysis are as follows [1-5]:

(a) Shallow pan: Such type of crucible is used for analyzing samples in which diffusion of

volatile substances plays the role as rate-limiting factor. The gaseous substances

released as decomposition products of samples such as polymers should escape out in

order to evaluate its weight loss. Under such circumstances, sample in the form of thin

layer is made and placed in the shallow type crucible such that the volatile decomposition

products escape out easily due to which weight loss profile for samples can be

determined accurately.

(b) Deep crucible: This type of crucible is utilized in certain case studies such as industrial

scale calcinations where side reactions become mandatory.

(c) Loosely covered crucible: Such type of crucible is used in isothermal studies where the

rate at which the temperature proceeds during analysis or weight loss of samples is

neglected.

(d) Retort cup: This type of crucible is used in determination of boiling point for samples.

The utilization of such crucibles helps in providing single plait of reflux for a boiling point

evaluation.

2.3. Furnace

The furnace should be designed appropriately so that 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 sample corresponds to the furnace

temperature. It is known that internal atmosphere of furnace can be affected by temperature

regime maintained in the furnace. Hence, it becomes adequate to select for a furnace specifically

suitable in accordance to temperature regime. Various types of materials used for making heating

coil according to temperature range are presented in Table 1. It should be ensured that there

exists no magnetic interaction among sample and heating coil present in the furnace. This is

because; presence of magnetic interaction can lead to change in weight of sample apparently.

8
Table 1: Materials used for heating coil and its corresponding temperature range [1-5]

S:No: Materials used Temperature (°C)

1 Nichrome wire <1300

2 Ribbon <1300

3 Platinum >1300

4 Platinum(90%)/Rhodium(10%) alloy <1800

5 Silicon carbide <1600

6 Silver <650

7 Steel <1000

8 Rhodium <1700

9 Graphite <2000

10 Tungsten <2400

In addition to this, size of the furnace also plays important role for accurate measurement. A

furnace with high mass may withstand up to enhanced temperature regime and ensure uniform

hot zone. However, increased time scale is required for achieving targeted temperature. On the

other hand, low weight furnaces can be able to provide quick heating with quite great difficulty in

controlling the rate of increase in temperature. Therefore, light weight furnaces do not allow for

proper maintenance of hot zone. Another significant parameter which affects the quality of

analysis is the position of furnace with respect to balance. Figure 5 presents the position of

furnace with respect to different types of microbalance. It can be seen from Figure 5(a) that the

weighing balance is present below the furnace in case of quartz spring type balance. In case of

beam type balance shown in Figure 5(b), it can be noticed that the weighing balance is present

above the furnace position. Also, the presence of weighing balance in different positions with

respect to same furnace position can be interpreted from Figure 5(b).

9
 Figure 5. Position of furnace with respect to (a) spring type and (b) beam type balances

[1-5]

2.4. Thermocouple

Thermocouple is used for measuring temperature. Similar to heating coil, various types of

material are used for fabrication of thermocouple which includes tungsten or platinum alloys.

Platinum alloys namely chromal and alumel are used as thermocouple for measuring temperature

conditions below 1100 °C. For temperature conditions above 1100 °C, tungsten material is used

for making thermocouple. The position at which the thermocouple is placed plays governing role

for precise measurement during analysis. The various positions of thermocouple that can be

possible in a microbalance are presented in Figure 6. The presence of thermocouple near to

crucible can be seen from Figure 6(a). In such type of design, it can be noticed that there is no

contact among thermocouple and sample container. This type of set-up is not usually preferred

under low pressure conditions. Figure 6(b) 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 conditions. In Figure 6(c), 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 Figure 6(c) is the widely preferred and generally employed design for accurate

measurement of temperature changes.

10
 Figure 6. Possible positions for thermocouple in thermo balance [1-5]

2.5. Temperature programmer

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

degree/minute in terms of Kelvin or Celsius scale. The rate of heating or cooling can be

considered as constant when the temperature versus time curve appears to be linear.

2.6. Data recording unit

The data recording unit is basically a chart recorder or microcomputer which is used for recording

the output provided by balance and furnace. The microcomputer enables the provision to both

save and plot the temperature versus weight loss curve using pre-installed software while

performing mathematical problems whereas this feature is not present in chart recorder. Also,

microcomputer 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 X-Y recorder and time-base potentiometric strip chart recorder.

11
3. Classification of TGA

TGA is classified into three types as follows

3.1. Dynamic TGA

In this method, temperature of the sample will be increasing continuously at a specific heating

rate. Therefore, temperature of the sample varies linearly with time.

3.2. Static or Isothermal TGA

In this method, sample is allowed to be maintained at constant temperature condition for a fixed

interval of time. During this time period, the mass change that occurs in the sample will be

recorded.

3.3. Quasistatic TGA

In this method, sample is heated to a constant weight at each of a series of increasing

temperature.

4. TG Curve

TG curve usually represents a plot of weight change as a function of temperature or time. An

example for a typical TG curve is shown in Figure 7. The TG curve shown in Figure 7 exhibits a

single stage of decomposition. 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 thermal stability of the sample being analyzed.

Figure 7. A typical TG curve

12
4.1. Interpretation of TG curve

Interpretation of TG curve can be done in several ways as follows

4.1.1. Types of TG curve

TG curve is classified in to seven types on the basis of shape as shown in Figure 8.

(a) Type 1: This type of curve exhibits no weight change throughout the complete

temperature range used for analysis. The possible reason for this phenomenon may be

due to the fact that the thermal stability of the sample is higher than the temperature

range.

(b) Type 2: This type of curve exhibits mass loss region which is then followed by a constant

line. TG curves of type 2 results during certain processes such as drying where volatile

compounds get evaporated and desorption.

Figure 8. Classification of TG curve based on shape [1-5]

13
 (c) Type 3: The TG curves which demonstrates single stage of weight loss or decomposition

corresponds to Type 3.

(d) Type 4: This type of curve can be exhibited by samples which undergo multi-stage

decomposition process.

(e) Type 5: This type of curve can be resulted when there is increment in weight for sample

due to surface oxidation reactions that take place in a reacting atmosphere.

(f) Type 6: This type of curve can be possible if there are multiple reactions with respect to

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

decomposition process of reaction products.

4.1.2. Plateau

Plateau is the region present in TG curve which corresponds to a constant line that follows after

the weight loss portion. In this region, mass of the sample is constant or otherwise no weight

change can be found. In Figure 8, plateau region can be visualized in case type 2 as well as type

3 curves.

4.1.3. Initial decomposition temperature

The initial decomposition temperature (Tinitial) corresponds to the temperature point where

cumulative weight change attains a magnitude that can be detectable by a thermo balance.

4.1.4. Final decomposition temperature

The final decomposition temperature (Tfinal) corresponds to the temperature point where

cumulative weight change attains a maximum and cannot change further.

4.1.5. Reaction interval

The temperature difference that occurs among initial and final decomposition temperatures

corresponds to reaction interval. In case of single stage of decomposition, there exists only single

14
reaction interval. For multi-stage decomposition profile, several reaction intervals may be present

which is according to decomposition stages revealed by the sample with respect to heating.

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 temperature when the sample undergoes heating in

a controlled temperature program.

4.1.7. Evolved gas analysis

It is well known that the evolution of gaseous compounds take place when the sample undergoes

decomposition under a controlled temperature program. When TGA is coupled to Fourier

transform infrared spectroscopy (FTIR) or gas chromatography-mass spectrometry instruments, it

is possible to analyze the functional composition of gaseous compounds released from sample

subjected to controlled temperature program.

4.1.8. Information from thermogram

The term thermogram refers to plot obtained by TGA which comprises weight loss versus

temperature data. The following information can be derived from a typical thermogram shown in

Figure 7.

(i) Thermal stability: Thermal stability is determined for a substance using TGA based on

its ability to maintain its characteristics as almost unaffected as likely upon exposure to

heat. The knowledge about thermal stability is very important for engineers such that it is

possible to predict the temperature regime of alloys, polymers and nanomaterials.

(ii) 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 in order to determine the composition of sample such that it is possible to

understand the reaction steps involved in decomposition process. Through weight loss

profile, it is also possible to identify the unknown compound present in the sample or

15
 evaluate the amount or percentage of a specific compound present among the mixture of

different compounds present in the sample.

(iii) Procedural decomposition temperature: With the help of thermogram, procedural

decomposition temperature which indicates evaporation or decomposition processes of a

substance can be evaluated.

5. Advanced TGA instruments

5.1. Simultaneous determination of TG and heat flow curves

At present, advanced instruments are available in the market for simultaneous determination of

TG and heat flow curves. For example, Perkin Elmer Company introduced product number STA

6000 and STA 8000 with advanced analytical technique to simultaneously determine the TG and

heat flow curves. Both STA 6000 and STA 8000 instruments measure the heat flow data using

differential scanning calorimetry (DSC) technique and weight loss data via TGA technique,

simultaneously. The DSC heat flow data is usually measured in milliwatts or Joules/gram. The

STA 6000/STA 8000 simultaneous thermal analyzer instrument is designed with leading edge

sensor technology in order to yield great accuracy as well as quality results. Also, STA 6000/STA

8000 instrument encompasses patent pending “SaTurnA” sensor and highly compact furnace

ensuring better temperature control, consistent measurements as well as fastest cool-down

timing as compared to other simultaneous TGA-DSC analyzer.

Figure 9 shows the TG curve for a pharmaceutical sample analyzed by STA 6000/STA 8000

instrument. In Figure 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 crystalline melt peak is present at 229 °C. It is visible that baseline

returns to a slightly lower position after the melt transition. This is an indication of lower heat

capacity exhibited by liquid phase as compared with 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 noticed from Figure 9 that the decomposition peak exhibited by DSC curve at

16
287 °C is exothermic in nature and this corroborates with the onset decomposition temperature of

287 °C extrapolated from TG curve.

Figure 9. Simultaneous DSC and TG curves for a pharmaceutical sample analyzed by STA

6000/STA 8000 thermal analyzer

5.2. Evolved gas analysis

Several techniques are now available for analysis of gaseous products from TG analysis and the

approach is termed as “evolved gas analysis” (EGA). The EGA approach involves a subset of

hyphenated techniques in which two or more instruments are integrated. The TGA-EGA

techniques followed currently are discussed as follows:

5.2.1. TGA coupled Fourier transform infrared spectrometer (TGA-FTIR)

The most general system used for EGA involves the utilization of TGA coupled with a Fourier

transform infrared spectrometer (TGA-FTIR). When a sample is subjected to heating in TG

analysis, volatile or combustion components are generated due to burning. Such volatile or

combustion components released will then be transferred to infrared (IR) cell through which

identification of released components are 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 presents featured IR spectra. The image for TGA-FTIR is presented in Figure 10(a).

17
5.2.2. TGA-mass spectrometry (MS)

Another type of integrated instrument used for EGA is TGA-mass spectrometry (MS) which is

useful for detection of very low level of impurities in real time. Like TGA-FTIR, gases released

during heating of sample are passed to MS where the compounds can be detected. TGA-MS

serves as a powerful tool for EGA because of its ability to identify even minute level 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. The image for TGA-MS is presented in Figure 10(b).

5.2.3. TGA-gas chromatography mass spectrometry (GC/MS)

In the recent years, there has been increasing approach in utilization of TGA coupled gas

chromatography/mass spectrometry (TGA-GC/MS) technique for EGA. Similar to TGA-MS, the

evolved gas during heating of sample is transferred to GC where the components are collected.

Thereafter, the gas sample collected is run using GC in order to separate the different

components and peaks are identified by MS. This technique gained popularity due to its ability in

detecting 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. The image for TGA-GC/MS is presented in Figure 10(c).

Figure 10. Different types of advanced TGA instruments used for evolved gas analysis

18
5. Case studies for applications of TGA

5.1. Determination of thermal stability under modified atmosphere

It is well known that poly(methyl methacrylate) (PMMA) serves as very significant thermoplastic

material in polymer industry. The drawbacks associated with PMMA include its poor thermal

stability as well as easy flammability. When PMMA gets burned, the methyl methacrylate (MMA)

monomer unit which gets released during burning further generates bubbles which in turn help in

production of flammable gas phase. Therefore, rate at which the mass loss occurs for PMMA gets

accelerated due to the generation of flammable MMA gas and so residue is not left after pyrolysis

takes place even in inert atmosphere. In order to overcome the above mentioned drawbacks,

fabrication of PMMA/inorganic hybrid composites has received great attention. Incorporation of

inorganic nanoparticles in 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 PMMA matrix is reported. In case study 1, thermal stability

of the PMMA/FePOH composites is analyzed to understand the thermal degradation behavior of

the composites under modified atmosphere conditions. The TGA data obtained for PMMA and

PMMA/FePOH composites under air and nitrogen atmospheric conditions are presented in Table

2. It is interpreted that the T10% (temperature at which 10% weight loss occurs) increased by ~19

°C for 6 wt% loading of FePOH in the PMMA matrix under air atmosphere. In case of nitrogen

atmosphere, the PMMA composites exhibited decrement in T10% values as compared to neat

PMMA. Under nitrogen atmosphere, chain end scission and random chain scission reactions are

accelerated due to which thermal stability of PMMA composites are affected. In air atmosphere,

random chain scission reaction takes place in a controlled manner and hence PMMA/FePOH

composites show improved thermal stability [6].

19
Table 2. TGA data for PMMA and PMMA/FePOH composites under different atmospheric

conditions [6]

Sample TGA data

Air atmosphere Nitrogen atmosphere

T10% T50% Residue T10% T50% Residue

(°C) (°C) % at (°C) (°C) % at
600 °C 600 °C
PMMA 231 308 0.9 260 355 0.2
PMMA/2wt% FePOH 232 323 4.5 221 362 3.2
PMMA/6wt% FePOH 250 342 12.2 249 363 8.1

In case study 2, the effect of amino group containing constituents on the thermal stability of

chitosan and chitosan/magnetite (Fe3O4) nanocomposites is investigated [7]. The amino groups

are introduced in the polysaccharide chain of chitosan (CS) and the derivatives of chitosan (CS1,

CS2 and CS3) thus prepared are used as matrix for incorporation of Fe3O4 nanoparticles in order

to fabricate modified chitosan/Fe3O4 nanocomposites (Fe3O4-CS1, Fe3O4-CS2 and Fe3O4-CS3).

Thereafter, TG analysis is performed to evaluate the thermal stability of neat CS, modified CS

and Fe3O4/modified CS nanocomposites. The synthesis route and structure for CS and modified

CS can be seen from Figure 11.

The TGA curves obtained for neat CS, modified CS and Fe3O4/modified CS nanocomposites

under nitrogen atmosphere can be seen from Figure 12. In case of CS, the initial weight loss

corresponds to removal of adsorbed water by hydrophilic groups present in CS. The main stage

of degradation that occurs between 200 to 500 °C is because of chain scission and ring opening

reactions. The carbon residue noticed during thermal degradation of neat CS under air

atmosphere at 800 °C corresponds to ~34%. Similar to CS, the derivatives CS-1 and CS-3 also

demonstrates three stages of weight loss. However, CS-2 showed complex degradation profile

with a minimum of four steps during degradation. In case of nanocomposites, four stages of

degradation are noticed due to the presence of inorganic filler.

20
 Figure 11. Synthesis route and structure for chitosan and modified chitosan [7]

The TGA curves obtained for neat CS, modified CS and Fe3O4/modified CS nanocomposites

under nitrogen atmosphere can be seen from Figure 13. For neat CS, three stages of degradation

are noticed under air atmosphere. The first stage corresponds to moisture loss and second stage

presents weight loss due to decomposition as well as oxidation reactions. Interestingly, complete

weight loss due to degradation of intermediates formed at earlier stages is noticed at 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 showed

similar degradation profile except CS-2 under air atmosphere also.

21
Figure 12. TG and DTG curves for (a) neat CS and modified CS and (b) Fe 3O4/modified CS

nanocomposites [7]

22
Figure 13. TG and DTG curves for (a) neat CS and modified CS and (b) Fe3O4/modified CS

nanocomposites [7]

23
 For precise interpretation of differences in thermal degradation behavior of all the samples,

comparative analysis of thermal parameters derived from TG analysis is carried out. The TGA

data obtained for CS, modified CS and Fe3O4/modified CS nanocomposites under nitrogen and

air atmospheric conditions is presented in Table 3. The higher mass loss exhibited by CS-2 and

Fe3O4/CS-2 in the first stage may be due to its ability to bind higher water content as compared to

other samples under both the atmospheric conditions. The higher residue content exhibited by

Fe3O4/CS-1 and Fe3O4/CS-3 samples under both the atmosphere is due to the formation of non-

volatile intermediates as compared to Fe3O4/CS-2.

Table 3. TGA data for CS, modified CS and Fe3O4/modified CS nanocomposites under

nitrogen and air atmospheric conditions [7]

Sample Nitrogen atmosphere Air atmosphere

First Second Third Residue First Second Third Residue

stage stage stage after stage stage stage after
∆m (%) ∆m (%) ∆m (%) 800 °C ∆m (%) ∆m (%) ∆m (%) 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

5.2. Prediction of thermal decomposition mechanism

Case study 3 demonstrates the application of thermal degradation profile obtained for polymer

composites in predicting the thermal decomposition mechanism. In case study 3, hypothetical

thermal degradation mechanism for poly(lactic acid)/sucrose palmitate (PLA/SP) biocomposites is

proposed based on the TG curve obtained for sucrose palmitate [8]. The TG and DTG curves

obtained for SP, PLA and PLA-SP biocomposites are presented in Figure 14. In this study, it is

noticed that the Tmax values remain unaffected for PLA-SP biocomposites till 5 wt% loading. With

further increase in SP loading, the Tmax value drastically reduced.

24
Figure 14. (a) TG and (b) DTG curves for SP, PLA and PLA-SP biocomposites [8]

25
The reason for 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 sucrose functional

+
group present in SP. It is reported that the H ions released during the thermal degradation of SP

diffuse into amorphous phase of PLA 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 the 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 Figure 15. The relatively higher concentration of H

released for higher loadings of SP triggers the hydrolysis of ester backbone present in PLA. The

increased acid terminal groups generated by 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.

Figure 15. Hypothetical mechanism for thermal decomposition of

PLA-SP biocomposites [8]

26
In case studies 4 and 5, advanced instrumental methods which 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, EVA is carried out for β-cyclodextrin

using integrated TG-MS/FTIR device [9]. The NIST mass spectral database was utilized to

interpret the mass spectra obtained during EVA. It is interpreted from the TGA/FTIR-MS analysis

that complex volatile mixture is generated during the thermal degradation of β-cyclodextrin.

Figure 16 shows the MS and FTIR spectra obtained during thermal degradation of β-cyclodextrin

at 308 °C. The evolved compounds identified in MS spectra include methanol (m/z values: 32 and

29), ethanol (m/z values: 46, 45 and 31), acetic acid (m/z values: 60, 45 and 43), furfural (m/z

values: 96, 95 and 39) and 2-methyl-furan (m/z values: 82 and 81). The FTIR spectra also

corroborated the identification made using MS spectra. The broad absorption band obtained in
-1
the range of 3500-3000 cm reveals the presence of alcoholic compounds evolved during
-1
thermal degradation of β-cyclodextrin. The sharp peak identified at 3239 cm corresponds to the
-1
stretching vibrations of amine based compounds. The absorption band obtained at 2816 cm
-1
reveals the stretching vibrations of alkyl groups. The signals found in the range of 2000-1628 cm
-1
confirms the presence of carboxyl and alkene moieties. The peak identified at 863 cm is due to

the C-H stretching vibration of furan compound.

(a) (b)

Figure 16. MS and FTIR spectra obtained during thermal degradation of β-cyclodextrin and

its derivatives at 308 °C [9]

27
Case study 5 deals with the analysis of fast co-pyrolysis 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

compounds evolved over time are identified via FTIR. . Different temperature conditions affected

the composition of major products formed during fast co-pyrolysis of cellulose and PP. The

products formed are again found to be dependent on feed composition. The influence of pyrolysis

temperature for cellulose/PP mixture with different feed composition on product distribution is

shown in Figure 17. It is reported that long chain alcohols are formed due to the interaction

among cellulose and PP. With rise in pyrolysis temperature, char yield is decreased and

generation of aromatic compounds is increased. For mixture with higher PP content, pyrolysis at

600 °C resulted in the formation of ~36% alcohols and ~45% hydrocarbons. Based on the

information obtained from product distribution profile, it is predicted that the dominant reactions

responsible for transformations to be hydroxyl, hydrogen and methyl abstraction.

Figure 17. Influence of temperature for cellulose/PP mixture with different feed

composition on product distribution [10]

28
The higher percentage of alcohols as well as hydrocarbons production noticed when the feed is

subjected to a temperature condition of 600 °C confirms the vapor phase interactions. Such

interactions are favored due to hydroxyl radical generation and β-chain scission reaction products

from degradation of cellulose and PP, respectively. Figure 18 depicts the possible intermediate

compounds responsible for formation of major alcohols during fast co-pyrolysis of cellulose/PP

mixture at 600 °C. It is predicted that linear alcohols like octanol, dodecanol and decanol are

formed due to 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.

Figure 18. Possible intermediate compounds responsible for formation of major alcohols

during fast co-pyrolysis of cellulose/PP mixture at 600 °C [10]

29
5.3. Determination of nanoparticle purity and amount of surface coatings

Case studies 6 and 7 deal with the determination of nanoparticle purity and measurement of

amount of surface coatings [11]. At present, proteins or lipid layers are being coated onto

nanoparticles before they are introduced into complex environments like biological fluids. Several

current analytical techniques face drawbacks in determination of nanoparticle purity as well as

presence of surface coatings. The case study 6 discusses the application of a microscale TGA or

µ-TGA for evaluation of purity and composition of carbon nanotube (CNT) by identifying the

oxidation temperature and residual mass remaining after carbon decomposition is completed.

Figure 19 shows mass (%) versus temperature curve obtained for CNTs using µ-TGA and

conventional TGA. In case of µ-TGA, spray coating process is used for uniform and thin film

coating of CNTs onto quartz crystal balance (QCM). Then, the sample is heated to 300 °C initially

and thereafter only 25 °C is raised at regular intervals till the temperature of 525 °C is reached.

This is done to capture the full oxidation of CNTs.

Figure 19. Mass (%) versus temperature curve obtained for (a) CNT with high purity and (b)

CNT with high metal content using µ-TGA (red line) and conventional TGA (blue line) [11]

It can be seen from Figure 19(a) that µ-TGA curve closely follows conventional TGA curve.

However, there is fluctuation in initial stages which is due to the presence of water content in

CNTs and limit towards detection of humidity by QCM. Decomposition of CNTs is initiated at

30
425 °C which is evident from both µ-TGA and conventional TG curves. It can be seen from Figure

19(a) that µ-TGA and conventional TG curves show a residual mass of ~17% and ~7%,

respectively. The residual mass (%) corresponds to the catalysts left over from synthesis

procedure or oxidation products released from catalysts remaining after complete decomposition

of carbon. In case of Figure 19(b), it can be seen that ~32% residual mass is remaining for CNT

with high metal content analyzed by µ-TGA. Through this analysis, it is possible to determine the

purity for different types of CNTs accurately by evaluating the residual mass remaining after

oxidation process. The results clearly indicate that CNTs with high metal content corresponds to

impure sample as it exhibits high residual mass left over after complete decomposition of carbon

content.

Case study 7 discusses the application of µ-TGA to confirm the presence of ligand coating on

gold nanoparticles as well as determine the quantity of surface bound coverage of ligand

moieties. Figure 20 shows mass (%) versus temperature curves for layer-by-layer coatings of

poly L- lysine (PLL) and deoxyribonucleic acid (DNA) on 30 nm gold (Au) nanoparticle which is

specially designed for gene delivery purpose.

Figure 20. Mass (%) versus temperature curves for layer-by-layer coatings of PLL and DNA

on 30 nm Au nanoparticle [11]

31
Through dynamic light scattering experiments, it is confirmed that the particle size for coated Au

nanoparticle increases with respect to addition 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 is presented in Table 4. Based on the mass (%) loss information obtained using

µ-TGA curves for different layers coated, the content of DNA deposited onto surface of Au

nanoparticle is determined accurately.

Table 4. Mass (%) left over after decomposition of all layers at 400 °C, size and DNA

content for layer-by-layer coated Au nanoparticles [11]

Sample Mass left over Size measured by DNA content

after 400 °C DLS (nm) estimated (ng/µL)
Au + PLL 86 34 -
Au + PLL + DNA 70 53 72
Au+ PLL +DNA + PLL + DNA 43 61 104

5.3. Evaluation of loading of drug or functional moieties

Case study 8 deals with the application of TGA in 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 3-aminopropyl triethoxy silane

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.

The weight loss that occurs in the temperature range of 100-600 °C is considered for all the

samples in order to determine the organic loading as well as curcumin loading. The weight (%) of

organic groups that are attached to the porous surface of mesoporous silica particles as well as

curcumin loading (%) is calculated from TGA profile obtained for respective samples and are

presented in Table 5. It can be seen from Table 5 that the weight loss (%) that occurs between

100-600 °C differs for samples S1 (without curcumin) and S2 (with curcumin). For sample S1, the

32
entire weight loss (%) noticed in the above mentioned temperature regime corresponds to organic

loading (%). In case of sample S2, the entire weight loss of ~11.76% that occurs between 100-

600 °C does not correspond to organic loading (%) alone. Rather, 11.76% of weight loss is due to

the combined decomposition of organic groups as well as curcumin. Since the weight loss that

occurs due to organic loading is already known for sample S1 (9.08%), curcumin loading can be

calculated by subtracting 9.058% from entire weight loss (11.76%). Therefore, the total amount of

curcumin loaded in KIT-6-AP support is estimated to be 2.68%.

Table 5. Organic and curcumin content (%) evaluated using TGA measurements [12]

Sample % Weight loss % Weight loss % Curcumin

(20-100 °C) (100-600 °C)
S1 (KIT-6-AP) 3.62 9.08 -
S2 (KIT-6-AP-CUR) 3.28 11.76 2.68
S3 (MSU-2-AP) 2.93 8.46 -
S4 (MSU-2-AP-CUR) 2.32 14.34 3.56
S5 (MCM-41-AP) 5.31 11.00 -
S6 (MCM-41-AP-CUR) 3.75 14.58 3.58

Case study 9 deals with application of TGA in 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-aminopropyl triethoxy silane 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

tethered with two surface silanol groups of PE-MCM-41 with one dangling alkoxyl group) and

tridentate grafting (mono and triamino ligands tethered with three surface silanol groups of PE-

MCM-41) phenomenon. The organic and amine loadings estimated for mono and triamine grafted

PE-MCM-41 based on the weight loss information obtained from TGA are presented in Table 6.

The weight loss that occurs between 200-550 °C is considered for the calculation of organic and

amine loadings. This is because, decomposition of organic groups functionalized in PE-MCM-41

takes place in the above mentioned temperature regime. It can be seen from Table 6 that organic

loading as well as amine loading remains same in case of monoamine functionalized PE-MCM-

33
 41. However, this is not applicable for triamine functionalized PE-MCM-41 due to the presence of

three nitrogen groups per organic chain.

Table 6. Estimated organic and amine content present in PE-MCM-41 using TGA [13]

Sample Organic loading Amine loading

2 2
mmol/g molecules/nm mmol(N)/g molecules(N)/nm

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

5.4. Gas adsorption studies

Case study 10 deals with the application of modified TGA instrument used for gas adsorption

measurements on zeolite 13X and triamine tethered pore-expanded mesoporous MCM-41

(TP-PE-MCM-41) silica material [14]. Figure 21 shows the modified TGA instrument utilized for

carbon dioxide adsorption measurements.

Figure 20. Modified TGA instrument for CO2 adsorption measurements [14]

34
In case study 10, TGA instrument is coupled with mass spectrometer for determination of carbon

dioxide (CO2) capacity and analyze the decomposition products released during degradation

studies carried out for zeolite 13X and TP-PE-MCM-41. For both CO2 measurements and

decomposition studies, specific amount of sample is loaded into platinum crucible. Initially,

activation of the sample is carried out under N2 atmosphere and at predetermined activation

temperature. Activation is carried out to remove pre-adsorbed gases on sample prior to CO2

adsorption measurements. Activation temperature is predetermined based on thermal stability

acquired by sample. Activation is performed until constant mass for sample is reached. Once

activation is completed, the balance is allowed to cool in order to reach the desired temperature

required for CO2 adsorption measurements. The feed used for analysis contains 5% CO 2 and

95% N2. The feed flow rate is controlled with the help of mass flow controller. The effect of

moisture on adsorption capacity is also studied by passing humid gas with a relative humidity of

27% to the TGA balance. Figure 22 shows the CO2 adsorption capacities measured for zeolite

13X and TP-PE-MCM-41 using modified TGA. It can be seen from Figure 22 that adsorption

capacity increases initially and almost tends to attain saturation with respect to time at a specified

temperature.

Figure 22. CO2 adsorption capacities with respect to time for zeolite 13X and

TP-PE-MCM-41 measured using modified TGA [14]

35
5.5. Determination of relative strength for catalysts

Case study 11 deals with the application of TGA for characterizing temperature programmed

desorption profiles of zeolites [15]. In general, distribution of acid sites in zeolites determines their

catalytic property. Initially, zeolite is preheated at 500 °C to remove the pre-adsorbed gases

under inert atmosphere until constant mass is reached. Thereafter, balance is allowed to cool in

order to reach analysis temperature of 100 °C. After equilibrium is attained, furnace purge is

changed to analysis gas containing the base. The adsorption of base on zeolites results in weight

gain for sample. Once constant mass is reached, the furnace purge is again switched to inert gas

flow. Now, loss of mass for sample can be achieved due to desorption of physisorbed base on

zeolite. After constant mass is reached, once again the balance temperature is increased to

600 °C. Figure 23 shows several steps involved in TGA-TPD experiment performed for zeolite

HZSM-5.

Figure 23. Steps involved in TGA-TPD experiment performed for zeolite HZSM-5 [15]

36
It can be seen from Figure 23 that two weight loss regions are present in TGA-TPD profile

obtained for zeolite HZSM-5. The weight loss due to physidesorption corresponds to desorption

of physically bound base ammonia on weak acidic sites of zeolite HZSM-5. The weight loss due

to chemidesorption corresponds to desorption of chemically bound base ammonia on strong

acidic sites of zeolite HZSM-5. Through this weight loss information, number of strong and weak

acidic sites for zeolite HZSM-5 is calculated to be 0.34 and 0.32 mmol/g, respectively.

5.6. Kinetic analysis

Case study 12 deals with the application of TGA in predicting thermal degradation kinetics for

polymer nanocomposites [16, 17]. In order to perform thermal degradation kinetic analysis,

PMMA and PMMA/nanoclay composites are subjected to TG analysis at three different heating

rates such as 5, 10 and 15 °C/min [16]. The TG data obtained at three different heating rates are

analyzed thermal degradation kinetic models such as Kissinger and Friedman. Using these

models, kinetic parameter called as “activation energy (Ea)” is determined for PMMA/nanoclay

composites. This is because, determination of activation energy for degradation helps to better

understand the thermal stability of polymer nanocomposites. For PMMA/nanoclay composites, it

is found that decomposition temperature increases with respect to rise in heating rate. This

phenomenon arises due to time-temperature superposition principle which explains that time

necessary for sample to reach desired temperature will decrease with rise in heating rate.

Figure 24 shows Kissinger and Friedman plots obtained for PMMA/nanoclay composites. The

activation energy via Kissinger method for PMMA/nanoclay composites is obtained by using

inflection point temperatures (Tmax) present in TG curve. The activation energy values calculated

using Kissinger and Friedman methods are presented in Table 7. It is found that activation energy

calculated by both the methods for composites increases with respect to increase in clay loading

in PMMA matrix. It can be seen from Figure 24(b) that the activation energy values for

composites are higher as compared to neat PMMA. This reveals that heat barrier effect is

provided by incorporation of nanoclay such that degradation of PMMA composites slows down.

37
 (a)

(b)

Figure 24. (a) Kissinger plot and (b) activation energy versus conversion plot obtained by

Friedman method for PMMA and PMMA/nanoclay composites [16]

38
Table 7. Activation energy (Ea) values for PMMA and PMMA/nanoclay composites obtained

by Kissinger and Friedman kinetic models [16]

Sample Ea (kJ/mol)
Kissinger method Friedman method
Neat PMMA 88 121
PMMA-3 126 167
PMMA-5 161 196
PMMA-7 212 200

In case study 13, TGA data obtained at a single heating rate is used by Coats-Redfern method to

determine the kinetic parameters associated with thermal degradation of polystyrene/organoclay

nanocomposites (PSNC) [17]. Figure 25 shows Coats-Redfern plots obtained for PS and PSNC

nanocomposites at a heating rate of 10 °C/min.

(a) (b)

(c) (d)

Figure 25. Coats-Redfern Plots for (a) PS, (b) PSNC-3, (c) PSNC-7 and (d) PSNC-20 [17]

39
The kinetic parameters such as activation energy, reaction order and pre-exponential factor

evaluated using Coats-Redfern method are presented in Table 8. It can be seen from Table 8 that

activation energy increases for PSNC composites up to 7wt% loading as compared with neat PS.

With further increase in loading, activation energy tends to decrease for PSNC composites. This

is because, the presence of large organic surfactant content available in composites generated

charred layers with less stability during degradation.

Table 8. Kinetic parameters evaluated using Coats-Redfern method at optimum correlation

co-efficient for PS and PSNC nanocomposites at 10 °C/min [17]

Sample Reaction order Activation Pre-exponential Correlation

(n) energy factor (A) co-efficient (R)
(Ea kJ/mol)
6
Neat PS 0.2 96 4.72 x 10 0.9996
13
PSNC-3 0.6 185 2.25 x10 0.9937
13
PSNC-7 1 186 2.59 x 10 0.9943
10
PSNC-20 0.4 155 9.49 x 10 0.9950

Case study 14 deals with the application of modified high pressure thermo-gravimetric analyzer to

study kinetics of CO2 adsorption on pore-expanded MCM-41 silica under different pressure 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 wide

range of pressure conditions (0.2-11 bar) are analyzed by kinetic models. The analysis of

experimental data using pseudo-first order and pseudo-second order models explains that

adsorption of CO2 on PE-MCM-41 occurs via physisorption. 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, rate controlling step associated with

CO2 diffusion is predicted. The intraparticle diffusion plots obtained for CO 2 adsorption kinetics on

PE-MCM-41 is shown in Figure 26. In this study, it is elucidated that film diffusion becomes rate

governing under low pressure and low temperature regime. On the other hand, pore diffusion

becomes dominating in case of high pressure and high temperature conditions.

40
 Figure 26. Prediction of CO2 adsorption kinetics on PE-MCM-41 using intraparticle

diffusion model (a) 30 °C, (b) 45 °C, (c) 60 °C and (d) 75 °C [18]

Case study 15 discusses the application of high pressure thermogravimetric balance used to

generate CO2 adsorption isotherm and kinetic data on mono (AP) and triamine (TP) tethered

pore-expanded MCM-41 (PE-MCM-41) silica [19]. The CO2 adsorption isotherm data is obtained

under four different temperature conditions (30, 45, 60 and 75 °C) and pressure regime ranging

from 0-5 bar. On the other hand, kinetic data is obtained under the pressure condition of 1 bar

and four different temperature conditions mentioned earlier.

The CO2 adsorption isotherm data is analyzed by two different isotherm models such as

Langmuir and Langmuir dual site model to understand whether adsorption takes place via

physisorption or chemisorption. Figure 27 shows the CO2 adsorption isotherm data analyzed by

Langmuir and Langmuir dual-site models. Based on the model fitting, it is predicted that

41
chemisorption tends to control the initial phases of adsorption and later phases of adsorption is

governed by physisorption. The kinetic uptake measurement data analyzed by pseudo-first order,

pseudo-second order and double-exponential models is shown in Figure 28. It is found that

double-exponential model closely followed the experimental kinetic uptake data indicating both

chemisorption and physisorption governs the CO2 uptake kinetics on both mono and triamine

tethered PE-MCM-41.

Figure 27. Isotherm model plots for CO2 adsorption on TP-PE-MCM-41 (a) 30 °C, (b) 45 °C,

(c) 60 °C and (d) 75 °C [19]

42
Figure 28. Kinetic model plots for CO2 adsorption on TP-PE-MCM-41 (a) 30 °C and (b) 75 °C

[19]

6. Conclusions

Thermogravimetry analysis serves as a valuable tool to understand thermal events associated

with nanomaterials and polymer composites when subjected to heating under predetermined

heating rate and temperature conditions. Different types of microbalances such as null point and

deflection type balances are described and discussed adequately. Several case studies which

deal with different applications of TGA are also addressed. Case studies 1 and 2 explain different

degradation patter for chitosan composites under modified atmosphere. Case studies 3-5

describe application of advanced TGA instruments such as TGA-FTIR, TGA-MS and TGA/GC-

MS for prediction of reaction intermediates evolved through EGA as well as hypothetical

mechanism for thermal degradation mechanism for polymer nanocomposites and biomass.

Case studies 6 and 7 discuss about µ-TGA used for determination of CNT purity and amount of

DNA content in layer-by-layer coating on Au nanoparticle, respectively. Case studies 8 and 9

explain the method to evaluate the amount of drug as well as functional moieties loading in

porous silica material. Modified TGA Instrumental set up used for CO 2 adsorption study is

described in case study 10. The experimental method for determination of acidic strength in

zeolites using TGA-TPD instrument is explained in case study 11. Case studies 12 and 13

explain the application of several thermal degradation kinetic models to TGA data in order to

43
derive activation energy values for polymer nanocomposites. Case study 14 and 15 describe the

application of high pressure thermogravimetry balance to elucidate the mechanism of CO 2

adsorption and diffusion kinetics on bare PE-MCM-41 and triamine tethered PE-MCM-41.

6. References

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Himalaya Publishing House, 5 Edition, 2002.

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[16] Kumar, V.; Kumar, M.; and Pugazhenthi, G. Effect of Nanoclay Content on the Structural,

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