ELECTROACTIVE POLYAMIDE/CuO COMPOSITE FOR

ANTICORROSIVE APPLICATIONS
Thesis submitted to
Visvesvaraya National Institute of Technology, Nagpur
In partial fulfilment of requirement for the award of
Degree of

BACHELOR OF TECHNOLOGY
(METALLURGICAL AND MATERIALS ENGINEERING)
Submitted By
K. SRIPATHI DEV SHARMA BT14MME032
KULDEEP CHOUDHARY BT14MME033
POTHAMSETTY ANIL BT14MME044
SUDARSHAN.R.SHELKE BT14MME060
AVTAR SINGH BT14MME010
Under the guidance of

Dr. R.C. Rathod Dr. S.S. Umare

Associate Professor Professor
Department of Metallurgical Department of Chemistry
And Materials Engineering, VNIT, Nagpur
VNIT, Nagpur

Department of Metallurgical and Materials Engineering

Visvesvaraya National Institute of Technology
Nagpur 440010 (India)
2017-2018
 DEPARTMENT OF METALLURGICAL AND

MATERIALS ENGINEERING

VISVESVARAYA NATIONAL INSTITUTE OF TECHNOLOGY

NAGPUR-440010

CERTIFICATE
This is to certify that the project entitled “Electroactive Polyamide/CuO composites for Anticorrosive
Applications” submitted by Avtar Singh, K. Sripathi Dev Sharma, Kuldeep Choudhary,
Pothamsetty Anil and Sudarshan. R. Shelke in partial fulfilment of the requirement of the award of
Bachelor of Technology in Metallurgical and Materials Engineering, VNIT, Nagpur is a record of
students own work carried out by them under my guidance and supervision.

Dr. R.C. Rathod Dr. S.S. Umare

Department of Metallurgical and Department of Chemistry

Materials Engineering, VNIT, Nagpur
VNIT, Nagpur

i
 DEPARTMENT OF METALLURGICAL AND

MATERIALS ENGINEERING

VISVESVARAYA NATIONAL INSTITUTE OF TECHNOLOGY

NAGPUR-440010

CERTIFICATE
Forward here with the thesis entitled “Electroactive Polyamide/CuO composites for Anticorrosive
Applications”. This thesis is being submitted by K. Sripathi Dev Sharma, Kuldeep Choudhary,
Pothamsetty Anil and Sudarshan. R. Shelke, Avtar Singh in partial fulfilment of the requirement of the
award of Bachelor of Technology in Metallurgical and Materials Engineering, VNIT, Nagpur is a
record of students own work carried out by them under my guidance and supervision.

The matter embodied in this dissertation is original and has not been submitted to any other institute for
the award of any degree.

Dr. J. G. Bhatt

Head of Department
Dept. of Metallurgical
And Materials engineering
V.N.I.T. Nagpur

ii
 DEPARTMENT OF METALLURGICAL AND

MATERIALS ENGINEERING

VISVESVARAYA NATIONAL INSTITUTE OF TECHNOLOGY

NAGPUR-440010

DECLARATION
This dissertation is submitted for the award of degree of Bachelor of Technology in Metallurgical and
Materials Engineering) at VNIT, Nagpur. The work reported herein was carried out under the
supervision of Dr. R.C.Rathod and Dr. S.S.Umare during the period 2017-2018.

To the best of my knowledge, this work is original, except where suitable references are made to previous
work. Neither this, nor any substantially similar dissertation has been submitted for any degree, diploma
or qualification at any other university or institution.

(Submitted by)

K. SRIPATHI DEV SHARMA - BT14MME032

KULDEEP CHOUDHARY - BT14MME033

POTHAMSETTY ANIL – BT14MME044

SUDARSHAN. R. SHELKE – BT14MME060

AVTAR SINGH - BT14MME010

iii
 ACKNOWLEDGEMENT

First I would like to express my deepest and sincere gratitude to my main supervisor, Associate
professor Dr. R. C. Rathod for his huge support and encouragement. His wide knowledge and logical
thinking have been of great value for us. It was a privilege being your student and we wish we would
keep learning from you.

I would like to thank my co-supervisor professor Dr. S. S. Umare for the valuable courses,
discussion and feedbacks regarding the project.

I also thank Dr. J. G. Bhatt, Head of the Department, Metallurgical and Materials Engineering,
VNIT Nagpur for extending the departmental facilities for my research.

I am grateful to Mr. Jeetendra Kumar Malav, Miss. Kavita Pande, Miss. Swamini Chopra and Mr.
Jeetendra Chauhan for their help to carry out my project successfully.

I am extremely grateful to all the faculty and staff of the Department of Metallurgical and
Materials Engineering.

iv
Electroactive polyamide/CuO composites for Anticorrosive applications

Abstract
This project presents the synthesis of Electroactive polyamide/ CuO composites using oligoaniline and 1-
4 phenylenediamine and CuO particles by oxidative coupling polymerization. The synthesized polymer
products have been characterized by using X-Ray diffraction, Fourier Transform Infrared spectroscopy,
TGA, Scanning electron microscopy and Conductivity measurement method. The structural and
morphological aspects of all synthesized samples have been confirmed using FTIR, SEM and XRD.
Thermogravimetric results revealed that CuO particles could improve the thermal stability of the
composites. The electrical properties of EPA/CuO composites did not show any significant effect on
increasing CuO content in the composites. It has been found from the polarization study that, the
EPA/CuO composite coated 304 SS showed better Anticorrosive properties than bare 304 SS samples.

v
TABLE OF CONTENTS

CHAPTER 1: INTRODUCTION 1

CHAPTER 2: LITERATURE SURVEY 4

2.1. POLYAMIDE (PA) 5
2.1.1 Structure of Polyamide 6
2.1.2 Synthesis Methods of Polyamide 6
2.1.3 Types and properties of Polyamide 9
2.1.4Application of Polyamide 11
2.2 ELECTROACTIVE POLYMERS (EPA) 12
2.2.1 Properties of Electroactive polyamides 12
2.2.2Applications of Electroactive polyamides 13
2.3 ELECTROACTIVE POLYAMIDE (EPA)/CuO COMPOSITES 13
2.3.1. Properties of CuO 13
2.3.2. Applications of CuO 14
2.3.3. EPA and CuO composite applications 14
2.4 CHARACTERIZATION TECHNIQUES OF EPA/CuO COMPOSITES 14
2.4.1. Electrical conductivity measurements 14
2.4.2. FTIR Spectral Analysis 15
2.4.3. X-Ray Diffraction (XRD) Analysis 15
2.4.4. Scanning Electron Microscope (SEM) 16
2.4.5. Thermogravimetric Analysis (TGA) 16

CHAPTER 3: EXPERIMENTAL WORK 18

3.1 Chemicals and Materials 19
3.2 Synthesis of Oligoaniline 19
3.3 Synthesis of Electroactive Polyamide 21
3.4 Synthesis of Electroactive Polyamide/ CuO composites 23

CHAPTER 4: CHARACTERIZATION OF EPA AND ITS COMPOSITES 24

4.1. Electrical Conductivity of EPA and its composite 25
4.2. FTIR Spectral Analysis 25

vi
4.3. X-Ray Diffraction (XRD) Analysis 26
4.4. Scanning Electron Microscopy (SEM) 27
4.5. Thermogravimetric Analysis (TGA) 28
4.6. Biologic Potentiostat 8 channel for Corrosion studies 29

CHAPTER 5: RESULTS AND DISCUSSION 31

5.1. Electrical Conductivity of EPA and its composite 32
5.2. Fourier Transform Infra Red studies of EPA and its composite 33
5.3. X-Ray Diffraction of EPA 38
5.4. Scanning Electron Microscope of EPA and its composite 43
5.5. Thermal Stability of EPA and its composite 48
5.6. Anticorrosive property of EPA/CuO composites 50

CHAPTER 6: CONCLUSION 52

REFERENCES 54

vii
LIST OF FIGURES
Figure Name Page no
number
Figure 2.1 Basic amide form 6
Figure 2.2 Synthesis of Polyamide from Solution polycondensation of 7
a di-amine and a di-acid chloride.
Figure 2.3 Transition metal catalyzed carbonylative coupling of 7
aromatic di-amines and di-halides
Figure 2.4 Synthesis of Polyamide by condensation reaction 8
involving acid and amine in presence of triphenyl
phosphate
Figure 2.5 Synthesis of Polyamide from Interfacial polycondensation 9
of di-amine and di-acid chloride
Figure 2.6 Schematics of the molecular structures of odd numbered 13
and even numbered nylons
Figure3.1 Schematic representation of synthesis of oligoaniline 20
Figure3.2 Schematic representation of synthesis of Electroactive 22
Polyamide
Figure 3.3 Schematic representation of synthesis of Electroactive 23
Polyamide/CuO composite
Figure 4.1 Schematic representation of Fourier Transform Infra red 26
Spectrophotometer
Figure 4.2 Schematic representation of X-Ray Diffractometer 27
Figure 4.3 Schematic representation of SEM JEOL 6380A 28
Figure 4.4 Schematic representation of Thermogravimetric Analysis 29
Figure 4.5 Schematic representation of Biologic Potentiostat 8 30
channel
Figure 5.1 FTIR spectra of oligoaniline 33
Figure 5.2 FTIR spectra of Electroactive polyamide 34

viii
Figure 5.3 FTIR spectra of EPA/3%CuO Composite 35
Figure 5.4 FTIR spectra of EPA/6%CuO Composite 36
Figure 5.5 FTIR spectra of EPA/9%CuO Composite 37
Figure 5.6 XRD pattern of EPA 38
Figure 5.7 XRD pattern of CuO 39
Figure 5.8 XRD pattern of EPA/3%CuO Composite 40
Figure 5.9 XRD pattern of EPA/6%CuO Composite 41
Figure 5.10 XRD pattern of EPA/9%CuO Composite 42
Figure 5.11 SEM IMAGE OF EPA 43
Figure 5.12 SEM image of CuO 44
Figure 5.13 SEM image of EPA/3%CuO composite 45
Figure 5.14 SEM image of EPA/6%CuO composite 46
Figure 5.15 SEM image of EPA/9%CuO composite 47
Figure 5.16 TGA analysis of EPA and EPA/CuO composites 49
Figure 5.17 Polarization behaviour of 304 SS, EPA and EPA/CuO 51
composites

ix
LIST OF TABLES

Table No Name Page No

Table 5.1 Electrical Conductivity of EPA and EPA/CuO 32
composites.
Table 5.2 Weight loss data for EPA and EPA/CuO (3, 6 and 9%) 48
composites at different temperatures.
Table 5.3 Polarization test results of Bare 304 SS, EPA and 50
EPA/CuO composites

x
CHAPTER 1

INTRODUCTION

1
1. INTRODUCTION:

Corrosion is the phenomena by which the surface of metals/alloys disintegrates within specific
environment. The high corrosion resistance of some metals compared to others can be attributed to
several factors like their chemical constituents, the nature of electrochemical reactions itself and other
such factors. The corrosion resistance of metals determines to a large extent the operational lifetime of
components in service. Also, there is a chance that corrosion might result in effects harmful to the
material usage, the environment or the technical systems of which these form a part. However, there are
numerous advantageous uses in respect of corrosion. Based on the good physical, mechanical, and
chemical properties of materials, they are used by human beings to achieve their technological prowess.
Based on reaction mechanism corrosion can be classified as hence it can be physical, chemical or
electrochemical. Corrosion involves knowledge of several fields like effects of oxygen and oxidizers,
temperature, velocity, corrosive concentration, galvanic coupling, metallurgical factors and others.
Corrosion is an adversely affecting environmental and technological issue, causing wastage of money.
Addressing to this problem, a good amount of work has been going on since the past few decades in the
field of anticorrosive product development. However, there have been a few drawbacks such as the
hazardous chemicals like chromates which are carcinogenic and zinc which requires high pigment volume
concentration leading to negative environmental effect are being used for protection of metals from
corrosion. This has become a major threat to environment and human health, aggravating the pollution
problems. Hence, considering the existing limitations of coating system and the pollution issues, there is a
need to develop a coating material with superior properties to protect the metals from corrosion.
While dealing with severe corrosion, selecting the right material is crucial. The solution to the failure due
to corrosion is by fabricating anticorrosion coatings with superior chemical and mechanical properties
compared to the parent material. These coatings enable more efficient metals/components, cost reduction,
efficient industrial operations, saving of scarce material resources and reduction in pollutant emissions.
For development of anticorrosive coatings, new materials including composites, nano-composites and
nano-particles are used since almost all engineering materials (metals, composites, alloys, polymers and
ceramics) can be used as coatings on materials surfaces.

Recent anticorrosive coating applications

Barrier creation between substrate materials and environments, inhibition of the corrosion processes, and
coating acting as sacrificial materials are the three common mechanisms for anti-corrosive coatings. Zinc
and chromium-based materials are used mostly as coatings but due to strict rules and regulations in terms
of Health, Safety and Environment by many agencies, the latter usage had drastically reduced in the last

2
decade. Further, the hybrid materials comprising of UFG (Unfuctionalised Graphene) and
polyetherimides were proclaimed as suitable materials for anti-corrosive coatings to protect low alloy
steel. Some recently researched anti-corrosive coatings include, deposition of diamond-like carbon
coating (DLC) on AZ31 magnesium alloy by ion beam deposition technique with CrN acting as inter-
layers, effect of inter-layers on the corrosion resistance of DLC on magnesium alloy. However, the results
obtained weren’t satisfactory. In 2004, new monomer multisilicon compounds which can act as more
durable adhesive and anticorrosion coating materials were developed by Hashem. He concluded that the
isomers were organo-multi-silicon monomer compounds which performed creditably well as durable
adhesive and anticorrosion coating materials.

The emergence of electronically conducting polymers as a new class of materials in the past few
decades has attracted much attention. A broad spectrum of potential commercial applications in
optical, biological, electronic and defence industries has been exhibited by this class. Polyaniline
(PANI), being one of the most remarkable conducting polymers is excellent for its low cost, good
environmental stability, easy synthesis, improved electrical properties, well behaved electrochemistry
and moderately high conductivity in the doped state made it a candidate for a variety of applications
such as electromagnetic interference shielding materials, electrochromic display devices,
electroluminescent, biosensor. The major drawbacks of PANI which include, containment of defect
sites, ill-defined structure, poor solubility and processability, has greatly impeded its practical
applications and a better understanding of the structure–property correlations and the conducting
mechanism of PANI. Oligoanilines, carrying remarkably similar electronic properties to those of PANI
and having a wide range of application, have been considered as ideal candidates of PANI. However,
the inadequate aspects of oligoanilines are lacking of good stability and mechanical properties
compared to that of polymers. Therefore to open new avenues for applications, attempts to synthesize
electroactive polymers with positive mechanical and physical properties based on oligoanilines might
be a wise choice. Adhering to this ideology, modification of conventional processable polymers with
oligoanilines via covalent bond has created a series of novel functional polymers, which could avoid
the drawbacks of agglomeration and phase separation in PANI/insulating polymer blends prepared by
physical mixing methods. Currently, aniline oligomer-derivating electroactive polyamide had attracted
considerable research attentions. Considering these standpoints, an attempt has been made to
synthesize Electroactive Polyamide – Copper Oxide composites and test their superiority as anti-
corrosives.

3
CHAPTER 2

LITERATURE SURVEY

4
2. LITERATURE SURVEY

2.1 POLYAMIDE

A polyamide is a macromolecule. It has repeating units linked by amide bonds (-CO-NH-) as an

integral part of the main polymer chain. Polyamides occur both naturally and artificially. Examples of
naturally occurring polyamides are proteins, such as wool and silk. Artificially made polyamides can
be made through solid-phase synthesis or step-growth polymerization yielding materials such as
nylons, aramids, and sodium poly (aspartate).They occupy a prominent position among the synthetic
high polymers. The first synthetic polyamide, polybenzamide was obtained by Harbordt in 1862.
Aliphatic polyamides show excellent mechanical properties including high tensile strength, high
flexibility, good resilience, low creep and high impact strength (toughness). They are easy to dye and
exhibit excellent resistance to wear due to a low coefficient of friction (self-lubricating). Both amides
have a high melting temperature (500 - 540 K) and glass transition temperature resulting in good
mechanical properties at elevated temperatures. Aromatic polyamides show high melting points
(generally above their decomposition temperature > 750 K), ultra-high tensile strength at low weight,
and excellent flame and heat resistance as well as good dimensional stability and solvent resistance at
room and elevated temperature. The first commercially produced aromatic polyamide was poly (m-
phenyleneisophthalamide). Some years later, development of the preparation of poly (p-
phenyleneterephthalamide) led to the commercialization of the Para-product Kevlar (DuPont) in the
early seventies. The major drawbacks in the fabrication of non-substituted aromatic polyamides are the
exhibition of a tendency to decompose during, or even before melting and their insolubility in most
common organic solvents. Therefore an increase in the interest to prepare polyamides with different
substituent or structural irregularities has been observed, in order to improve their processability.
Polyamides (PAs) are produced either by the reaction of a di-acid with a di-amine or by ring-opening
polymerization of lactams. Polyamides are particularly tough, have very good mechanical properties
and show excellent sliding and wear characteristics. Depending on the type, polyamides absorb
different amounts of moisture, which also affect the mechanical characteristics as well as the
dimensional accuracy. Engineering polyamides are used for power tool housings, valves and vending
for various machines and pumps and for many electrical, electronic parts including switches, sockets,
plugs and antenna-mounting devices. The properties of the polyamides (nylons), which include high
strength, abrasion resistance, and resilience, make them very important in the manufacture of clothing
and carpets. An important development is the use of polyamides to make safety airbags. Synthetic
polyamides are commonly used in textiles, automotive applications, carpets and sportswear due to
their high durability and strength. The transportation manufacturing industry is the major consumer,
5
accounting for 35% of polyamide (PA) consumption. More than 60 percent of the aliphatic polyamides
produced are used in commercial fibre applications. This includes carpets, garments, seatbelts,
upholstery, ropes and tire reinforcements. However, fabrics made from Nylon have less wrinkle
resistance than cloth made from polyesters is more expensive. For these reasons, Nylon fibres have
lost some market share to PET fibres over the years. Nylon fibres and mineral reinforced polyamide
resins are also widely used for engineering and industrial applications. The unreinforced grades have
an upper temperature for continuous use of around 340 - 350 K, and the glass and mineral reinforced
grades of about 370 - 390 K. Applications include almost every industry and market. For example, in
the automotive industry, nylon is used for wire and cable jacketing, cooling fans, air intake, turbo air
ducts, valve and engine covers, brake and power steering reservoirs, gears for windshield wipers and
speedometers. Engineering polyamides are also used for power tool housings, valves and vending for
various machines and pumps and for many electrical/electronic parts including switches, sockets, plugs
and antenna-mounting devices. The aromatic polyamides are much more expensive but have excellent
mechanical properties. They are used for very demanding applications in many industries. Examples
include ropes and cables, bulletproof vests, tennis strings, hockey sticks (as a composite), snowboards,
jet engine enclosures, brake and transmission friction parts, and gaskets.

2.1.1 STRUCTURE OF POLYAMIDE

The main chain polyamide composition, categorizes the structure to be either Aliphatic (linear p
olyamide), Semi-aromatic or Aromatic polyamide (R' and R" are two carbon atoms of an aromatic
ring). Due to the thermal stability, Aromatic polyamides are the ones highly in use.

Figure 2.1: Basic amide form

2.1.2 SYNTHESIS METHODS OF POLYAMIDES

2.1.2.1 SYNTHESIS OF POLYAMIDE

1. Polycondensation of di-amines and di-acid chlorides at low temperature

To prepare high molecular weight polyamides, low temperature polycondensation (<100°C) of di-
amines and di-acid chlorides has been used experimentally and commercially. This method was
6
developed by Du Pont and can be carried out in solution or at the interface of two solvents. A reaction
between di-amine and di-acid chloride in an amide solvent such as NMP, hexamethyl-phosphoramide
(HMPA), or DMAC is done with the help of solution polycondensation process.

2 (a) Interfacial polycondensation of di-amine and di-acid chloride

An adaptation of the well known Schotten-Baumann reaction, the so-called interfacial
polycondensation method brings monomers to react at the interface of two phases. In this method, two
fast reacting intermediates are dissolved in a pair of immiscible liquids, one of which is preferably
water. To neutralize the by product acid, the water phase generally contains the di-amine and usually
an inorganic base. The other phase contains the acid chloride in an organic solvent such as hexane,
toluene or dichloromethane.

Figure 2.2: Synthesis of Polyamide from interfacial polycondensation of di-amine and di-acid
chloride.

After vigorous stirring of the two-phase system, high molecular weight polymers are obtained. The
difference between interfacial polymerization and conventional step polymerization is that, in the
interfacial polymerization the monomer diffusing to the interface reacts only with the end of the
polymer chain resulting in high molecular weight polymer. Due to low temperature requirement, the
side reactions are minimized. Further, the polymers which are unstable at high temperatures can be
synthesized.

2 (b) Solution polycondensation of di-amine and di-acid chloride:

A reaction between di-amine and a di-acid chloride in an amide solvent such as HMPA, NMP, DMAc
or tetramethyl urea (TMU) is involved in a solution polycondensation process.

Figure 2.3: Synthesis of Polyamide from Solution polycondensation of a di-amine and a

di-acid chloride.

7
Also, for the hydrogen chloride produced in the reaction, the amide solvent serves as an acid acceptor.
Other polar aprotic solvents such as dimethyl sulfoxide and dimethyl formamide cannot be used due to
their reactive nature in the presence of acid chlorides. The solvent should allow maximum solubility
(swellablity) of the polymer formed at the early stage of polycondensation. An increment in the
solvation properties of amide solvents can usually be observed by the addition of salts such as CaCl2 or
LiCl.

3. Transition metal-catalyzed polycondensation of aromatic di-amines, di-halides and carbon

monoxide

Polyamides can also be synthesized by palladium-catalyzed carbonylative coupling of di-amines and

di-halides .

Figure 2.4: Transition metal catalyzed carbonylative coupling of aromatic

2.1.3 Types
diamines of Polyamide
and dihalides.

4. Polycondensation of di-isocyanates and di-carboxylic acids

A direct formation of polyamides with the elimination of CO2 without the use of any condensing
agents is obtained through this route. Several polyamides and co-polyamides have been prepared by
this method. A commercial scale preparation of aromatic polyamides from 1,3-phenylene di-
isocyanate and isophthalic acid in the presence of a catalyst has been reported. Polyamides have also
been prepared by the reaction of aromatic di-isocyanates with aromatic hydrocarbons in the presence
of Friedel Crafts catalyst.

5. High temperature solution polycondensation of di-carboxylic acids and di-amines

8
This reaction involves the formation of a complex of the acid with triphenyl phosphite in NMP and
pyridine, which further reacts with di-amine to give the product.CaCl2 and LiCl were used along with
NMP to improve the molecular weight of polymers. The role of CaCl2 and LiCl is quite complicated.
They can form complexes with pyridine and are more soluble than the salts alone, and NMP with a
higher content of metal salt can solubilise polyamide formed in the reaction medium more effectively,
leading to high molecular weight products.

Figure 2.5: Synthesis of Polyamide by condensation reaction involving acid and amine in
presence of triphenyl phosphite

2.1.3. TYPES AND PROPERTIES OF POLYAMIDES

2.1.3.1 Aromatic Polyamides:

Aromatic polyamides, better known as commercial aramids are considered to be high-performance
organic materials due to their outstanding mechanical and thermal resistance. Examples of aromatic
aramids are poly(p-phenylene terephthalamide), also known as known as Kevlar, and poly(m-
phenylene isophthalamides.

Structure of Repeat unit:

9
 Properties:

 They have excellent mechanical and thermal properties which arise from their aromatic
structure and amide linkages, which result in stiff rod-like macromolecular chains that interact
with each other via strong and highly directional hydrogen bonds.
 Aramids show higher strength, better solvent, flame and heat resistance and greater
dimensional stability than the all aliphatic amides.
 They have ultrahigh tensile strength at low weight, and excellent flame and heat resistance.
 The fully aromatic structure and the strong hydrogen bonds between the aramid chains results
in high melting points (generally above their decomposition temperature > 750 K).

2.1.3.2 Semi-aromatic Polyamides:

Semi-aromatic polyamides (also known as polyphthalamides (PPA) are combinations of aromatic and
aliphatic functionalities.

Properties:

1. PPA are generally aimed at the performance gap between aliphatic nylons such as PA6,6 and
PA6, and higher price polymers.
2. They are crystalline and offer high strength and stiffness at elevated temperatures.
3. They can offer better resistance to chemicals and environmental stress cracking.
4. They can offer better toughness and elongation up to break.
5. They can offer lower water absorption, better dimensional stability and mechanical properties
that are less susceptible to moisture.

2.1.3.3 Aliphatic polyamide:

Aliphatic polyamides are the class of thermoplastic polymers which contain the amide repeat linkage in
the polymer backbone. Examples of aliphatic polyamides are PA6, PA66, PA11, PA12.
Structure of Repeat unit:

Properties:

10
 Aliphatic polyamides are semi-crystalline as they consist of crystalline and amorphous phases.
 Crystallinity results from the polar amide groups, which undergo hydrogen bonding between the
carbonyl and NH groups in adjacent sections of the PA chains.
 The crystalline regions contribute to the hardness, yield strength, chemical resistance, creep resistance
and temperature stability.
 The regular spatial alignment of amide groups allows a high degree of hydrogen bonding to develop
when chains are aligned together.
 The amorphous areas contribute to the impact resistance and high elongation.
 Polyamides are important engineering plastics because of their toughness over wide range of
temperatures. Also they have good resistance to impact and abrasion. They are easy to dye and exhibit
excellent resistance to wear due to a low coefficient of friction (self-lubricating)

2.1.4 APPLICATIONS OF POLYAMIDES

 The aramids, poly (p-phenylene terephthalamide) and poly (m-phenylene isophthalamide), in

the aerospace and armament industry, bullet-proof body armour, protective clothing, sport
fabrics, electrical insulation, asbestos substitutes, and industrial filters, among others.
 These are also used in advanced technologies and have been transformed into high-strength
and flame resistant fibres and coatings, with applications in the aerospace and armament
industry.
 Nylon filaments are mainly used in carpets, apparel, in tire reinforcements and in other
industrial applications.
 Moulding and extrusion compounds find many applications as replacements for metal parts,
for instance in car engine components. Intake manifolds in nylon are tough, corrosion
resistant, lighter and cheaper than aluminium and offer better air flow due to a smooth internal
bore instead of a rough cast one. Its self-lubricating properties make it useful for gears and
bearings.
 Electrical insulation, corrosion resistance and toughness make nylon a good choice for high
load parts in electrical applications as insulators, switch housings and the ubiquitous cable ties.
Another major application is for power tool housings.
 Polyamide fibres are used in racing car tires and airplane tires owing to their excellent
strength, adhesion to rubber and fatigue resistance in these demanding applications.
 Thermoplastic polyamides are used in many automotive applications such as gears, bearings.
 Reinforced nylons are used for exterior body compartments such as fender extensions,
decorative louvers, filler plates, head lamp housings, cross-over panels and many other
11
 applications. In electrical and electronic area, polyamides are used in making plugs, sockets,
switches, connectors.
 Polyamide is commonly used for food packaging where the oxygen barrier characteristics of
nylon and moisture barrier capabilities of PE are required. Other applications include shoes,
ski boots, combs, bicycle wheels, cigarette lighters, racket frames, propellers, fans and toys.
 Aramids aromatic polyamides are used in Formula 1 racing cars. High strength allied to light
weight is essential in components used in this competitive sport.
 Aramids have good perm-selective properties and are used as hollow-fibre permeation
separation membranes to purify sea and brackish water or for the evaporation of numerous
types of salts from water.

2.2 ELECTRO ACTIVE POLYAMIDE:

2.2.1 PROPERTIES OF ELECTROACTIVE POLYAMIDES

Aromatic polyamides are well-known high-performance polymers that have excellent thermal,
mechanical and electrical properties as well as outstanding chemical resistance. However, most of them
have high melting or softening temperature and are insoluble in most of organic solvents because of the
rigidity of the backbone and strong intermolecular interactions. The multiple bonds in polyamide
molecules that mainly contain oxygen, nitrogen and sulphur atoms help them in getting adsorbed on the
metal surface (surfactants). Compounds like ethoxylated fatty acid, ethoxylated fatty amines and
propenethoxylatediol had been used as corrosion inhibitors for aluminium and steel in acidic solutions.
Temperature has a significant role to play in the corrosion inhibition. Hence, for effective corrosion
inhibition a wide range of conditions like temperature, exposure duration, pH, metal composition and
structure of inhibitor molecule come into play within the system and the inhibition efficiency depends on
these parameters. Electroactive polymers or conducting polymers possess properties such as light weight,
low cost, good processability, good mechanical toughness, non-toxic property and good thermal and
chemical stability and therefore can be considered as potential candidates for coating materials.
Electroactive polymers include ferroelectric and piezoelectric polymers. Recently, researchers have found
interest in developing polyamide composites due to their surfactant nature. Odd – numbered polyamides
(nylons) are classified under ferroelectric and piezoelectric polymers. The –NH AND –C=O groups
facilitate formation of stable polar elements in the polymer due to the hydrogen bonds formed by them,
giving rise to piezoelectricity. Further, the ferroelectric nature of the polyamide was based its crystal
phases and chemical structure. In 1991, Scheinbeim performed experimentation to confirm
ferroelectricity in nylons and reported a typical ferroelectric hysteresis loop from the electric

12
displacement D versus the applied electric field E test of nylon 11 films. He produced the film by melt-
quench and cold-stretching method. The results obtained were astonishing. Not only did they prove the
ferroelectric nature of nylon 11 but also enhanced the existing piezoelectric properties of the polymer.
This achievement set the pace for research and development in the field of electroactive polyamides like
nylon 5, nylon 7 and nylon 9. These properties make them generally intractable or difficult to process;
thus, their applications are restricted in some fields. To overcome these limitations, many efforts have
been made to improve the processing characteristics of these intractable polymers while other
advantageous properties are retained. A schematic representation of the molecular structures odd and
even numbered nylons is shown in Fig 1

Figure 2.6: Schematics of the molecular structures of odd numbered and even numbered nylons

2.2.2 APPLICATIONS OF EPA

 They are used in electromagnetic shutter, switching window and display technologies.
 EPA whose properties are changed drastically upon stimuli (electric field, light, pH,
temperature, etc) is used as a key actuator, sensor and smart window material.
 They are used in Biomimetics and switching technologies.

2.3 ELECTROACTIVE POLYAMIDE (EPA) /CuO COMPOSITES

2.3.1 PROPERTIES OF CuO

Copper oxide (CuO) being a transition metal oxide has a monoclinic structure and a narrow bandgap of

1.2 eV (indirect) with p-type semiconductor material. It shows good physical properties and has a density
13
of 6.31 g/cc. CuO has a melting temperature of 1201°C making it applicable for high temperature

applications. Having an ambit of technological applicability, CuO (copper oxide) has been wideley used

in areas such as solar energy materials, electronic materials, gas sensor, magnetic media, optical devices,

batteries and catalyst and constructing junction devices such as p-n diode, as well as for photoconductive,

photothermal, and photoelectrochemical applications. Considering these standpoints CuO can be used as

a potential additive/reinforcement to obtain better physical and mechanical properties in the electroactive

polymers being used for anticorrosive applications.

2.3.2 APPLICATIONS OF CuO:

 Doping materials in semiconductors are among the most demanding applications for CuO nano
particles.
 As an efficient anti-micro bacterial agent and as good catalysts for various cross coupling
reactions.
 Moreover, the ability of Copper Oxide for chemical sensing and energy storing can provide
great results. This property has established the use of CuO in applications such as chemical
sensors, energy storage performance in battery system.

2.3.3 POTENTIAL APPLICATIONS OF EPA AND CuO COMPOSITES

CuO nano-powder is added with different kinds of polymers (polypropylene, polyamide, PVA, etc). In
CuO-modified polymeric materials, due to the anti microbial effect of CuO the microorganisms, such as
bacteria get eradicated. Hence they can be used as delivery materials for medical purposes. Further, on
addition of CuO to PVA, an improvement in optical absorption and ionic diffusivity occurs. This property
of CuO based polymer composite gives rise to applications such as photonic and electronic devices. Also,
CuO nano-particles are known to improve thermal stability of the composite and hence can be suitable for
high temperature applications, especially for preventing high temperature corrosion.

2.4 CHARACTERIZATION TECHNIQUES OF EPA/CuO COMPOSITES

There are various methods for characterization of polymer composite. Some of them are given below:

2.4.1 ELECTRICAL CONDUCTIVITY

Electrical conductivity is measure of a materials ability to conduct electric current. It is commonly
represented by Greek later (σ) and its unit is Siemens per centimetre (S/cm). In general conductivity can

14
be measured by either the two probes or four probes techniques. For a high resistance material, the two
probe method is useful. It is simple and inexpensive. In this two electrodes are connected on both sides of
the sample in order to measure the resistance.

2.4.2. FOURIER TRANSFORM INFRARED SPECTROSCOPY

FTIR spectra provide useful information about the structure of a more quickly. In this technique almost
all groups characteristically with in a definite range. A shift in the position of absorption for a
particular group takes place with the change in structure of molecule. Any structural change like
substitution or addition of groups or atoms in a molecule affects the relative modes of vibration of the
group resulting into
(1) Change in band position
(2) Change in relative intensity and appearances of new bands
(3) Splitting single peak into two or more peaks.
Fourier Transform Infrared Spectroscopy (FTIR) method allows one to characterize vibrations in
molecules by measuring the absorption of light of certain energies that correspond to the vibrational
excitation of the molecules from lower to higher states. For the purpose of this thesis, Bruker IFS 66/S
FTIR spectrometer was used to characterize all the samples.

2.4.3. X-RAY POWDER DIFFRACTION ANALYSIS

X-ray has become the important tool for the analysis and study of matter in the solid state. X-ray
powder diffraction techniques for identification of crystalline substance have been applied to a wide
variety of analysis with useful results. They also used to reveal the other characteristics such as
crystalline size, orientation and strain.
Basic physical properties of a polymer are governed by super a molecule structure. Since polymer
cannot be completely crystalline, they do not have perfect crystal lattice. According to original
micellar theory of polymer crystallization, the polymeric material consists of numerous small
crystallites which are randomly distributed and linked by the intervening amorphous regions. The
polymers are part of several crystallites and of amorphous regions. In general, all polymers can be
divided into two groups. The criteria of this classification are furnished by X-ray diffraction.
 Crystalline polymer: this type of polymer gives sharply defined reflection on X-ray photograph
or maxima on diffraction pattern.
 Amorphous polymer: this type of polymer gives haloes instead of distinct reflections.
X-rays are short electromagnetic radiations. The intensity and direction of X-ray that have been
diffracted by a crystal are recorded by a quantum detector or by a photographic technique. Now day’s
commercial X-ray diffractometers use powder technique for X-ray diffraction studies. The coherence
length (L) of the crystalline order in the sample is calculated using Scherrer formula
15
λ= Wavelength in Å, θ= Bragg’s angle, ß= Tip width of the line (the distance between the pointat
which the intensity is half of the maximum intensity)

2.4.4. SCANNING ELECTRON MICROSCOPY (SEM)

SEM is technique of imaging the surface of the materials with the aid of signal derived from the
interaction between the probe electrons and the specimen. SEM is concerned with the surface structure
(morphology) of polymers. The objective of SEM is to observe the relationship between adjacent
particles and small part of the surface. SEM is similar in many ways to the X-ray microanalysis. The
basic SEM principle can be applied in different way to give the surface SEM (in which the electrons
strike the surface of a solid specimen with energy of several KeV). In SEM, the specimen is irradiated
by a finely focused beam. This releases secondary electrons, backscattered electrons, characteristic X-
ray and several other type of radiation from a small part of the surface. The intensity of these signals
will depend in the some way on the shape, chemical composition, and crystal orientation of the
irradiated volume.
The electro column is on the left, and scanning and display circuits are in the centre and on the right.
The electron column consists of an electron gun, de magnifying lenses, beam-defining apertures, and
scanning coils. These form a fine form of electrons that can be moved over the surface of the
specimen. A detector that is sensitive to the chosen output signal from the specimen is connected
through a video-amplifier to the grid of the cathode ray tube that is in synchronism with the beam on
specimen. In other words, the brightness at any point on the screen will depend on the strength of the
signal from the corresponding point on the specimen. In this way an image on the specimen surface is
built up on the cathode-ray tube screen point.

2.4.5. THERMAL ANALYSIS

Thermal analysis can be used to detect the physical or chemical changes in a material related to
thermal properties. This technique includes thermogravimetric analysis (TGA), and differential
thermal analysis (DTA).

Thermogravimetric Analysis (TGA)

Thermogravimetric analysis (TGA) is a technique that permits the continuous weighing of a sample as
a function of temperature and as a function of time at a desired temperature.TGA used either alone or
in combination with differential thermal analysis techniques. (DTA) is chief diagnostic tool used to
study the thermal decomposition of polymer. The TG curve of a polymer obtained in presence of air
16
provides information about its thermal stability. The TG curve of a polymer in an inert atmosphere,
gives information about nature of thermal degradation. In the course of thermal analysis on thermal
energies is transmitted to the sample. Hence at low temperature moisture is released and at higher
temperature polymer degrade. The TGA curve followed a relatively simple sigmoidal path. The shape
of TGA curve depends primarily on the kinetic parameter like, order of reaction (n), Pre-exponential
factor (A) and Activation energy (Ea).These parameters can be major importance in the elucidation of
mechanism of polymer degradation and in determination of the thermal stability of polymers.
The TGA curve may be complex, if a material degrades by a multistep mechanism which involves
several rate controlling steps. If the activation energy of rate controlling step are similar in magnitude.
The simple sigmoidal curve may be obtained which gives activation energy for overall process of the
degradation. If the activation energy for the rate controlling step is differs, the TGA curve may involve
two or more sigmoids. If the reaction order of the various rate controlling steps is grater then zero, two
or more inflection point may be observed. The separate sigmoidal curve may be individually analysed
for Ea, n and A by methods similar to those employed for TG curve analysis of one sigmoid curve
several method has been proposed for estimation kinetic parameters from dynamic TGA. These
methods are based on assumption that
(1) Thermal and diffusion barriers are negligible.
(2) Arrhenius equation is valid.

17
CHAPTER 3
EXPERIMENTAL WORK

18
3. EXPERIMENTAL
3.1 CHEMICALS AND MATERIALS:
Sebacoyl chloride, N-phenyl-p-phenylenediamine, Triethylamine, Dichloromethane and Ether, 1,4-
phenylenediamine, Ammonium Persulfate (APS), HCl, CuO nanoparticles, distilled and deionized
water was used.

3.2 SYNTHESIS OF OLIGOANILINE:

A solution of 1 g (4 mmol) sebacoyl chloride in 20 mL dichloromethane was added dropwise over a
period of 1 h while stirring to a mixture of N-phenyl-p-phenylenediamine 1.5 g (8 mmol) and
triethylamine (3 mL) in 13 mL of dichloromethane. The reaction, carried out in an atmosphere of dry
nitrogen to avoid oxidation of the N-phenyl-p-phenylenediamine, did proceed readily at room
temperature, forming a gray solution. The reaction mixture was stirred for 3 h, and the macromonomer
of oligoaniline precipitated as a fine gray particulate. The product, filtered from solution, was
subsequently washed with dichloromethane and ether, filtered, and dried under dynamic vacuum at
room temperature for 24 hr

19
Sebacoyl chloride(4mmol)

Mixture 1
+

Dichloromethane (20 ml)

N-phenyl N-phenylenediamine (8mmol)

+ Mixture 2

trimethylamine(3ml) +

dichloromethane (13ml)

Stirring for 3 hrs

Filtered with Dichloromethane +water+ acetone

Precipitate dried in oven at 60 0c for 12hrs

Figure 3.1: Schematic representation of synthesis of oligoaniline

20
3.3 SYNTHESIS OF ELECTROACTIVE POLYAMIDE
EPA was prepared by simultaneously dissolving 0.27 g (0.5 mmol) oligoaniline and 0.054 g (0.5 mmol)
1,4-phenylenediamine into 11 mL of a mixing solution containing 10 mL NMP, 0.5 mL distilled water,
and 0.5 mL concentrated hydrochloric acid. Subsequently, a solution containing 0.25 g of APS and
1.5 mL of an aqueous 1.0 M HCl solution was added dropwise while stirring at room temperature. The
resulting solution was allowed to react for another 12 h. Then, it was poured into 300 mL distilled water
to precipitate the product. The black powder was filtered and washed several times with distilled water.
The as-obtained product was then dried under dynamic vacuum at 40 °C for 24 h.

21
 Oligoaniline(0.5mmol)

+ Solution 1

1-4 phenylenediamine (0.054 g)

NMP (10 ml)

Distilled water (0.5 ml) Solution 1

+
Concentrated HCl (0.5 ml)

APS (0.25 g)

+ Solution 2

HCl (1M,1.5 ml)

Stirring for 12 hrs continuously

Pour the solution in distilled water to make

300 ml of solution

Filter the solution with water

Figure 3.2 Schematic representation of

synthesis of Electroactive Polyamide Dry in oven at 600C for 24 hours

22
3.4 .SYNTHESIS OF ELECTROACTIVE POLYAMIDE/ CuO COMPOSITE
Electroactive polyamide/ CuO composite is prepared by adding CuO during synthesis of electroactive
polyamide(EPA)

A solution l of 10 ml NMP and 0.5ml distilled water and 0.5ml concentrated HCL was prepared. Now
simultaneously o.27gm oligoaniline and 0.054gm 1,4-phenylenediamine is dissolved into the solution l
prepared above. Now CuO nanoparticles of (3, 6, 9 wt%) is added to the solution ll prepared above.
solution lll is prepared containing 0.25gm of APS and 1.5ml of an aqueous 1.0M HCL and this is
added dropwise to the solution 1 .The resulting solution was allowed to react for another 12hours with
continuous stirring. Then it was poured into 300ml distilled water to precipitate the product. The black
powder was filtered and washed several times with distilled water and then the product is then dried
under vacuum at 400 for 24 hours.

Figure 3.3 Schematic representation of synthesis of Electroactive Polyamide/CuO composite

23
CHAPTER 4

CHARACTERIZATION OF EPA AND ITS COMPOSITES

24
4. CHARACTERIZATION OF EPA AND ITS COMPOSITES:
4.1. ELECTRICAL CONDUCTIVITY:

Electrical conductivity of compressed pellet of EPA and EPA/CuO composites was measured by two
probe method at room temperature at a frequency of 1 KHz. The sample pellets were prepared with the
help of hydraulic press (Kimaya Engineers, India) by applying a pressure of 5 N/m2 for 30 sec in steel
die. These pellets were then subjected to D.C. resistance measurement on 928 AUTO LCR Q TESTER
(Systronics). The pellet which was used for the measurement of resistance was circular in shape with
thickness of ~1.4 mm and diameter of 1.3 cm. The recorded resistance was converted resistivity using
formula:
ρ= RA/l
where,
R is the resistance of the pellet,
A is the surface area of the pellet (calculated from πr 2, where r =radius of the pellet),
L is the thickness of the pellet.
Resistivity is inversed to obtain the conductivity (σ).

4.2 FOURIER TRANSFORM INFRA RED (FTIR) SPECTROSCOPY:

The FTIR spectrum of Oligoaniline, EPA and EPA/CuO Composites was recorded on Fourier
Transform Infra Red Spectrophotometer IR Affinity–I (shimadzu). FTIR measurements were taken
from 4000-400 cm-1. 2mg of sample was mixed and grind with a pure 100 mg KBr in a mortar. The
powder mixture was then placed in the assembly through which the beam of the spectrometer can pass.
A beam of infra red light is produced, passed through an interferometer and split into two separate
beams. The beam was passed through a slitter, which quickly alter rates of the beams enters the
detector. The two signals are then compared and a print out is obtained.

25
Figure 4.1: Schematic representation of Fourier Transform Infra red Spectrophotometer

4.3 X- RAY DIFFRACTION ANALYSIS (XRD):

XRD pattern of EPA has been recorded using PANanalyticalX`Pert Pro MPD Diffractometer. The X-
ray tube is operated at Generator Setting 40 mA and 45 Kv, The XRD pattern are recorded in the 2
theta range from 100 to 1000 (start position 10.0014 to end position 99.9824). Approx 0.2 gm of
powdered sample was taken on a glass slide .The sample was spread uniformly on it and compressed
by using another glass slide. The glass slide along with the sample is mounted in plate such that the
beam of radiation is properly incident on the sample. The Nickel filtered CuK α radiation (y =1.5406
A0) is used for recording X-ray diffraction pattern.

26
Figure 4.2: Schematic representation of X-Ray Diffractometer

4.4 SCANNING ELECTRON MICROSCOPE (SEM):

The surface morphology of EPA and EPA/CuO Composites was examined using scanning electron
microscope (SEM) on JEOL JSA -840A equipped with an electron probe- micro-analyser system.
2mg of powder sample was dispersed in 5 ml methanol under ultrasonic agitation. The upper part of
dispersed particles from the beaker is taken out with the help of micropipette and transfer on the clean
copper grid. The methanol was allowed to evaporate. Then sample were coated with thin layer of gold
by sputtering. SEM microscope was recorded by inserting the copper grid with the sample on the
mounting table of SEM instrument.

27
Figure 4.3: Schematic representation of SEM JEOL 6380A

4.5 THERMOGRAVIMETRIC ANALYSIS (TGA):

Thermogravimetric analysis of the prepared EPA and EPA/CuO composites was performed on
simultaneous TGA and DTA, Perkin Diamond Instrument. One mg approx. powder sample was taken
in the platinum pan. The sample was heated at a rate of 100C /min in the temperature range from 40 to
8000C under purging of nitrogen at a flow rate of 200 ml/min.

28
Figure 4.4: Schematic representation of Thermogravimetric Analysis

4.6 BIOLOGIC POTENTIOSTAT 8 CHANNEL FOR CORROSION STUDIES:

Corrosion analysis of the prepared EPA/CuO composites was performed on BioLogic Science
Instruments – VMP 300. 10 mg approx. powder sample was taken and mixed with NMP. This mixture
was then coated over the 304 stainless steel samples and kept for drying at 70°C for 24hr. Post drying
these samples were tested by dipping in 3.5% NaCl solution, for 1 hr on EIS and further for
polarization results.
Also, the corrosion rate had been calculated using the formula,
C.R (mpy) = (0.13× iCORR ×equivalent weight)/density

where,
iCORR is in µA
equivalent weight of 304 SS
density of 304 SS = 7.87 g/cc

29
Figure 4.5: Schematic representation of Biologic Potentiostat 8 Channel

30
CHAPTER 5

RESULTS AND DISCUSSIONS

31
5. RESULTS AND DISCUSSIONS:

5.1 ELECTRICAL CONDUCTIVITY STUDIES:

The results of electrical conductivity are presented in Table 5.1. EPA/CuO composites’ conductivity
did not show significant change on variation of CuO content in the composites. EPA shows the room
temperature conductivity of 2.0970×10-6 Siemens/cm.

Table 5.1: Electrical Conductivity of EPA and EPA/CuO composites

Name of the Siemens/cm
sample
EPA 2.0970×10-6
EPA/3%CuO 1.337×10-7
EPA/6%CuO 2.803×10-7
EPA/9%CuO 8.410×10-7

It is seen from Table 5.1 that the conductivity of composite is slightly less of one order as compared to
that of EPA. Such decrease in conductivity of composite is due to the presence of CuO particles. The
presence of CuO particles hinders the movement of electrons which in turn results in decreased
conductivity of the composite. The conductivity values show an increasing trend with increase in the
CuO content.

32
5.2 FTIR STUDIES

180.0

1. FTIR STUDIES
170

160

565
150
577
516

140
3747

130 3390
666

903
%T 120 3296 693
2139 881
2102
110 1935 746

1077 963
1872 820
100 1446 1127 1037
1729 1588
1654
90
2937
2870 1266
1236
80 1322 1170
2738 2497

70 2532 1535

65.0 2605
4000.0 3600 3200 2800 2400 2000 1800 1600 1400 1200 1000 800 600 450.0
cm-1
Figure 5.1: FTIR spectra of oligoaniline

Figure 5.1 shows FTIR spectroscopy confirming the structure of a macromonomer of oligoaniline. The
characteristic absorption peaks found at approximately 3390 cm-1 and 3296 cm-1 can be attributed to
the N-H stretching vibration, while at 2937 cm-1 can be attributed to the C-H stretching vibration. The
peak at 1654 cm-1 can be assigned to the C=O stretching vibration, and the peak at 1322 cm-1 can be
assigned to the C=C stretching vibrations. The peak at 820 cm-1 is attributed to cut-of-plane C-H
deformation of aromatic ring. The peak at 1170 cm-1 is attributed to C-N stretching of secondary
aromatic amine

33
 148.3

140

130

120

110

%T 100
3307 518

90 750 509
3726
881
80
826
1152
70 2615
1508 1303
1248
59.0
4000.0 3000 2000 1500 1000 450.0
cm-1
Figure 5.2: FTIR spectra of Electroactive polyamide

Figure 5.2 shows FTIR spectroscopy confirming the structure of electroactive polyamide.EPA shows
characteristic absorption bands at 1303 cm−1, 1508 cm−1, and 3307 cm−1. The peak at 1303 cm-1
corresponds to C-N stretching of aromatic amide. The peak at 1303 cm-1 corresponds to C=C
stretching vibrations of the benzoid rings. The peak at 3307 cm-1 corresponds to N-H stretching
vibration.

34
 Figure 5.3: FTIR spectra of EPA/3%CuO Composite

Figure 5.3 shows FTIR spectroscopy confirming the structure of electroactive polyamide and 3%CuO
composite. The peak at 1668cm-1 is assigned to C=O stretching vibrations. The peak at 3300 cm-1 is
assigned to N-H stretching vibration. The peak at 1263 cm-1 corresponds to C-N stretching of aromatic
amide. The peak at 1306 cm-1 corresponds to C=C stretching vibrations of quinoid and benzoid rings
respectively. The N-H bend is observed from 1572-1668 cm-1. Simultaneously structure of CuO is
confirmed by the peak at 1901 cm-1.

35
 Figure 5.4: FTIR spectra of EPA/6% CuO Composite

Figure 5.4 shows FTIR spectroscopy confirming the structure of electroactive polyamide and 6%CuO
composite. The peak at 1667cm-1 is assigned to C=O stretching vibrations. The peak at 3301 cm-1 is
assigned to N-H stretching vibration. The peak at 1263 cm-1 corresponds to C-N stretching of aromatic
amide. The peak at 1305 cm-1 corresponds to C=C stretching vibrations of quinoid and benzoid rings
respectively. Simultaneously structure of CuO is confirmed by peak at 1892 cm-1.

36
 Figure 5.5: FTIR spectra of EPA/9% CuO Composite

Figure 5.5 shows FTIR spectroscopy confirming the structure of electroactive polyamide and 9%CuO
composite. The peak at 1671cm-1 is assigned to C=O stretching vibrations. The peak at 3322 cm-1 is
assigned to N-H stretching vibration. The peak at 1259 cm-1 corresponds to C-N stretching of aromatic
amide. The peak at 1306 cm-1 corresponds to C=C stretching vibrations of quinoid and benzoid rings
respectively. Simultaneously structure of CuO is confirmed by peak at 1902 cm-1. The FTIR spectrums
of EPA /CuO shows all the prominent peaks of EPA and CuO observed in the range of 500-800 cm-1,
suggesting the interaction between EPA and CuO.

37
5.3. XRD ANALYSIS

The X-ray diffraction pattern of EPA is shown in Figure 5.6. The EPA exhibited peak around 2θ =26.09
with d-spacing 3.49Å which explain the polymer has amorphous structure. Thus XRD analysis confirms
the amorphous nature of the electroactive polyamide.

Counts
CHITRA EPA 24-11-2016

64

36

16

0
20 30 40 50 60 70 80 90

Position [°2Theta]

Figure 5.6: XRD pattern of EPA

38
The X-ray diffraction pattern of CuO is shown in Figure 5.7. The EPA exhibited significant peaks around
2θ =32.2º, 35.4° and 38.6º with d-spacing 2.77, 2.53 and 2.32 Å respectively. This XRD data has been
considered to compare and analyse the XRD results of EPA/CuO composites. The XRD pattern of CuO
shows several sharp and well defined peaks indicating the crystalline nature of CuO.

Counts
CuO

400

300

200

100

0
20 30 40 50 60 70 80 90

Position [°2Theta]

Figure 5.7: XRD pattern of CuO

39
The X-ray diffraction pattern of EPA/3%CuO composite is shown in Figure 5.8. The EPA/3%CuO
Composite exhibited peak around 2θ = 35.3º and 38.5° with d-spacing 2.53 and 2.33 Å respectively,
which show the presence of CuO nanoparticles within the EPA powder matrix. The peaks of CuO are
less pronounced due to less content of CuO in the EPA /CuO composites.

Counts
3% EPA

400

200

0
20 30 40 50 60 70 80 90

Position [°2Theta]

Figure 5.8: XRD pattern of EPA/3%CuO Composite

40
The X-ray diffraction pattern of EPA/6%CuO Composite is shown in Figure 5.9. The EPA/6%CuO
Composite exhibited peaks around 2θ = 32.2º, 35.3º and 38.5º with d-spacing 2.77, 2.53 and 2.33 Å
respectively, which show the presence of CuO nanoparticles within the EPA powder matrix. The peaks
of CuO are more pronounced due to more content of CuO in the EPA /CuO composites.

Counts
6% EPA

400

300

200

100

0
20 30 40 50 60 70 80 90

Position [°2Theta]

Figure 5.9: XRD pattern of EPA/6%CuO Composite

41
The X-ray diffraction pattern of EPA/9%CuO Composite is shown in Figure 5.10. The EPA/9%CuO
Composite exhibited peaks around 2θ = 32.2º, 35.3º and 38.5ºwith d-spacing 2.77, 2.53 and 2.33 Å
respectively, which show the presence of CuO nanoparticles within the EPA powder matrix. The peaks
of CuO are more pronounced suggesting good interaction between EPA and CuO in the composites.

Counts
9% EPA

300

200

100

0
20 30 40 50 60 70 80 90

Position [°2Theta]

Figure 5.10: XRD pattern of EPA/9%CuO Composite

42
5.4. Morphological studies of EPA and its composites

A series of SEM micrographs of the as-synthesized EPA, CuO and EPA/CuO composite samples are
shown in Figure 5.11, 5.12, 5.13, 5.14 and 5.15.

Figure 5.11: SEM IMAGE OF EPA

The morphological structure consisted of EPA, which shows a continuous phase which is amorphous in
nature.

43
Figure 5.12: SEM image of CuO

The morphological structure consisted of CuO nanoparticles showing spherical structures and in most of
the regions agglomerated nanoparticles of CuO are observed.

44
Figure 5.13: SEM image of EPA/3%CuO composite

It has been observed that the morphological structure consisted of clustered structures of EPA and
spherical CuO nanoparticles. The CuO particles are not seen throughout the EPA matrix and this may be
due to very less content of CuO in the EPA/CuO composites.

45
Figure 5.14: SEM image of EPA/6%CuO composite

It has been observed that the morphological structure consisted of clustered structures of EPA and
spherical CuO nanoparticles. It can also be observed that upon increasing the CuO content the size of
clusters formed has decreased mildly. Further, these morphological studies demonstrated that CuO nano-
particles had been successfully dispersed within the EPA matrix.

46
Figure 5.15: SEM image of EPA/9%CuO composite

It has been observed that the morphological structure consisted of clustered structures of EPA and
spherical CuO nanoparticles. It can also be observed that upon further increasing the CuO content the size
of clusters formed has decreased significantly. Hence, these morphological studies demonstrated that
CuO nano-particles had been successfully dispersed within the EPA matrix and this may be due to the
more content of CuO in the EPA/CuO composites.

47
5.5 THERMOGRAVIMETRIC ANALYSIS (TGA)

Thermal stability and % weight loss with respect to temperature are measured. Figure 5.16 depicts TG
thermo grams of EPA and EPA/CuO composites. The TGA of EPA shows a weight loss; initial weight
loss up to 1200C is attributed to the loss of moisture and solvent. A 24.1% weight loss was observed at
370ºC and a 51.6% weight loss was observed at 452°C. The weight loss from 4000C to 4520C is steep
weight loss due to backbone chain degradation. The weight loss above 4520C is attributed to the main
chain degradation of polyamide chain. EPA/CuO composites show similar decomposition step as EPA
but have higher thermal stability and on increasing the content of CuO in composite, the thermal
stability of the composite is increasing due to more incorporation inorganic component.

Table 5.2: Weight loss data for EPA and EPA/CuO (3, 6 and 9%) composites at 550°C temperature

Temperature Weight loss %

EPA 100

EPA/CuO (3%) 88

EPA/CuO (6%) 74

EPA/CuO (9%) 52

48
Figure 5.16: TGA analysis of EPA and EPA/CuO composites.

49
5.6 ANTICORROSIVE PROPERTY OF EPA/CuO composites

Potentiodynamic polarization curves for bare 304 SS, EPA and EPA/CuO composite coated 304 SS in
3.5% NaCl solution are shown in Figure 5.17. Polarization results obtained, are presented Table 5.3.

Table 5.3: Polarization test results of Bare 304 SS, EPA and EPA/CuO composites

Samples ECORR iCORR Corrosion

(V) (A/cm2) Rate (mpy)
Bare 304 SS -0.225 0.575×10-6 0.2611
EPA coating -0.200 0.101×10-6 0.0458
EPA/CuO (3%) -0.117 0.042×10-6 0.0190
EPA/CuO (6%) -0.138 0.019×10-6 0.008630
EPA/CuO (9%) -0.047 0.008×10-6 0.003634

It is evident that ECORR of EPA and EPA/CuO composites coatings are less active than 304 SS. This
indicates that coating of EPA and EPA/CuO composites have a lesser tendency to corrode than 304
SS. It is also evident that iCORR of EPA and EPA/CuO composite coatings are one or two order of
magnitude less than bare 304 SS. This indicates that EPA and EPA/CuO composite coatings are highly
protective. It is also noted from the above Table 5.3 that the best anticorrosive properties are obtained
at higher content of CuO in the EPA/CuO composites.

50
Figure 5.17: Polarization behaviour of bare 304 SS, EPA and EPA/CuO composites

51
CHAPTER 6
CONCLUSIONS

52
6. CONCLUSIONS:

1. The Electroactive polyamide/CuO composites have been prepared by oxidative coupling

polymerization.

2. The structural and morphological aspect of all synthesized samples has been confirmed using FTIR,
SEM and XRD method.

3. From the electrical conductivity measurement it is found that the electrical conductivity of the
EPA/CuO composites did not show any significant effect on increasing CuO content in the composites.

4. Thermogravimetric results reveal that on increasing CuO nanoparticles content in the thermal stability
has improved due to interaction of CuO and Polyamide backbone.

5. The better anticorrosive properties of EPA/CuO composite coatings on 304 SS can be obtained due to
inhibiting property of EPA and passive oxide layer.

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