Chapter III

Results and Discussion of Synthesis

and Characterization of Nanosized
Polyaniline and its Nanocomposites
 CHAPTER III
Results and Discussion of Synthesis and Characterization of
Nanosized Polyaniline and its Nanocomposites

Introduction
We have prepared nanosized polyanilines and their nanocomposites by an in
situ chemical oxidative polymerization using interfacial polymerization process.
Synthesized products were subjected for various physico chemical characterization
techniques viz UV-Vis, FT-IR, XRD, TG-DTA, SEM/TEM etc. to confirm their
structural features.
This chapter describes the results and discussion about the Synthesis and
characterizations of naosized conducting organic polymer polyaniline (PANI) and its
nanocomposite

3.1 Optimization of Parameters

3.1.1 Organic Solvents
Organic solvent is the most important variable for interfacial polymerization
as it controls the interfacial tension and thus interface area between the immiscible
biphasic system [1]. These parameters were determined the rate of reaction, solubility
of growing polymer, morphology of the formed products [2]. In order to select the
best solvent we have tried six different organic solvents as mention in the table 3.1.
We observed that not only yield but morphology and doping level were also affected
by the solvents. Among these solvents chloroform was found to be good solvent in all
respect i.e. yield of polymer, doping level and homogeneity in the morphology and
hence we have carried out all the synthesis by using chloroform (CHCl 3) as solvent.
Among these solvents chloroform is having moderate polarity while all other solvents
are non- polar. Moderate polarity of chloroform increases the interactions with water
molecules which decreases the interfacial tension between aqueous – water
immiscible biphasic system than the other biphasic systems [3,4]. Due to decrease in
interfacial tension more interfacial area is developed at the interface of aqueous-
chloroform biphasic system, therefore maximum number of monomer from organic
phase and oxidising agent from aqueous phase meet and react at the interface and are
responsible for increasesing the extent of polymerisation.

46
 Table 3.1 Shows The % Yield Of Formed Polymer In Different Solvents
Sr. No. Solvent used % yield

1 Chloroform 42.74

2 Ether 38.83

3 Toluene 34.56

4 O-xylene 33.78

5 M-xylene 33.4

6 P-xylene 31.06

Increased interfacial area leads to co-axial allignment of polymer matrix

resulting the formation of homogenous nanofibers [5] FE-SEM micrographs as
shown in Fig. 3.1 reveals the homogenous morphology of nanosized polyaniline
obtained in chloroform, as compared to other solvents. Electronic spectra is a
powerful technique to acertain the extent of doping in the polymer chains. Fig. 3.2
represents the optical absorption spectra of polyanilines synthesized different organic
solvents.These spectras shows the presence of peak at 465 nm and increased
absorption tail at about 800 nm in all polymers which are characteristics of doping
state of polyaniline. From the attentative observation of the spectras one can see that
absorption at 800 nm is very intense in polymer synthesized using chloroform than
the all other solvents. Therefore we came to conclusion that the chloroform acts as a
good solvent for synthesis of nanosized polyaniline by liquid liquid interfacial
polymerization and we have selected the chloroform as a solvent for synthesis of
nanosized polyanilines and their nanocomposites.

3.1.2 Effect of Protonic Acids Used for Doping of the Polymer

Conductivity of organic conducting polymers can be varied by doping it with
different protonic acids. In order to choose the best dopant we have syntheised
polyaniline using various protonic acids such as Hydrochloric acid (HCl), Sulphuric
acid (H2SO4), Dodecyl benzene sulphonic acid (DBSA) and p-Toluene sulphonic acid
(p-TSA) and studied their effect on the conducting properties and solubility of the
synthesized polymers by conductivity measurement and electronic spectra. Table 3.2

47
Fig 3.1: Morphology of Polyanilines obtained in different organic solvents

48
Fig. 3.2 UV-Vis absorption spectra for the PANI Nano fibers in various organic
solvents (a-Toluene, b-Ether, c- P-Xylene, d- O-Xylene, e- Chloroform, f- M-
Xylene).

49
Table 3.2 shows the conductivity of Polyanilines doped with different protonic
acids

Sr. No. Protonic acid as dopant Conductivity of polyanilines in S/cm

1 Hydrochloric acid (HCl) 0.55 x10-5

2 Sulphuric acid (H2SO4) 0.96 x10-5

Dodecyl benzene sulphonic

3 0.12 x10-4
acid (DBSA)

Para Toluene sulphonic acid

4 1.01 x10-4
(PTSA)

Fig. 3.3 UV-Vis spectras of polyanilines doped with different protonic acid

50
shows the conductivity of Polyanilines synthesized using various protonic acids.
Polyanilines doped with PTSA shows higher conductivity compared to that doped
with HCl, H2SO4, and DBSA. This is also supported from its electronic absorption
spectra as shown in Fig. 3.3.
Absorption at about 800 nm was found to be greater and appears like a free
carrier tail in PTSA doped Polyaniline indicates effective doping. Due to larger size
and excess –SO3H group PTSA acts as an efficient dopant for polyaniline [6] and
forms PANI with high conductivity, solubility and mechanical stability. Thus
improving the overall performance of PANI for different applications. Relatively
larger size dopant reduces the interactions between conjugated polymer chains
resulting in polymers soluble in various organic solvents with high conductivity [7].

3.1.3 Ratio of Monomer to Oxidizing Agent

Extent of Polymerization at the interface of immiscible biphasic system is not
only depends upon the nature of organic solvent but also decided by the ratio of
monomer to oxidizing agent. For the synthesis of polyanilines, we have carried out
the polymerization using different ratios such as 1:0.5, 1:1 and 1:1.5. When ratio of
monomer to oxidizing agent is 1:0.5 i.e. as compared to monomer oxidizing agent is
less there is incomplete polymerization leads to very poor yield of polyanilines. When
the ratio is 1:1.5 there is agglomeration of polymer chains and yield is also decreased
by over oxidation [8]. But when the ratio is 1:1, the polymer was obtained with very
good yield and morphology. Fig.3.4 shows yield and morphology of the synthesized
polyanilines. Therefore throughout the synthesis we have kept the ratio of monomer
to oxidizing agent as 1:1.

51
 Fig. 3.4 Yield and morphology of polyanilines obtained at various ratios of
monomer to oxidizing agent

Therefore parameters optimized for synthesis of nanosized polyanilines and their

nanocomposites are:

1. Solvent i.e. organic phase:-

Chloroform
2. Doping agent:- Para toluene
sulphonic acid (PTSA)
3. Ratio of monomer to oxidizing
agent:- 1:1

52
PART- A
3.2 Synthesis and Characterization of Nanosized Polyanilines
3.2.1 Synthesis
Nanosized polyaniline was synthesized by chemical oxidative polymerization
of aniline using ammonium per sulphate as an oxidizing agent in an aqueous acidic
medium as shown in scheme I.

Scheme I Polymerization of Aniline using Ammonium Per Sulphate

Mechanism of Polymerization:-
Chemical oxidative polymerization was prorogated by radical mechanism [9,10]. It
consists of four steps.

Step I- Oxidation of Aniline to radical cation: - oxidizing agent force the aniline to
loose electron to form a radical cation. It has resonance stabilization .It is the slow
step and hence rate determining step.

53
Step II- Coupling of radical cation to form dicationic dimer
Formed N-radical cation couples with Para radical cation to form dicationic
dimer [11]. This subsequently loses proton to return to its original aromatic state and
gives an intermediate P-aminodiphenylammine [12,13].

Step-III – Chain Propagation to Form Trimer

Formed dicationic dimer further reacts with Para radical to form trimer and
subsequently forms tetramer and finally thus polymer in fully oxidized form
(Pernigraniline form).

Step IV – Reduction of Pernigraniline salt to Emeralidine salt

When all oxidized forms are used up then Pernigraniline salt is reduced by
unused aniline to green coloured conducting Emeralidine salt form [14].

54
Interfacial Polymerization
Interfacial polymerization is rapid, but more controlled approach is to take
advantage of the fast kinetics of the Polymerization at the interface between two
immiscible phases. Interfacial polymerization involves the reaction of monomer
dissolved in an organic phase with an oxidizing agent dissolved in an aqueous phase
at the interface between the two non-miscible phases In an interfacial polymerization
process/reaction, the polymerization was initiated at the boundary or at the interface
of an immiscible organic/aqueous system. The monomer molecules present in the
organic phase comes in contact with the oxidizing agent and acid, present in aqueous
phase and the polymerization get initiated. The initially formed polyaniline molecules
has affinity towards the water and get diffused in water phase from the boundary,
thereby second front of the monomer molecules come in contact with the oxidizing
agent and acid and the polymerization proceeds until all the monomer molecules
present in organic phase get reacted to form polyaniline. After completion of
reaction, the dark green coloured PANI was found to be diffused in the aqueous phase
as shown in Fig. 3.5.
3.2.2 Characterizations of nanosized polyaniline
To confirm the structural features of synthesized product characterization is an
important step after the synthesis. Polyanilines were characterized by various physical
and chemical characterization techniques. Spectroscopic techniques such as UV-Vis
and FT- IR are useful in investigating the oxidation and doping state of the
polyaniline. XRD technique is beneficial for studying the crystalline nature of the
polymer. To study the thermal stability of polyaniline, TG/DTA analysis is helpful.
To reveal the morphology of the polymer Scanning electron microscopy and
transmission electron microscopy are used. Electrochemical properties were studied
by cyclic voltammetry, galvanostatic charge-discharge electrochemical impedance
spectroscopy Conductivity was determined by two probe technique.

55
Fig.3.5 Schematic of the interfacial polymerization of aniline and formation of
polyaniline Nano fibers

56
3.2.2.1 UV-Vis Spectroscopic Study
The UV-Visible spectrum of the polyaniline dispersion in water was recorded
using Perkin Elmer Lambda -25 double beam spectrophotometer in the range of 300–
900 nm. Electronic spectra of polyaniline were recorded by dispersing the polyaniline
in aqueous solvent by sonication. Electronic absorption of conducting polymers is
useful in investigating the oxidation and doping state of the polymer backbone. The
optical absorption spectras of the polyaniline doped with p-TSA and dedoped
polyaniline (after treating with Ammonia) are presented in Fig. 3.6 (a) and (b)
respectively. Polyaniline doped with P-TSA exhibits s peak at 340 nm which
corresponds to the π-π* transition of the benzenoid rings, while the shoulder at 465
nm is attributed to the localized polarons which are characteristic of the protonated
polyaniline. The broad increasing absorption at higher wavelength (~ 800) nm with
free carrier tail confirms the presence of conducting emeraldine salt (ES) phase of the
polyaniline [15].
UV-Vis spectrum of emeraldine base form (EB) form of Polyaniline gives
two peaks with maxima at 325 nm for -* transition of benzenoid ring and at 635nm
for quinoid excitation bands [16,17]. Absence of a characteristic peaks at 465 and 800
nm confirms the doped form of polyaniline is converted to dedoped state after treating
with base NH3.

3.2.2.2 FT-IR Spectroscopic Study

To ensure the oxidative polymerization of monomer aniline into polyaniline
IR spectroscopy is an excellent technique. Using this vibrational spectroscopic tool
one can elaborate the structure of polyaniline FTIR spectroscopy of PANI reveals that
PANI is formed by 1- 4 coupling of aniline monomers and eliminates the possibility
product to a considerable extent. One can gain information about the presence of the
bands corresponding to both imine and amine type of rings in emeraldine state of
PANI [18,19]. Formation of copolymers, presence of a functional group on the
polymer backbone or change in the protonation-deprotonation equilibrium of
emeraldine can be deduced from the presence of corresponding bands in the FTIR
spectra. Fig. 3.7(a) & (b) illustrates the FT-IR spectra of polyaniline doped form
(emeraldine salt) and undoped form (emeraldine base) and shows all characteristics
vibrational frequencies of polyaniline which are in good agreement with theoretical
expectations[20].

57
 Fig. 3.6 (a) UV-VIS spectra of polyaniline in doped state (Emeraldine salt)

Fig. 3.6 (b) UV-VIS spectra of polyaniline in dedoped state (Emeralidine base)

58
 The presence of the two bands in the vicinity of 1500 cm-1 and 1600 cm-1 are
assigned to the non-symmetrical C6 ring stretching modes. The higher frequency
vibration at 1600 cm-1 has a major contribution from the quinoid rings while, the
lower frequency mode at1500 cm-1 depicts the presence of benzenoid ring units [21-
23]. The presence of these two bands clearly shows that the polymer is composed of
amine and imine units, which support our UV-Vis. spectroscopic characterization,
discussed earlier in which, different phases are observed in the spectrum. Band at
3300 cm-1 has been assigned to secondary ammine stretching vibration. Less
significant band at 3000cm-1 is because of aromatic C-H stretching. The vibrational
band at 1307cm-1 is arises due to C-N stretching of secondary aromatic amine
whereas the vibrational frequency at 1247 cm-1 is due to C-N+• stretching vibration.
Peak at 1155cm-1 has been attributed for NH+• stretching and indicating the
polyaniline is in the doped state. Doping state is supported by the peak at 1001 cm-1
due to S-O stretching of -SO3H group. Significantly the band at 1155 cm-1 is much
intense in case of FTIR spectra of doped polyaniline. Para coupling of phenyl rings in
polymerization of aniline has been confirmed by the appearance of a peak at 825 cm-1
which is a characteristic of C-H bending vibration of Para coupled diphenyl rings. All
vibrational frequencies for polyanilines are summarized in table 3.3

Table 3.3 Characteristic Frequencies of p-TSA doped Nanosized Polyaniline

Wavenumber (cm−1) Band Characteristics
668 C–S stretching of the benzenoid ring of p-TSA
825 C–H stretching indicating Para-coupling
1001 S-O stretching of p-TSA
NH+•, indicating PANI nanofibers is in the
1155
doped state
1160 stretching vibrations of the SO3H group
1247 C–N+• stretching
1307 C–N stretching of the secondary aromatic amine
1493 C=C stretching of benzenoid ring.
1573 C=C stretching of quinoid ring
3005 O-H stretching of PTSA
3300 free N–H stretching

59
 Fig.3.7(a) FT-IR spectra of polyaniline Emeraldine salt

Fig.3.7 (b) FT-IR Spectra Of Polyaniline Emeraldine Base

60
3.2.2.3 Morphological studies by FE-SEM and HR-TEM Analysis
To reveal the morphology of synthesized polyaniline, Scanning Electron
microscopy (SEM) is one of the most widely used technique. In this microscopic
approach high energy electron beam scan the sample surface and collect the
information regarding particle size and shape.
Figure 3.8 (a) and (b) shows the FE-SEM and HR-TEM micrographs of nano
sized polyaniline synthesized via static interfacial polymerization method. The
magnifications are selected such that the morphology could be seen clearly. The
morphology of the polymer, synthesized by interfacial polymerization methods offers
very interesting features and observed the Fibrillar/rod type of structure with
thickness ~ 90-100 nm and length up to few microns. By observing TEM images we
realized that formed fibers are hollow. The formation of the nanorods/Nano fibers
offered by the interfacial polymerization process is due to the controlled availability
of the monomer, at the junction of the organic and aqueous phase during the
polymerization. Very limited amounts of monomer molecules present in the organic
phase are interacting with the oxidizing agent, present in the aqueous phase.

3.2.2.4 X-ray Diffraction studies

X-ray diffraction technique was used to probe the structure of the polyaniline
nanofibers. Figure 3.9 shows the XRD pattern of the polyaniline Nano fibers
synthesized by static interfacial polymerization process. From the figure, it is
observed that two broad bands are centered at 2θ = 20o and 25o show that these Nano
fibers are partially crystalline. The sharp peak at 25o is characteristic peak for the
extent of π conjugation in the polyaniline. (The results coincide with the JCPDS file
no. 53-1891 and file no. 53-1717). This sharpness of the peak shows the longest order
of π conjugation [24,25].
The characteristic peaks appeared at 200 and 25°, corresponding to (020) and
(200) crystal planes of PANI. It is observed that the benzenoid and quinoid units are
more orderly arranged in p-TSA doped polyaniline. Synthesized via interfacial
polymerization [26]. By considering the higher intensity peak at 25o the average
particle size has been estimated by using Debye- Sherrer formula is about 78 nm
which is very good in agreement with particle size obtained in SEM analysis.

61
Fig. 3.8 (a) FE-SEM Micrographs of PTSA doped Nanosized polyaniline.

Fig. 3.8 (b) HR-TEM Micrographs of PTSA doped Nanosized polyaniline

62
3.2.2.5 Thermo gravimetric Analysis
Fig. 3.10 displays the thermal profile (TG/SDTA) of the polyaniline Nano
fibers synthesized by interfacial method using p-TSA as a dopant. From the figure it
is observed that the polymer exhibits a three-step decomposition pattern similar to that
of polyaniline synthesized by bulk polymerization process. The first step in the
decomposition pattern from RT-100°C is obviously due to the removal of free water
molecules/ moisture present in the polymer matrix. It is accompanying by sharp
endothermic peak observed at approximately 75oC signifies dehydration. The second
step loss starting from 100 to 3000 C is mainly due to the loss of the dopant ion from
the polymer chains (thermal dedoping), It is observed the endothermic peak at 275oC
is associated with removal of dopant ions present in the polymer matrix.
Dopant ions have remarkable effect on the thermal stability of doped
polymer. PTSA doped polyaniline shows greater thermal stability. Due to strong
electron withdrawing effect of –SO3H group attached to polymer chains prevent the
decomposition of polyaniline [27]. As second step weight loss is mainly due to loss of
dopant ion, one can estimate the weight of dopant from the weight loss as a function
of temperature. From 100-300oC there is about 15 % weight loss corresponds to
weight of dopant. Whereas the third step loss starting from 3000C onwards is
accounted for the degradation and decomposition of the skeletal polymer backbone
after the elimination of the dopant ion [20]. The sharp exothermic peak found at
350oC in PANI, at this point polyaniline chains starts to degrade into smaller chains.
The first derivative plot also reveals the similar weight loss pattern.

3.2.2.6 Conductivity Measurement

The room temperature solid state conductivity of the polymer was measured
on pressed pellets having a diameter of 1.5 cm using the two-probe conductivity
measurement technique. The conductivity of p-TSA doped polyaniline nanofibers is
found to be 1.01x10-4 S/cm, which is higher than that of synthesized by bulk
polymerization process.

63
 Fig. 3.9 XRD pattern of the p-TSA doped Nano sized polyaniline

Fig.3.10 Thermal profile of the p-TSA doped Nano sized polyaniline

64
PART B Polyaniline Nanocomposites

3.3 Polyaniline-Silver (PANI-Ag) nanocomposite

3.3.1 Synthesis of Polyaniline- Silver Nanocomposite, and Nanocomposite
Coated Cotton Fabric
When a precursor silver nitrate is used along with oxidising agent ammonium
persulphate (APS), Ag+ ions also serve as an oxidant for aniline monomer to produce
metallic silver nanoparticles along with polyaniline [28,29]. These metal
nanoparticles are attracted towards the polymer chains due to strong interactions of
metal nanoparticles and reactive immine groups of polymer and thus form PANI -Ag
nanocomposites (Scheme II). An in situ polymerization involves simultaneous
oxidation of monomer and reduction of precursor and distributes the filler metal
nanoparticles more homogenously in the polymer matrix than the ex –situ method.
Interfacial polymerization is a very controlled synthetic route for polyaniline as well
as it’s nanocomposite. Here advantage is taken of the limited availability of monomer
and oxidizing agent at the interface of the immiscible biphasic system. Polymerization
is takes place due to redox reaction of monomer aniline with oxidising agent only at
the interface, leads to formation of Fibrillar shaped Nano sized polyaniline along with
silver (Ag) metal nanoparticles, resulting in the formation of polyaniline silver
nanocomposite. In the presence of dopant sulphonic acid, it is obtained in its
hydrophilic emeraldine salt form. Highly hydrophilic nature drives nanocomposite
from the reaction site and diffused into the upper aqueous layer allow and next layer
of monomer reacts with oxidising agent and so avoids the overgrowth of polymer
chains resulting into the Nano size of material.
In an aqueous phase due to formation of weak Hydrogen bonding interactions
between -NH group of polymer and -OH group of cellulose, formed nanocomposite
gets attracted on the cotton fibre surfaces, convert nanocomposite into Ag-PANI-
cellulose ternary nanocomposite. And develops silver-polyaniline coated cellulose
fibres [30,31]. The very broad nature of N-H stretching was observed at 3440 cm-1 in
the IR spectrum supports these interactions.

65
 Scheme II Polymerization of aniline by Silver Nitrate [32 ]
3.3.2 Characterizations
3.3.2.1 UV-Vis Spectra
Typical electronic absorption spectra of PANI -Ag nanocomposites are shown
in Fig. 3.11.The spectrum shows two absorption peaks at about 330nm and 450nm,
and one absorption peak at 900nm. The peak at 330nm is attributed to the π-π*
transition of benzenoid rings of polyaniline. A shoulder at 450nm is due to the η-π*
excitation of the quinonediimine structure (N=Q=N-quinoid) in PANI. The surface
Plasmon resonance of the silver nanoparticles embedded in the polymer matrix
appears at the wavelength 448nm which is overlapped by the polaranic peak of PANI.
Increasing absorption at about 900nm may be due to the conducting emeraldine salt
phase of the Polyaniline, and it conforms the effective doping of the polymer [33].

3.3.2.2 FT-IR Spectra

Figure.3.12 represents the FTIR spectra of PANI –Ag nanocomposite. The
presence of characteristic peaks of PANI indicates the successful polymerization

66
 Fig.3.11 UV-VIS spectra of Polyaniline-Silver nanocomposite.

Fig.3.12 FT-IR Spectra Of Polyaniline-Silver (PANI-Ag) Nanocomposites

67
of aniline. Peak at 3440 cm-1 shows free N-H stretching, and this peak shifts to 3100-
3300 cm-1 and becomes broader, indicating that there is interaction of –NH group with
silver nanoparticles in PANI-Ag nanocomposites [34] as well as –OH group of
cellulose fibers, indirectly proving the presence of Ag nanoparticles in the
nanocomposites. This peak is supported by appearance of a peak at 800 cm-1 due to
N-H out of plane bending vibration for benzenoid unit. The peaks around 1000-1300
cm-1 are due to C-C and C-N stretching vibrations of the polymer. Peaks at 1584 and
1500 cm-1 indicates quinonediimine and benzenoid diamine ring stretching,
respectively. Whereas the bands at 1300-1200 cm-1 is assigned to the C-N stretching,
vibration modes of the benzene ring. Peak at 1144 cm-1 indicates PANI nanofibers are
in doped state.

3.3.2.3 X-ray diffraction

In order to examine the structure and composition of formed nanocomposite
X-ray diffraction technique was used. Figure 3.13 (a) depicts the XRD pattern of the
PANI -Ag nanocomposite. The presence of characteristic Bragg diffraction peaks
with 2 = 38.11, 44.30, 64.43 and 77.5 can be seen in the XRD patterns of
nanocomposite are the characteristic of silver nano particles, which correspond to the
face centered cubic (FCC) phase of silver. The observed four peaks are corresponding
to (111), (200), (220) and (311) planes of silver respectively that matches with the
JCPDS file No.04-0783 [35]. These sharp peaks clearly indicate the existence of
silver nanoparticles in the composites and their crystalline nature. Along with these
sharp peaks two broad bands centered at 2 - 20.02o and 25.84o are characteristic
diffraction of amorphous polymer. The peaks appeared at 20.02 and 25.84 are
corresponds to (020) and (200) planes of polyaniline coincide with JCPDS file nos.
53-1819 and 53-1717. Appearance of all characteristic peaks related to polymer and
silver nanoparticles certainly explained the in situ development of polyaniline–silver
nanocomposite. It is very well supported from its Elemental analysis by EDX as
shown in fig. 3.13 (b). By considering the highest intensity peak at 38.11 the average
particle size for silver nanoparticles present in the composite determined ( by using
sherrer equation) is around 28 nm which is very close in size obtained by SEM
analysis.

68
Fig. 3.13 (a) X-ray diffraction pattern and (b) Elemental analysis of silver
nanocomposites showing by EDX

69
3.3.2.4 Morphological studies by FE-SEM and TEM analysis

FE-SEM Analysis
The morphology of PANI–Ag nanocomposite was studied by scanning
electron microscopy and Transmission electron microscopy. Interracial
polymerization allows the reaction along the interface and offers very interesting
Fibrillar morphology for the polymer confess well from its FE-SEM images. The
Fig.3.14 shows the micrographs of nanocomposite at various magnifications
illustrating the fiber like morphology of the material. The average diameter of the
resultant PANI-Ag fiber is found to be about 50-60 nm. Fig. 3.15 shows the FE-SEM
micrographs of cotton fibers coated with PANI-Ag nanocomposite. From the
micrographs it is observed that there is a uniform coating of the nanocomposite on the
cotton fibers.

 HR-TEM Analysis
The presence of spherical silver nanoparticles in the polymer matrix were
revealed by TEM micrographs of nanocomposite material. Fig. 3.16 shows the
presence of black coloured spherical silver nanoparticles are distributed in the
polymer matrix. Interaction of silver nanoparticles with reactive immine groups of
polymer encloses metal nanoparticles inside the polyaniline fibres seen under high
magnification which are also confirmed by XRD and EDX analysis of resultant
nanocomposite. The average size of the silver nanoparticle is around 15-20nm.

70
Fig.3.14 FE- SEM images of Polyaniline-silver (PANI-Ag) nanocomposite

71
Fig.3.15 SEM images of Cotton Fibres Coated With PANI-Ag Nanocomposite

Fig. 3.16 TEM Images Of Polyaniline- Ag Nanocomposite (a-d)

72
3.4 Polyaniline – MWCNTs ( PANI-MWCNTs) Nanocomposite
3.4.1 Formation of Nanocomposite
Introduction of carboxylic groups on the sidewalls of CNTs via chemical
functionalization plays a crucial role in the development of PANI-MWCNTs
nanocomposites and more than that improve its electrical conductivity, solubility/
dispersibility in aqueous medium. The carboxylic groups at the CNTs are apparently
acting as sites of interactions for monomer aniline. Fig.3.17 represents the schematics
of functionalization and formation of MWCNTs nanocomposites Chemical
interactions occur between polar –COOH group of CNTs and most reactive imine
group of polyaniline [36]. Besides these interactions there is also strong -
interactions between polymer chains and hexagonal lattice of CNTs [37,38] entailed
the formation of core shell like structure of the composite. FE-SEM characterization
reveals the uniform wrapping of MWCNTs by thin layer of polyaniline chains.

Fig. 3.17 Schematic of the synthesis of Core –Shell type polymer nanocomposite

73
3.4.2 Characterizations
3.4.2.1 UV-Vis Spectroscopy
Fig. 3.18 represents the UV-Vis spectra of PANI-MWCNTs nanocomposite. It
shows characteristic absorption bands at 315nm contributed for -*transition of
benzenoid rings of PANI. The peak at 465 nm is corresponds to the excitation of
Quinone diimmine structure (N=Q=N, Q: quinoid) of polyaniline. While, the
increasing absorption at higher wavelength (~ 800) nm associated with the transition
from valence band to polaron band characteristics of the emeraldine salt form of
PANI confirms the conducting state of the polymer.Functionilized MWCNTs does
not shows any absorption above 300 nm.

Fig.3.18 UV-VIS Spectra of Polyaniline –MWCNTs (PANI-MWCNTs)

Nanocomposite.

74
3.4.2.2 FT-IR Spectroscopy
FT-IR spectroscopy is an excellent technique for structural investigations of
PANI-MWCNTs nanocomposite. Fig.3.19 shows the FT-IR spectras of non-
functionalised MWCNTs, Functionalised MWCNTs and PANI-MWCNTs
nanocomposite. Spectra of functionilised MWCNTs shows characterstic peak at
1641 cm-1 and broad peak at 3444 cm-1 are assigined to C=O and –O-H stretching of –
COOH group respectively. Appearance of both these peaks in the IR spectrum
confirms the presence of -COOH groups in the sidewall of MWCNTs [39-41].
The composite contains all the characteristics peaks of PANI in emeraldine salt
form which in turn indicates the successful polymerization of aniline. The
characteristic peaks at 1496 cm-1 and 1541 cm-1 are due to C=C stretching vibrations
of quinoid and benzenoid rings respectively. Both these peaks confirm the presence of
amine and imine units along the polymer backbone. The vibrational frequency at 3748
cm-1 is assign to N-H stretching vibration mode which is supported by the appearance
of peaks in the region of 1218cm-1 due to C-N stretching.
In IR spectra of pure polyaniline the N-H stretching vibration peak is appears at
3300cm-1 which is shifted at 3700cm-1 in polyaniline–CNT nanocomposite ascertained
the formation of amide type of bonding between reactive immine group of polyaniline
and carbonyl group of MWCNTs. .In addition to these above peaks, the presence of
MWCNTs in the composites results in the appearance of a peak at 1641 cm-1 and 3444
cm-1 relates to the C=O stretching and –OH stretching of –COOH groups present at
the sidewalls of CNTs, as these peaks are absent in the IR spectra of pure polyaniline.

3.4.2.3 X-ray diffraction studies

The strongest diffraction peak at the angle 2θ of 25.5° can be indexed as the (002)
reflection of the hexagonal graphite structure [42,43]. The other characteristic
diffraction peaks of graphite at 2θ of about 43°, 53° and 77° are associated with
C(100), C(004) and C(110) diffractions of graphite, respectively [44]. The appearance
of high intensity peaks at 2θ=19.04 and 25.79 are indicative of dominance of
polyaniline in the nanocomposite

75
Fig.3.19 FT-IR spectras of a) Non functionalized MWCNTs b) functionalized
MWCNTs c) Polyaniline –MWCNT (PANI-MWCNTs) d) pure polyaniline
(PANI)

Fig. 3.20 XRD spectrum of PANI –MWCNTs Nanocomposite

76
3.4.2.4 Morphological studies ( FE-SEM and HR-TEM Analyais)

Introduction of carboxylic groups on the sidewalls of CNTs via chemical

functionalization plays a crucial role in the development of PANI-MWCNTs

nanocomposites. The carboxylic groups at the CNTs are apparently acting as sites of

interactions for polymer chains. Chemical interactions occur between polar –COOH

group of CNTS and most reactive imine group of polyaniline. Besides these

interactions there is also strong - interactions between polymer chains and

hexagonal lattice of CNTs entailed the formation of core shell like structure of the

composite. FE-SEM and TEM characterization reveals the uniform wrapping of

MWCNTs by thin layer of polyaniline chains. Fig 3.21 and 3.22 represents FE-SEM

and TEM micrographs respectively of the nanocomposite material. It illustrates the

core shell like structure with average diameter  28-50 nm and length up to few

microns. Interfacial polymerization of monomer aniline in the presence of MWCNts

provides the formation PANI-MWCNTs nanocomposite at the interface of aqueous –

organic biphasic system due to the controlled avaibility of monomer and oxidant. As

the formed polyaniline is in its hydrophilic emeraldine salt form gets diffuses in the

aqueous layer and interacted towards the dispersed CNTs results in development of

sulphonic acid doped PANI-MWCNTs nanocomposite.

77
Fig. 3.21 FE-SEM images of PANI-MWCNTs nanocomposite

Fig. 3.22 HR- TEM images of PANI-MWCNTs nanocomposite

78
3.5 PANI-MnO2 Nanocomposite
3.5.1 Formation of PANI-MnO2 nanocomposite
In an interfacial polymerization, there is a redox reaction at the interface of
water-chloroform immiscible biphasic system, Where monomer aniline from organic
phase was chemically oxidised by MnO4- ions present in the aqueous phase and itself
get reduces to manganese dioxide (MnO2). Formed MnO2 get embedded in the
polymer matrix and finally gives PANI-MnO2 nanocomposite. As synthesized
nanocomposite is obtained in the hydrophilic emeraldine salt form get diffused into
aqueous layer.
3.5.2 Characterizations
3.5.2.1 UV-Vis spectra
Electronic structure of the resultant material was revealed from its electronic
structure. Fig. 3.23 represent the Uv-Vis spectra of the PANI-MnO2 nanocomposite.
A very sharp, low intensity absorption peak at 340 nm is due to manganese oxide
nanoparticles [45]. The characteristic absorption peak at 470 nm and 800 nm are
attributing for π –polaron and polaron –π* excitation confirms the formation of
doping state of polyaniline. Very high absorption of polyaniline characteristic peaks
as compared to MnO2 peak prove the dominance of polyaniline in the nanocomposite.
3.5.2.2 FT-IR spectroscopy
FT-IR spectra was used to ascertain the composition of nanocomposite.
Inorganic oxides usually show absorption peaks in the fingerprint region. MnO2
shows the corresponding antisymmetric stretching modes are recorded in the FTIR
spectrum at 517 and 621 cm-1.The bands at 515 and 480 cm-1 correspond to the Mn–
O bond stretching [46,47]. Along with all characteristic peaks of MnO2 FTIR spectra
of nanocomposite shows the presence of all characteristics peaks for polyaniline
confirms the formation of polyaniline –MnO2 nanocomposite. Peak at 3440 cm-1
shows free N-H stretching, and this peak is supported by observation of a peak at 800
cm-1 due to N-H out of plane bending vibration for benzenoid unit. The peaks around
1000-1300 cm-1 are due to C-C and C-N stretching vibrations of the polymer. Peaks at
1584 and 1500 cm-1 indicates quinonediimine and benzenoid diamine ring stretching,
respectively. Whereas, the bands at 1300-1200 cm-1 is assigned to the C-N stretching,
vibration modes of the benzenoid ring. Peak at 1144 cm-1 indicates PANI nanofibers
are in doped state.

79
 Fig. 3.23 UV Vis spectra of PANI-MnO2 nanocomposite

Fig. 3.24 FT-IR spectras of PANI-MnO2 nanocomposite and Pure PANI

80
3.5.2.3 XRD Analysis
Powder X-ray diffraction method is used to study the degree of crystallinity of
the material. Fig.3.25 illustrates the XRD pattern of Polyaniline-MnO2 nanocomposite
and pure polyaniline. The appearance of high intensity peaks at 2θ=19.04 and 25.79
are indicative of dominance of polyaniline in the nanocomposite .All characteristic
peaks of MnO2 are broad and indicate the mixed phase of MnO2.Tthe peaks at 2θ=
28.67 36.59, 43.1, 50.30 are index able to γ-MnO2 phase [48] (JCPDS card.no.14-
0644) and peaks at 2θ = 11.9,18.1,28.6, 37.4, 49.8 can be indexed to a pure tetragonal
phase of α-MnO2 [50] (JCPDS 44-0141). The broadness of the peaks indicates that
the formed compound has predominantly nanophase.By considering the peak of
higher intensity at 2θ =19.04o the average particle size has been estimated by using
Debye –Sherrer formula is about 30 nm which is in very good agreement with the
results obtained from SEM analysis.
3.5.2.4 Thermo gravimetric Analysis
TG-DTA analysis is used to study the thermal behavior of PANI-MnO2
nanocomposite in comparison with polyaniline. It is observed from fig 3.26, the TGA
of both PANI and PANI-MNO2 nanocomposite shows three step decomposition
pattern. In the fist there is about 5% loss upon heating from room temp to 150 oC due
to loss of surface water from both polymer matrix and oxide[49]. it is accompanying
by sharp endothermic peak observed at approximately 75oC signifies dehydration.
Afterwards from temperature 150-400oC there is a loss of 15% weight and observed
the endothermic peaks between 300-350oC are associated with removal of dopant ions
as well as water present in the polymer matrix[51]. From 400oC onwards the massive
weight loss is started is attributed for degradation and decomposition of polymer[52].
About 93 % wt. lost is occurs in the range of 400-800oC. The sharp exothermic peak
found at 350oc in PANI. At this point polyaniline chains starts to degrade into smaller
chains. But in the TGA of nanocomposite this exothermic peak is shifted at higher
temperature at about 430oc convinced the presence of MnO2 assist the nanocomposite
with high thermal stability. This high thermal stability is due to adsorption of
polymer chains on the surface of MnO2 nanoparticles, results in the restriction of
segmental mobility and serves to put down the redistribution and chain transfer
reactions [53] The two small exothermic peaks in the range of 500 -650oc are
observed in TGA of nanocomposite corresponds to conversion of MnO2 to Mn2O3.

81
Fig. 3.25 XRD pattern of PANI-MnO2 and Pure PANI

82
Fig. 3.26 (a) Thermo gram of nanosized Polyaniline (PANI)

Fig. 3.26 (b) Thermo gram of PANI- MnO2 nanocomposite

83
These peaks are not observed in the TGA curve of polyaniline indirectly prove the
composition of PANI-MnO2 nanocomposite.

3.5.2.5 Morphological Studies (FE-SEM/HR-TEM analysis) Morphological

features of the as prepared PANI-MnO2 nanocomposite are studied by FESEM and
HRTEM analysis. Fig. 3.27 display the FE-SEM images of the resultant composite
at different magnifications. The micrographs clearly shows that highly homogenous
nanofibers with average diameter 15- 25 nm are orderly arranged to offer very
attractive marigold flowers like morphology. The high resolution FESEM pictures
shown in figure clearly exhibits the flowers are seems with open petals to form
unique hollow microstructure with well-defined mesoporosity. Therefore it has more
surface area and more uniform pore size distribution. That will be more advantageous
for charge storage, electrolyte transport and avaibility of active sites in
electrochemical applications [54].
The hollow sphere morphology can be revealed from its formation
mechanism. In interfacial polymerization ,very slow reaction at the interface of
immiscible biphasic system favours the self-accumulation of nanofibers into hollow
spheres. The presence of spherical MnO2 nanoparticles embedded in the polyaniline
fibres are seen in the TEM images presented as figure 3.28 (a-c). Which is also
confirmed from its EDS spectra presented as Fig. 3.28 (d) shows the presence of
element of Mn.

84
Fig. 3.27 FE-SEM images of Polyaniline-MnO2 nanocomposite

85
Fig. 3.28 TEM images and EDX spectrum of Polyaniline – MnO2 nanocomposite.

86
3.5.2.6 Surface Area Analysis
PANI-MnO2 nanocomposite was also characterized by Nitrogen adsorption
desorption tests, to investigate the specific surface area and pore size distribution and
the resulting isotherm is given in fig. (3.29). The observed shape of the isotherm
corresponds to the mixed II and IV types of isotherm according to IUPAC. These
shapes suggests the presence of Meso and macropores in the nanocomposite. The
material shows a BET surface area of 34.31m2g-1. According to Barrett–Joyner–
Halenda (BHJ) pore size distribution data the average pore size is in the range of 10-
80 nm confirming the meso and macro porosity in the material and also evident the
Formation of hierarchical architectures resembles flower, obtained from aggregates
of petal like particles as shown in SEM micrographs. BET isotherm shows that
primary adsorption occurs relatively at low pressure upto 0.1 but there is a linear
absorption between 0.1 to 0.9 relative pressures, indicates the largest mesophorous
region of the fraction. An account of uniform, large pore diameter and a high surface
area, mesophorous material acts as an excellent host [55].At 0.9p/po, there is highten
the uptake of N2, confirms the presence of macropores in the sample.

250
Adsorption
Desorption
Adsorbed volume(V/cm3(STP)g-1

200
0.8

0.7

0.6

0.5
150
dVp/dlog(rp)

0.4

0.3

0.2

0.1

0.0
100 0 50 100
rp/nm

50

0.0 0.2 0.4 0.6 0.8 1.0

P/P0

Fig.3.29 N2 adsorption-desorption isotherm with their respective pore size

distribution for PANI-MnO2 nanocomposite ( inside graph)

87
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