Thermal characterization of doped polyaniline and its composites with CoPc

Thermal diffusivity of the composites of camphor sulphonic acid (CSA) doped polyaniline (PANI) and its composites with cobalt phthalocyanine (CoPc) has been measured using open cell photoacoustic technique. Analysis of the data shows that the effective thermal diffusivity value can be tuned by varying the relative volume fraction of the constituents. It is seen that polaron assisted heat transfer mechanism is dominant in CSA doped PANI and these composites exhibit a thermal diffusivity value which is intermediate to that of CSA doped PANI and CoPc. The results obtained are correlated with the electrical conductivity and hardness measurements carried out on the samples

Thermal characterization of doped polyaniline and its composites with CoPc

Thermal diffusivity of the composites of camphor sulphonic acid (CSA) doped polyaniline (PANI) and its composites with cobalt phthalocyanine (CoPc) has been measured using open cell photoacoustic technique. Analysis of the data shows that the effective thermal diffusivity value can be tuned by varying the relative volume fraction of the constituents. It is seen that polaron assisted heat transfer mechanism is dominant in CSA doped PANI and these composites exhibit a thermal diffusivity value which is intermediate to that of CSA doped PANI and CoPc. The results obtained are correlated with the electrical conductivity and hardness measurements carried out on the samples.

New studies on the versatile roles of Polyaniline and its composites in polymer based optoelectronic and energy storage devices

From the early stages of the twentieth century, polyaniline (PANI), a well-known and extensively studied conducting polymer has captured the attention of scientific community owing to its interesting electrical and optical properties. Starting from its structural properties, to the currently pursued optical, electrical and electrochemical properties, extensive investigations on pure PANI and its composites are still much relevant to explore its potentialities to the maximum extent. The synthesis of highly crystalline PANI films with ordered structure and high electrical conductivity has not been pursued in depth yet. Recently, nanostructured PANI and the nanocomposites of PANI have attracted a great deal of research attention owing to the possibilities of applications in optical switching devices, optoelectronics and energy storage devices. The work presented in the thesis is centered around the realization of highly conducting and structurally ordered PANI and its composites for applications mainly in the areas of nonlinear optics and electrochemical energy storage. Out of the vast variety of application fields of PANI, these two areas are specifically selected for the present studies, because of the following observations. The non-linear optical properties and the energy storing properties of PANI depend quite sensitively on the extent of conjugation of the polymer structure, the type and concentration of the dopants added and the type and size of the nano particles selected for making the nanocomposites. The first phase of the work is devoted to the synthesis of highly ordered and conducting films of PANI doped with various dopants and the structural, morphological and electrical characterization followed by the synthesis of metal nanoparticles incorporated PANI samples and the detailed optical characterization in the linear and nonlinear regimes. The second phase of the work comprises the investigations on the prospects of PANI in realizing polymer based rechargeable lithium ion cells with the inherent structural flexibility of polymer systems and environmental safety and stability. Secondary battery systems have become an inevitable part of daily life. They can be found in most of the portable electronic gadgets and recently they have started powering automobiles, although the power generated is low. The efficient storage of electrical energy generated from solar cells is achieved by using suitable secondary battery systems. The development of rechargeable battery systems having excellent charge storage capacity, cyclability, environmental friendliness and flexibility has yet to be realized in practice. Rechargeable Li-ion cells employing cathode active materials like LiCoO2, LiMn2O4, LiFePO4 have got remarkable charge storage capacity with least charge leakage when not in use. However, material toxicity, chance of cell explosion and lack of effective cell recycling mechanism pose significant risk factors which are to be addressed seriously. These cells also lack flexibility in their design due to the structural characteristics of the electrode materials. Global research is directed towards identifying new class of electrode materials with less risk factors and better structural stability and flexibility. Polymer based electrode materials with inherent flexibility, stability and eco-friendliness can be a suitable choice. One of the prime drawbacks of polymer based cathode materials is the low electronic conductivity. Hence the real task with this class of materials is to get better electronic conductivity with good electrical storage capability. Electronic conductivity can be enhanced by using proper dopants. In the designing of rechargeable Li-ion cells with polymer based cathode active materials, the key issue is to identify the optimum lithiation of the polymer cathode which can ensure the highest electronic conductivity and specific charge capacity possible The development of conducting polymer based rechargeable Li-ion cells with high specific capacity and excellent cycling characteristics is a highly competitive area among research and development groups, worldwide. Polymer based rechargeable batteries are specifically attractive due to the environmentally benign nature and the possible constructional flexibility they offer. Among polymers having electrical transport properties suitable for rechargeable battery applications, polyaniline is the most favoured one due to its tunable electrical conducting properties and the availability of cost effective precursor materials for its synthesis. The performance of a battery depends significantly on the characteristics of its integral parts, the cathode, anode and the electrolyte, which in turn depend on the materials used. Many research groups are involved in developing new electrode and electrolyte materials to enhance the overall performance efficiency of the battery. Currently explored electrolytes for Li ion battery applications are in liquid or gel form, which makes well-defined sealing essential. The use of solid electrolytes eliminates the need for containment of liquid electrolytes, which will certainly simplify the cell design and improve the safety and durability. The other advantages of polymer electrolytes include dimensional stability, safety and the ability to prevent lithium dendrite formation. One of the ultimate aims of the present work is to realize all solid state, flexible and environment friendly Li-ion cells with high specific capacity and excellent cycling stability. Part of the present work is hence focused on identifying good polymer based solid electrolytes essential for realizing all solid state polymer based Li ion cells.The present work is an attempt to study the versatile roles of polyaniline in two different fields of technological applications like nonlinear optics and energy storage. Conducting form of doped PANI films with good extent of crystallinity have been realized using a level surface assisted casting method in addition to the generally employed technique of spin coating. Metal nanoparticles embedded PANI offers a rich source for nonlinear optical studies and hence gold and silver nanoparticles have been used for making the nanocomposites in bulk and thin film forms. These PANI nanocomposites are found to exhibit quite dominant third order optical non-linearity. The highlight of these studies is the observation of the interesting phenomenon of the switching between saturable absorption (SA) and reverse saturable absorption (RSA) in the films of Ag/PANI and Au/PANI nanocomposites, which offers prospects of applications in optical switching. The investigations on the energy storage prospects of PANI were carried out on Li enriched PANI which was used as the cathode active material for assembling rechargeable Li-ion cells. For Li enrichment or Li doping of PANI, n-Butyllithium (n-BuLi) in hexanes was used. The Li doping as well as the Li-ion cell assembling were carried out in an argon filled glove box. Coin cells were assembled with Li doped PANI with different doping concentrations, as the cathode, LiPF6 as the electrolyte and Li metal as the anode. These coin cells are found to show reasonably good specific capacity around 22mAh/g and excellent cycling stability and coulombic efficiency around 99%. To improve the specific capacity, composites of Li doped PANI with inorganic cathode active materials like LiFePO4 and LiMn2O4 were synthesized and coin cells were assembled as mentioned earlier to assess the electrochemical capability. The cells assembled using the composite cathodes are found to show significant enhancement in specific capacity to around 40mAh/g. One of the other interesting observations is the complete blocking of the adverse effects of Jahn-Teller distortion, when the composite cathode, PANI-LiMn2O4 is used for assembling the Li-ion cells. This distortion is generally observed, near room temperature, when LiMn2O4 is used as the cathode, which significantly reduces the cycling stability of the cells.

Electron spin resonance absorption in organic metal polyaniline and its blend with PMMA

The electron spin resonance absorption in the synthetic metal polyaniline (PANI) doped with PTSA and its blend with poly(methylmethacrylate) (PMMA) is investigated in the temperature range between 4.2 and 300 K. The observed line shape follows Dyson's theory for a thick metallic plate with slowly diffusing magnetic dipoles. At low temperatures the line shape become symmetric and Lorentzian when the sample dimensions are small in comparison with the skin depth. The temperature dependence of electron spin relaxation time is discussed. (C) 1999 Elsevier Science Ltd. All rights reserved.

Creep Behaviour of AE42 Magnesium Alloy and Its Composites Using Impression Creep Technique

The creep behaviour of a creep-resistant AE42 magnesium alloy has been examined in the temperature range of 150 to 240 degrees C at the stress levels ranging from 40 to 120 MPa using impression creep technique. A normal creep behaviour, i.e., strain rate decreasing with strain and then reaching a steady state, is observed at all the temperatures and stresses employed The stress exponent varies from 5.1 to 5.7 and the apparent activation energy varies from 130 to 140 kJ/mol, which suggests the high temperature climb of dislocation controlled by lattice self-diffusion being the dominant creep mechanism in the stress and temperature range employed The creep behaviour of the AE42 alloy has also been compared with its composites reinforced with Saffil short fibres and SiC particles in four combinations. All the composites exhibited a lower creep rate than the monolithic AE42 alloy tested at the same temperature and stress levels and the decrease in creep rate was greater in the longitudinal direction than in the transverse direction, as expected. All the hybrid composites, i.e., the composites reinforced with a combination of Saffil short fibres and SiC particles, exhibited creep rates comparable to the composite reinforced with 20% Saffil short fibres alone at all the temperature and stress levels employed, which is beneficial from the commercial point of view.

Protonation of polyaniline and its polyelectrolyte complexes at different ionic strength: contribution of Donnan effect

UV-visible spectra of polyaniline and its polyelectrolyte complexes show evidence for different degree of protonation when equilibrated with different ionic strength at a particular pH, due to the Donnan effect. For pure polyaniline, when the fixed charge on the film is positive, protonation is higher ionic strength whereas, when the polyaniline is doped with a polyelectrolyte resulting in a net negative fixed charge on the film, the protonation is less at higher ionic strength.

Water soluble polyaniline and its blend films prepared by aqueous solution casting

Polyaniline (PAn) was doped with phosphonic acid containing hydrophilic tails. The solubility of the doped PAn in water was controlled by changing the length of hydrophilic chain in the dopant. When poly(ethylene glycol) monomethyl ether (PEGME) with molecular weight M-w = 550 was used as the hydrophilic chain of the dopant, the doped PAn was entirely soluble in water. The film cast from aqueous solution showed good electrochemical redox reversibility, Aqueous solution blending of PAn with poly(ethylene glycol) (PEG, M-w = 20 000) and poly(N-vinyl pyrrolidone) (PVP, M-w = 360 000) was achieved. Percolation threshold of the composite film was lower than 3 wt.%. Electrical conductivity of the composite film was in the range of 10(-1)-10(-5) S cm(-1), depending on molecular weight of the acid and the content of PAn in the composite. (C) 1999 Elsevier Science Ltd. All rights reserved.

Transport property of polyaniline and its molecular weight dependence

The electrical conductivity of polyaniline doped with camphor sulfonic acid (PAn-CSA) was studied. The results indicate that there is a critical temperature (T-c) and the temperature dependence of PAn-CSA conductivity shows metallic and semiconductor characteristics above and below T-c, respectively. The higher the molecular weight of PAn, the lower the T-c. The conductivity was enhanced remarkably when PAn-CSA film was stretched, its room temperature conductivity is up to 750 S/cm when elogonation is 60%; however, T-c was independent of elongation.

SOLUTION PROPERTIES OF POLYANILINE AND ITS DERIVATIVES

Solutions of polyaniline (PAn), poly(ortho-toluidine) (POT) and poly(ortho-anisidine) (PAs) in N-methyl pyrrolidinone (NMP) were examined by viscometric, gel permeation chromatographic (GPC) and theological methods. Strong intermolecular interaction and molecular aggregation are shown.

THERMAL BEHAVIORS OF INTRINSIC POLYANILINE AND ITS DERIVATIVES

Thermal properties of polyaniline (PAn), polytoluidine(POT) and polyanisidine(PAs) were examined by TG and DSC techniques. The weight-uptake of POT at 200-300 degrees C was observed and carefully discussed.

STUDIES ON THE DIELECTRIC BEHAVIOUR OF POLYPYRROLE AND ITS COMPOSITES WITH POLY (VINYL CHLORIDE)

Polypyrrole/poly (vinyl chloride) semi-interpenenzrtirtg networks of different compositions are prepared using anunonitun per sulfate initiator at room temperature in pellet.form and lilrrt form and their dielectric properties are studied at different microwave frequencies. An HP 8510 Vector network analyzer interfaced with a computer is used. The cavity-perturbation technique is employed for the study

Thermo-analyses of polyaniline and its derivatives

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Corrosion and tribocorrosion behaviour of Al-Si-Cu-Mg alloy and its composites reinforced with B4C particles in 0.05M NaCl solution

The corrosion behaviour of metal matrix composites (MMCs) is strictly linked with the presence of heterogeneities such as reinforcement phase, microcrevices, porosity, secondary phase precipitates, and interaction products. Most of the literature related to corrosion behaviour of aluminium matrix composites (AMCs) is focused on SiC reinforced AMCs. On the other hand, there is very limited information available in the literature related to the tribocorrosion behaviour of AMCs. Therefore, the present work aims to investigate corrosion and tribocorrosion behaviour of Al-Si-Cu-Mg alloy matrix composites reinforced with B4C particulates. Corrosion behaviour of 15 and 19% (vol) B4C reinforced Al-Si-Cu-Mg matrix composites and the base alloy was investigated in 0.05M NaCl solution by performing immersion tests and potentiodynamic polarisation tests. Tribocorrosion behaviour of Al-Si-Cu-Mg alloy and its composites were also investigated in 0.05M NaCl solution. The tests were carried out against alumina ball using a reciprocating ball-on-plate tribometer. Electrochemical measurements were performed before, during, and after the sliding tests together with the recording of the tangential force. Results suggest that particle addition did not affect significantly the tendency of corrosion of Al-Si-Cu-Mg alloy without mechanical interactions. During the tribocorrosion tests, the counter material was found to slide mainly on the B4C particles, which protected the matrix alloy from severe wear damage. Furthermore, the wear debris were accumulated on the worn surfaces and entrapped between the reinforcing particles. Therefore, the tendency of corrosion and the corrosion rate decreased in Al-Si-Cu-Mg matrix B4C reinforced composites during the sliding in 0.05M NaCl solution. © 2013 Elsevier B.V.

Investigations on polyaniline based systems for technologically important applications and some novel polymers as prospective candidates for fabricating polymer light emitting diodes

Light emitting polymers (LEP) have drawn considerable attention because of their numerous potential applications in the field of optoelectronic devices. Till date, a large number of organic molecules and polymers have been designed and devices fabricated based on these materials. Optoelectronic devices like polymer light emitting diodes (PLED) have attracted wide-spread research attention owing to their superior properties like flexibility, lower operational power, colour tunability and possibility of obtaining large area coatings. PLEDs can be utilized for the fabrication of flat panel displays and as replacements for incandescent lamps. The internal efficiency of the LEDs mainly depends on the electroluminescent efficiency of the emissive polymer such as quantum efficiency, luminance-voltage profile of LED and the balanced injection of electrons and holes. Poly (p-phenylenevinylene) (PPV) and regio-regular polythiophenes are interesting electro-active polymers which exhibit good electrical conductivity, electroluminescent activity and high film-forming properties. A combination of Red, Green and Blue emitting polymers is necessary for the generation of white light which can replace the high energy consuming incandescent lamps. Most of these polymers show very low solubility, stability and poor mechanical properties. Many of these light emitting polymers are based on conjugated extended chains of alternating phenyl and vinyl units. The intra-chain or inter-chain interactions within these polymer chains can change the emitted colour. Therefore an effective way of synthesizing polymers with reduced π-stacking, high solubility, high thermal stability and high light-emitting efficiency is still a challenge for chemists. New copolymers have to be effectively designed so as to solve these issues. Hence, in the present work, the suitability of a few novel copolymers with very high thermal stability, excellent solubility, intense light emission (blue, cyan and green) and high glass transition temperatures have been investigated to be used as emissive layers for polymer light emitting diodes.

Fabrication and electrocatalytic properties of polyaniline/Pt nanoparticle composites

Polyaniline (PANI)/Pt nanoparticle composites can be prepared by the spontaneous redox reaction of K2PtCl4 with PANI, to yield thin films that show electrocatalytic properties in both acidic and neutral aqueous media.