Oligo(p-Phenylenevinylene) Derived Organogels: A Novel Class of Functional Supramolecular Materials

The main objective of the present study is to have a detailed investigation on the gelation properties, morphology and optical properties of small π-conjugated oligomers. For this purpose we have chosen oligo(p-phenylenevinylene)s (OPVs), a class of molecules which have received considerable attention due to their unique optical and electronic properties. Though a large number of reports are available in the literature on the self-assembly properties of tailor made OPVs, none of them pertain to the design of nanostructures based on organogels. In view of this, we aimed at the creation of functional chromophoric assemblies of π-conjugated OPVs through the formation of organogels, with the objective of crafting nanoscopic assemblies of different size and shape thereby modulating their optical and electronic properties.In order to fulfill the above objectives, the design and synthesis of a variety of OPVs with appropriate structural variations were planned. The design principle involves the derivatization of OPVs with weak H-bonding hydroxymethyl end groups and with long aliphatic hydrocarbon side chains. The noncovalent interactions in these molecules were expected to lead the formation of supramolecular assembly and gels in hydrocarbon solvents. In such an event, detailed study of gelation and extensive analysis of the morphology of the gel structures were planned using advanced microscopic techniques. Since OPVs are strongly fluorescent molecules, gelation is expected to perturb the optical properties. Therefore, detailed study on the gelation induced optical properties as a way to probe the nature and stability of the selfassembly was planned. Apart from this, the potential use of the modulation of the optical properties for the purpose of light harvesting was aimed. The approach to this problem was to entrap an appropriate energy trap to the OPV gel matrix which may lead to the efficient energy transfer from the OPV gel based donor to the entrapped acceptor. The final question that we wanted to address in this investigation was the creation of helical nanostructures through proper modification of the OPV backbone With chiral handles.The present thesis is a detailed and systematic approach to the realization of the above objectives which are presented in different chapters of the thesis.

Aqueous Sol-gel Process for Nanocrystalline Photocatalytic Titania, Transparent Functional Coatings and Ceramic Membrane

The present thesis develops from the point of view of titania sol-gel chemistry and an attempt is made to address the modification of the process for better photoactive titania by selective doping and also demonstration of utilization of the process for the preparation of supported membranes and self cleaning films.A general introduction to nanomaterials, nanocrystalline titania and sol-gel chemistry are presented in the first chapter. A brief and updated literature review on sol-gel titania, with special emphasis on catalytic and photocatalytic properties and anatase to rutile transformation are covered. Based on critical assessment of the reported information the present research problem has been defined.The second chapter describes a new aqueous sol-gel method for the preparation of nanocrystalline titania using titanyl sulphate as precursor. This approach is novel since no earlier work has been reported in the same lines proposed here. The sol-gel process has been followed at each step using particle size, zeta potential measurements on the sol and thermal analysis of the resultant gel. The prepared powders were then characterized using X-ray diffraction, FTIR, BET surface area analysis and transmission electron microscopy.The third chapter presents a detailed discussion on the physico-chemical characterization of the aqueous sol-gel derived doped titania. The effect of dopants such as tantalum, gadolinium and ytterbium on the anatase to rutile phase transformation, surface area as well as their influence on photoactivity is also included. The fourth chapter demonstrates application of the aqueous sol-gel method in developing titania coatings on porous alumina substrates for controlling the poresize for use as membrane elements in ultrafiltration. Thin coatings having ~50 nm thickness and transparency of ~90% developed on glass surface were tested successfully for self cleaning applications.

Optical and thermal characterization of dye intercalated montmorillonites and rare earth doped materials

The advent of high optical quality transparent nano—structured glasses, the so-called transparent glass ceramics or vitroceramics disclosed the possibility of producing nano-sized photonic devices based on rare-earth doped up—converters. Transparent glass ceramics have been investigated as hosts for lanthanide ions envisioning the production of materials that are easy to shape and with high performance for photonic applications. Rare earth doped glasses have been extensively studied due to their potential applications in optical devices such as solid state lasers and optical fibers. Various photothermal and optical techniques have been successfully applied for the thermal and optical characterization of these rare earth doped materials. In the present thesis, the effective thermal parameters like thermal diffusivity and thermal effusivity of complex materials for various applications have been investigated using photothermal methods along with their optical characterization utilising the common optical absorption as well as fluorescence spectroscopic techniques. These sensitive optical procedures are also essential for exploiting these materials for further photonic applications.

On conduction mechanism in paramagnetic phase of Gd based manganites

Materials belonging to the family of manganites are technologically important since they exhibit colossal magneto resistance. A proper understanding of the transport properties is very vital in tailoring the properties. A heavy rare earth doped manganite like Gd0·7Sr0·3MnO3 is purported to be exhibiting unusual properties because of smaller ionic radius of Gd. Gd0·7Sr0·3MnO3 is prepared by a wet solid state reaction method. The conduction mechanism in such a compound has been elucidated by subjecting the material to low temperature d.c. conductivity measurement. It has been found that the low band width material follows a variable range hopping (VRH) model followed by a small polaron hopping (SPH) model. The results are presented here

Towards Realization of Magnetocaloric and Magnetoelectric Applications based on Bulk and Thin film forms of Sodium substituted Lanthanum Manganites

The present thesis work focuses on hole doped lanthanum manganites and their thin film forms. Hole doped lanthanum manganites with higher substitutions of sodium are seldom reported in literature. Such high sodium substituted lanthanum manganites are synthesized and a detailed investigation on their structural and magnetic properties is carried out. Magnetic nature of these materials near room temperature is investigated explicitly. Magneto caloric application potential of these materials are also investigated. After a thorough investigation of the bulk samples, thin films of the bulk counterparts are also investigated. A magnetoelectric composite with ferroelectric and ferromagnetic components is developed using pulsed laser deposition and the variation in the magnetic and electric properties are investigated. It is established that such a composite could be realized as a potential field effect device. The central theme of this thesis is also on manganites and is with the twin objectives of a material study leading to the demonstration of a device. This is taken up for investigation. Sincere efforts are made to synthesize phase pure compounds. Their structural evaluation, compositional verification and evaluation of ferroelectric and ferromagnetic properties are also taken up. Thus the focus of this investigation is related to the investigation of a magnetoelectric and magnetocaloric application potentials of doped lanthanum manganites with sodium substitution. Bulk samples of sodium substituted lanthanum manganites. Bulk samples of sodium substituted lanthanum manganites with Na substitution ranging from 50 percent to 90 percent were synthesized using a modified citrate gel method and were found to be orthorhombic in structure belonging to a pbnm spacegroup. The variation in lattice parameters and unit cell volume with sodium concentration were also dealt with. Magnetic measurements revealed that magnetization decreased with increase in sodium concentrations.

Synthesis, Characterization and Applications of Modified TiO2 Systems

This thesis is divided in to 9 chapters and deals with the modification of TiO2 for various applications include photocatalysis, thermal reaction, photovoltaics and non-linear optics. Chapter 1 involves a brief introduction of the topic of study. An introduction to the applications of modified titania systems in various fields are discussed concisely. Scope and objectives of the present work are also discussed in this chapter. Chapter 2 explains the strategy adopted for the synthesis of metal, nonmetal co-doped TiO2 systems. Hydrothermal technique was employed for the preparation of the co-doped TiO2 system, where Ti[OCH(CH3)2]4, urea and metal nitrates were used as the sources for TiO2, N and metals respectively. In all the co-doped systems, urea to Ti[OCH(CH3)2]4 was taken in a 1:1 molar ratio and varied the concentration of metals. Five different co-doped catalytic systems and for each catalysts, three versions were prepared by varying the concentration of metals. A brief explanation of physico-chemical techniques used for the characterization of the material was also presented in this chapter. This includes X-ray Diffraction (XRD), Raman Spectroscopy, FTIR analysis, Thermo Gravimetric Analysis, Energy Dispersive X-ray Analysis (EDX), Scanning Electron Microscopy(SEM), UV-Visible Diffuse Reflectance Spectroscopy (UV-Vis DRS), Transmission Electron Microscopy (TEM), BET Surface Area Measurements and X-ray Photoelectron Spectroscopy (XPS). Chapter 3 contains the results and discussion of characterization techniques used for analyzing the prepared systems. Characterization is an inevitable part of materials research. Determination of physico-chemical properties of the prepared materials using suitable characterization techniques is very crucial to find its exact field of application. It is clear from the XRD pattern that photocatalytically active anatase phase dominates in the calcined samples with peaks at 2θ values around 25.4°, 38°, 48.1°, 55.2° and 62.7° corresponding to (101), (004), (200), (211) and (204) crystal planes (JCPDS 21-1272) respectively. But in the case of Pr-N-Ti sample, a new peak was observed at 2θ = 30.8° corresponding to the (121) plane of the polymorph brookite. There are no visible peaks corresponding to dopants, which may be due to their low concentration or it is an indication of the better dispersion of impurities in the TiO2. Crystallite size of the sample was calculated from Scherrer equation byusing full width at half maximum (FWHM) of the (101) peak of the anatase phase. Crystallite size of all the co-doped TiO2 was found to be lower than that of bare TiO2 which indicates that the doping of metal ions having higher ionic radius into the lattice of TiO2 causes some lattice distortion which suppress the growth of TiO2 nanoparticles. The structural identity of the prepared system obtained from XRD pattern is further confirmed by Raman spectra measurements. Anatase has six Raman active modes. Band gap of the co-doped system was calculated using Kubelka-Munk equation and that was found to be lower than pure TiO2. Stability of the prepared systems was understood from thermo gravimetric analysis. FT-IR was performed to understand the functional groups as well as to study the surface changes occurred during modification. EDX was used to determine the impurities present in the system. The EDX spectra of all the co-doped samples show signals directly related to the dopants. Spectra of all the co-doped systems contain O and Ti as the main components with low concentrations of doped elements. Morphologies of the prepared systems were obtained from SEM and TEM analysis. Average particle size of the systems was drawn from histogram data. Electronic structures of the samples were identified perfectly from XPS measurements. Chapter 4 describes the photocatalytic degradation of herbicides Atrazine and Metolachlor using metal, non-metal co-doped titania systems. The percentage of degradation was analyzed by HPLC technique. Parameters such as effect of different catalysts, effect of time, effect of catalysts amount and reusability studies were discussed. Chapter 5 deals with the photo-oxidation of some anthracene derivatives by co-doped catalytic systems. These anthracene derivatives come underthe category of polycyclic aromatic hydrocarbons (PAH). Due to the presence of stable benzene rings, most of the PAH show strong inhibition towards biological degradation and the common methods employed for their removal. According to environmental protection agency, most of the PAH are highly toxic in nature. TiO2 photochemistry has been extensively investigated as a method for the catalytic conversion of such organic compounds, highlighting the potential of thereof in the green chemistry. There are actually two methods for the removal of pollutants from the ecosystem. Complete mineralization is the one way to remove pollutants. Conversion of toxic compounds to another compound having toxicity less than the initial starting compound is the second way. Here in this chapter, we are concentrating on the second aspect. The catalysts used were Gd(1wt%)-N-Ti, Pd(1wt%)-N-Ti and Ag(1wt%)-N-Ti. Here we were very successfully converted all the PAH to anthraquinone, a compound having diverse applications in industrial as well as medical fields. Substitution of 10th position of desired PAH by phenyl ring reduces the feasibility of photo reaction and produced 9-hydroxy 9-phenyl anthrone (9H9PA) as an intermediate species. The products were separated and purified by column chromatography using 70:30 hexane/DCM mixtures as the mobile phase and the resultant products were characterized thoroughly by 1H NMR, IR spectroscopy and GCMS analysis. Chapter 6 elucidates the heterogeneous Suzuki coupling reaction by Cu/Pd bimetallic supported on TiO2. Sol-Gel followed by impregnation method was adopted for the synthesis of Cu/Pd-TiO2. The prepared system was characterized by XRD, TG-DTG, SEM, EDX, BET Surface area and XPS. The product was separated and purified by column chromatography using hexane as the mobile phase. Maximum isolated yield of biphenyl of around72% was obtained in DMF using Cu(2wt%)-Pd(4wt%)-Ti as the catalyst. In this reaction, effective solvent, base and catalyst were found to be DMF, K2CO3 and Cu(2wt%)-Pd(4wt%)-Ti respectively. Chapter 7 gives an idea about the photovoltaic (PV) applications of TiO2 based thin films. Due to energy crisis, the whole world is looking for a new sustainable energy source. Harnessing solar energy is one of the most promising ways to tackle this issue. The present dominant photovoltaic (PV) technologies are based on inorganic materials. But the high material, low power conversion efficiency and manufacturing cost limits its popularization. A lot of research has been conducted towards the development of low-cost PV technologies, of which organic photovoltaic (OPV) devices are one of the promising. Here two TiO2 thin films having different thickness were prepared by spin coating technique. The prepared films were characterized by XRD, AFM and conductivity measurements. The thickness of the films was measured by Stylus Profiler. This chapter mainly concentrated on the fabrication of an inverted hetero junction solar cell using conducting polymer MEH-PPV as photo active layer. Here TiO2 was used as the electron transport layer. Thin films of MEH-PPV were also prepared using spin coating technique. Two fullerene derivatives such as PCBM and ICBA were introduced into the device in order to improve the power conversion efficiency. Effective charge transfer between the conducting polymer and ICBA were understood from fluorescence quenching studies. The fabricated Inverted hetero junction exhibited maximum power conversion efficiency of 0.22% with ICBA as the acceptor molecule. Chapter 8 narrates the third order order nonlinear optical properties of bare and noble metal modified TiO2 thin films. Thin films were fabricatedby spray pyrolysis technique. Sol-Gel derived Ti[OCH(CH3)2]4 in CH3CH2OH/CH3COOH was used as the precursor for TiO2. The precursors used for Au, Ag and Pd were the aqueous solutions of HAuCl4, AgNO3 and Pd(NO3)2 respectively. The prepared films were characterized by XRD, SEM and EDX. The nonlinear optical properties of the prepared materials were investigated by Z-Scan technique comprising of Nd-YAG laser (532 nm,7 ns and10 Hz). The non-linear coefficients were obtained by fitting the experimental Z-Scan plot with the theoretical plots. Nonlinear absorption is a phenomenon defined as a nonlinear change (increase or decrease) in absorption with increasing of intensity. This can be mainly divided into two types: saturable absorption (SA) and reverse saturable absorption (RSA). Depending on the pump intensity and on the absorption cross- section at the excitation wavelength, most molecules show non- linear absorption. With increasing intensity, if the excited states show saturation owing to their long lifetimes, the transmission will show SA characteristics. Here absorption decreases with increase of intensity. If, however, the excited state has strong absorption compared with that of the ground state, the transmission will show RSA characteristics. Here in our work most of the materials show SA behavior and some materials exhibited RSA behavior. Both these properties purely depend on the nature of the materials and alignment of energy states within them. Both these SA and RSA have got immense applications in electronic devices. The important results obtained from various studies are presented in chapter 9.

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.