Made available in DSpace on 2014-12-17T14:07:07Z (GMT). No. of bitstreams: 1 MarcioCSM_TESE.pdf: 957118 bytes, checksum: 7c10d815ada900ecb0efde8936a6064e (MD5) Previous issue date: 2011-07-29 / The growing concern with the solid residues management, observed in the last decade, due to its huge amount and impact, has motivated the search for recycling processes, where these residues can be reprocessed to generate new products, enlarging the cycle of materials and energy which are present. Among the polymeric residues, there is poly (ethylene terephthalate) (PET). PET is used in food packaging, preferably in the bottling of carbonated beverages. The reintegration of post-consumer PET in half can be considered a productive action mitigation of environmental impacts caused by these wastes and it is done through the preparation of several different products at the origin, i.e. food packaging, with recycling rates increasing to each year. This work focused on the development and characterization mechanical, thermal, thermo-mechanical, dynamic mechanical thermal and morphology of the pure recycled PET and recycled PET composites with glass flakes in the weight fraction of 5%, 10% and 20% processed in a single screw extruder, using the following analytical techniques: thermogravimetry (TG), differential scanning calorimetry (DSC), tensile, Izod impact, Rockwell hardness, Vicat softening temperature, melt flow rate, burn rate, dynamic mechanical thermal analysis (DMTA) and scanning electron microscopy (SEM). The results of thermal analysis and mechanical properties leading to a positive evaluation, because in the thermograms the addition of glass flakes showed increasing behavior in the initial temperatures of thermal decomposition and melting crystalline, Furthermore was observed growing behavior in the mechanical performance of polymer composites, whose morphological structure was observed by SEM, verifying a good distribution of glass flakes, showing difference orientation in the center and in the surface layer of test body of composites with 10 and 20% of glass flakes. The results of DMTA Tg values of the composites obtained from the peak of tan ? showed little reductions due to poor interfacial adhesion between PET and recycled glass flakes. / A crescente preocupa??o com a gest?o de res?duos s?lidos, observada na ?ltima d?cada, em virtude de sua enorme quantidade e impacto ambiental, tem motivado a busca por processos de reciclagem, onde estes res?duos podem ser reprocessados de modo a gerarem novos produtos, ampliando o ciclo dos materiais e energia neles contidos. Dentre os res?duos polim?ricos, destaca-se o poli(tereftalato de etileno) (PET). O PET ? utilizado em embalagens de alimentos, preferencialmente, no envase de bebidas carbonatadas. A reintegra??o do PET p?s-consumo ao meio produtivo pode ser considerada uma a??o mitigat?ria dos impactos ambientais causados por estes res?duos e j? ? realizada por meio da obten??o de diversos produtos diferentes ao da origem, ou seja, embalagens para alimento, com taxas de reciclagem crescente a cada ano. Este trabalho focou o desenvolvimento e a caracteriza??o mec?nica, t?rmica, termo-mec?nica, termo-din?mico-mec?nica e morfol?gica do PET reciclado processado e dos comp?sitos de PET reciclado com flocos de vidro na fra??o em peso de 5%, 10% e 20% processados em uma extrusora rosca simples, utilizando as seguintes t?cnicas de an?lise: termogravimetria (TG), calorimetria explorat?ria diferencial (DSC), tra??o uniaxial, impacto Izod, dureza Rockwel, temperatura de amolecimento Vicat, ?ndice de fluidez, taxa de queima, an?lise termo-din?mico-mec?nica (DMTA) e microscopia eletr?nica de varredura (MEV). Os resultados das an?lises t?rmicas e das propriedades mec?nicas conduziram a uma avalia??o positiva, pois nos termogramas as adi??es dos flocos de vidro mostraram comportamento crescente nas temperaturas inicial de decomposi??o t?rmica e de fus?o cristalina, al?m disso, observou-se comportamento crescente no desempenho mec?nico dos comp?sitos polim?ricos, cuja estrutura morfol?gica foi observada por MEV, verificando uma boa distribui??o dos flocos de vidro, apresentando diferen?a na orienta??o no centro e na camada superficial do corpo de prova dos comp?sitos com 10 e 20% de flocos de vidro. Nos resultados de DMTA os valores de Tg dos comp?sitos obtidos a partir do pico de tan ?, apresentaram pequenas redu??es, devido a pobre ades?o interfacial entre o PET reciclado e os flocos de vidro.

Metal ion contamination in surface and ground water is a major threat as it has a direct implication on the health of terrestrial and aquatic flora and fauna. Lead (Pb2+), mercury (Hg2+), cadmium (Cd2+), nickel (Ni2+), copper (Cu2+) and cobalt (Co2+) are few of these metal ions which are classified under the high risk category. Of these, lead and mercury are of greater concern, as even nanomolar concentrations can be lethal, as they can be bio-accumulated and result in physiological as well as neurological disorders. In Asian countries like India and China, heavy metal pollution is more prevalent, as a consequence of poor governmental policies or ineffective or inadequate measures to combat this problem. In recent times, the monitoring and assessment of water pollution is a critical area of study, as it has a direct implication for its prevention and control. The major techniques used for metal ion detection are atomic absorption spectroscopy (AAS), X-ray fluorescence, ion chromatography, neutron activation, etc. Alternatively, the electrochemical, optical and electrical methods provide a platform for the fabrication of portable devices, which can facilitate the on-site analysis of samples in a rapid and cost-effective manner. This has led to a new field of research called chemical sensors or chemo sensory devices. The main aim of this study is to develop various chemosensory materials and test their response towards metal ion sensing. In this study, electroactive polymers have been synthesized for various sensor applications. The focus has been to design synthesize and test various functionalized electroactive polymers (FEAP) for the development of electrochemical, optical and chemoresistive sensors. Electroactive polymers like polyaniline, polypyrrole, polypyrrole grafted to exfoliated graphite oxide and dipyrromethene conjugated with p-(phenylene vinylene) have been synthesized and evaluated after functionalizing with metal coordinating ligands. These metal coordinating ligands were selected, in order to enhance their metal uptake capacity. Various metal ligands like imidazole, tertiary amine group, iminodiacetic acid, and dipyrromethene incorporated either in the polymer backbone or as a part of the backbone have been chosen for the metal binding. These functionalized electroactive polymers (FEAP) served as active material for metal ion sensing. The present investigation is subdivided into three sections. The first part includes design and chemical synthesis of the functionalized polymers by a series of organic reactions. The synthesis has been followed up by characterization using spectroscopic methods including NMR, FTIR, GCMS and Mass spectrometry. In the second part of the investigation, the synthesized polymer has been characterized for the changes in electronic, electric and optical properties after interaction with the selected metal ions. For this, the FEAP is allowed to interact with various metal ions and the changes in the relevant properties have been measured. This includes the study of changes in the conductivity, electronic properties like absorption or emission of the polymer, changes in the redox properties, etc. The third phase of investigation deals with the fabrication of the devices using the active FEAP. The sensor devices comprised of either films, or electrode modified with FEAP or solution of the FEAP, in combination with an appropriate technique has been used for the sensing. The major objectives are enumerated below 1. Functionalzation of polyaniline with imidazole functional group to get imidazole functionalized polyaniline (IMPANI) and study of the electronic, electrical and optical properties of the same. 2. Preparation of films of IMPANI and study of the change in conductivity of the film upon interaction with various metal ions, namely Cu2+, Co2+ and Ni2+ in their chloride form. 3. Synthesis of amine functionalized aniline monomer and chemical graft polymerization onto exfoliated graphite oxide as a substrate to synthesise the amine funtionalised polyaniline grafted to exfoliated graphite oxide (EGAMPANI). Modification of the carbon paste electrode (CPE) with EGAMPANI and study of the electrode characteristic. 4. Study of the electrode properties of EGAMPANI modified carbon paste electrode. 5. Evaluation of the EGAMPANI modified carbon paste electrode as a multi-elemental voltammetric sensor for Pb2+, Hg2+ and Cd2+ in aqueous system. 6. Functionalization of polypyrrole with iminodiacetic acid and characterization of the polymer to synthesis iminodiacetic acid functionalized polypyrrole (IDA-PPy). 7. Modification of the CPE with IDA-PPy by drop casting method and evaluation of the Pb2+ sensing properties. 8. Study of the effect of other metal ions say Hg2+, Co2+, Ni2+, Zn2+, Cu2+ and Cd2+ on the anodic stripping current of Pb2+ using EGAMPANI modified CPE. 9. Synthesis of dipyrromethene-p-(phenylene vinylene) conjugated polymer for heavy metal ion sensing. 10. Study of the changes in the optical absorption and emission properties of the polymer in THF and evaluation of the change in these optical properties upon interaction with the metal ions as analyte. The salient findings of the research work are highlighted as follows, In the first synthesis, aniline has been functionalized with imidazole group and this monomer has been chemical oxidatively polymerized to obtain imidazole functionalized polyaniline (IMPANI). The synthesized polymer possesses a nano-spherical structure, as confirmed from the morphological characterisation using scanning electron microscopy. The IMPANI has been interacted with a representative metal ion, copper (II) chloride, and the copper complexed polymer (Cu-IMPANI) has been subjected to various studies. The coordination of copper with IMPANI results in an increase of molecular weight of the polymer as a result of aggregation, as observed from dynamic light scattering measurements. Apart from this, a significant finding is the decrease of the pH of the system after copper ion coordination attesting to the generation of a secondary hydrochloride ion during the coordination of the copper to the imidazole side chain. This is further confirmed by an increase in conductivity of the Cu-IMPANI compared to IMPANI, measured using the four-probe technique. The increase of conductivity due to copper coordination is one order of magnitude higher. The films which have been prepared from IMPANI and Cu-IMPANI exhibit different morphology. The Cu-IMPANI film prepared by prior co-ordination of Cu ion with IMPANI powder shows a flaky structure, which is not preferable for the conductivity measurements, as a consequence of discontinuity in the medium. To overcome this problem, IMPANI films were initially prepared and then interacted with copper ions for a desired duration, before measurement of the conductivity. This latter procedure enabled the preparation of smooth films for the development of chemoresistive sensors. In continuation of the initial study highlighted above, IMPANI films of thickness 0.02 ± 0.001 mm have been prepared using IMPANI and PANI in DMPU in the ratio of 7:3 by mass. After exposure of the films with respective metal chlorides, such as Ni2+, Co2+ and Cu2+, a change in conductivity is observed in the concentration range of 10-2 to 1 M of metal chlorides. The sensor response may be arranged in the sequence: Ni2+ > Cu2+ > Co2+ at 1M concentration. On the contrary, films prepared from PANI-EB under identical conditions do not exhibit any appreciable change in conductivity. The optimum exposure time is determined to be 10 min for a maximum change in conductivity, after exposure to the chosen metal ions. In the second system taken up for investigation, a tertiary amine containing polyaniline (AMPANI) has been grafted to exfoliated graphite oxide. The amine containing polyaniline grafted to exfoliated graphite oxide (EGAMPANI) has been characterised for structural, morphological and elemental composition. The grafting percentage has been determined to be 7 % by weight of AMPANI on the EGO surface. The synthesized EGAMPANI (5 weight %) has been used to modify carbon paste electrode (CPE) for electrochemical sensor studies. Based on the differential pulse anodic stripping voltammetric studies, the electrochemical response may be arranged in the following sequence: Pb 2+>Cd 2+>Hg 2+ The minimum detection levels obtained are 5×10-6, 5×10-7, and 1.0×10-7 M for Hg2+, Cd2+ and Pb2+ ions respectively. In the next study, an iminodiacetic acid functionalized polypyrrole (IDA-PPy) has been synthesized and characterised for its elemental and structural properties. This has been further used to modify the CPE by drop casting method and used for the specific detection of Pb2+ in acetate buffer. Various parameters governing the electrode performance such as concentration of depositing solution, pH of depositing solution, deposition potential, deposition time, and scan rate, have been optimized to achieve maximum performance and found to be 20 μl, 4.5, -1.3 V, 11 min, 8 mV s-1 respectively for the chosen parameters. Additionally, the influence of other heavy metal ions on the lead response has been studied and it is observed that Co, Cu and Cd ions are found to be interfering. Further, the response of Cd, Co, Cu, Hg, Ni and Zn on IDA-PPy functionalized electrode has been evaluated. The selectivity of IDA-PPy modified electrode for Pb2+ is observed in the concentration range of 1 × 10-7 M and below. The IDA-PPy modified CPE shows a linear correlation for Pb2+ concentration in the range from 1×10-6 to 5×10-9 M and with a lowest limit of detection (LLOD) of 9.6×10-9 M concentration. The efficacy of the electrode for lead sensing has also been evaluated with an industrial effluent sample obtained from a lead battery manufacturing unit. The fourth synthesis pertained to the development of an optical sensor for Fe2+, and Co2+ ions. For this, dipyrromethene as a metal coordinating ligand in conjugation with p-phenylenevinylene has been synthesized and tested for its structural as well as optical properties. It is observed that the polymer shows three absorptions, namely at 294 nm, 357 nm and a major absorption observed as a broad band ranging from 484 to 670 nm. The emission spectrum of the polymer excited at 357 nm shows a characteristic blue emission with a maximum intensity centered at 425 nm. The emission quenching in the presence of various metal ions have been tested and are found to be quenched in presence of Fe2+ and Co2+ ions. All the other metal ions tested namely, Cr3+, Cu2+, and Zn2+ are not found to exhibit any change in the emission spectra below the concentration of 1 × 10-4 M. The linear correlation of the emission intensity with the concentration of the Co2+ and Fe2+ ions has been determined using Stern-Volmer plot. For Co2+ the Stern-Volmer regime is observed from 1×10-4 to 9×10-4 M concentration and the quenching constant Ksv is determined to be 8.67 ×103 M-1. For Fe2+, the linearity is found to be in the regime of 1×10-5 to 9×10-5 M and the quenching constant Ksv is determined to be 7.90 × 103 M-1. In conclusion, different electroactive polymers functionalized with metal coordinating ligands have been synthesized, characterised and evaluated for metal sensing applications. Techniques like electrochemical, optical and conductivity have been used to characterise the response of these FEAP towards metal sensing. It is can be concluded that the electrochemical sensors are more reliable for sensing especially at very low concentrations of metal ions such as Pb, Cd and other techniques like optical and conductimetric are good for detecting metal ions namely Fe, Co, Ni, Cu. The selectivity towards the metal ions is a function of the metal chelating ligand and the extent of sensitivity is dependent upon the technique employed.

The present thesis deals with a theoretical study of electronic structures in -conjugated molecular materials with focus on their application in organic elec-tronics. We also discuss a modified and efficient symmetrized DMRG algorithm for studying excited states in these systems. In recent times, organic conjugated systems have emerged as potential candidates in a wide range of fascinating fields by virtue of their tunable electronic properties, easy processability and low cost. Tunability in the electronic and optical properties primarily are centered on the or-dering and nature of the low-lying excited states. Probing these important excited states also demands development of efficient and adaptable techniques. Chapter 1 provides a basic overview of conjugated organic polymers which have been utilized over decades in diverse fields as in organic light emitting diodes (OLED), organic solar cells (OSC) and non-linear optical (NLO) devices. These systems also contribute significantly to theoretical understanding as they pro vide important insights of one and quasi-one dimensional systems. In this chapter, we have given basic description of the electronic processes in OLED and OSC along with a brief theoretical description of -conjugated organic systems. Chapter 2 gives an account of the numerical techniques which are necessary for the study of low-dimensional strongly correlated systems like -conjugated sys-tems. For this purpose, effective low-energy model Hamiltonians viz. Huckel,¨ Hubbard and Pariser-Parr-Pople Hamiltonians are discussed. Exact diagonalization technique within the diagrammatic valence bond (DVB) basis and density matrix renormalization group (DMRG) technique are discussed in details. We have also given brief accounts of the methods employed to study real-time dynamics. A short description of different computational techniques for the study of NLO properties in -conjugated systems is also provided. Engineering the position of the lowest triplet state (T1) relative to the first excited singlet state (S1) is of great importance in improving the efficiencies of organic light emitting diodes and organic photovoltaic cells. In chapter 3, we have carried out model exact calculations of substituted polyene chains to understand the fac-tors that affect the energy gap between S1 and T1. The factors studied are backbone dimerization, different donor-acceptor substitutions and twisted backbone geome-try. The largest system studied is an eighteen carbon polyene which spans a Hilbert space of about 991 million in the triplet subspace. We show that for reverse inter-system crossing (RISC) process, the best choice involves substituting all carbon sites on one half of the polyene with donors and the other half with acceptors. Singlet fission (SF) is a potential pathway for significant enhancement of efficiency in OSC. In chapter 4, we study singlet fission in a pair of polyene molecules in two different stacking arrangements employing exact many-body wave packet dy-namics. In the non-interacting model, SF is absent. The individual molecules are treated within Hubbard and Pariser-Parr-Pople (PPP) models and the interac-tion between them involves transfer terms, intersite electron repulsions and site-charge—bond-charge repulsion terms. Initial wave packet is construc ted from ex-cited singlet state of one molecule and ground state of the other. Time develop-ment of this wave packet under the influence of intermolecular interactions is fol-lowed within the Schrodinger¨ picture by an efficient predictor-corrector scheme. In unsubstituted Hubbard and PPP chains, 21A state leads to significant SF yield while the 11B state gives negligible fission yield. On substitution by donor-acceptor groups of moderate strength, the lowest excited state will have sufficient 2 1A char-acter and hence gives significant SF yield. Because of rapid internal c onversion, the nature of the lowest excited singlet will determine the SF contribution to OSC effi - ciency. Furthermore, we find the fission yield depends considerably on th e stacking arrangement of the polyene molecules. In chapter 5, we have given an account of a new modified algorithm for symmetry adaptation within symmetrized density matrix renormalization group (SDMRG) technique. SDMRG technique has been an efficient method for studying low-lying eigenstates in one and quasi-one dimensional electronic systems. However, SDMRG method until now, had bottlenecks involving construction of linearly in-dependent symmetry adapted basis states as the symmetry matrices in the DMRG basis were not sparse. Our modified algorithm overcomes this bottleneck. T he new method incorporates end-to-end interchange symmetry (C2), electron-hole symmetry (J) and parity or spin-flip symmetry (P) in these calculations. The one-to-one correspondence between direct-product basis states in the DMRG Hilbert space for these symmetry operations renders the symmetry matrices in the new ba-sis with maximum sparseness, just one non-zero matrix element per row. Using methods similar to those employed in exact diagonalization technique for Pariser-Parr-Pople (PPP) models, developed in the eighties, it is possible to construct or-thogonal SDMRG basis states while bypassing the slow step of Gram-Schmidt orthonormalization procedure. The method together with the PPP model which incorporates long-range electronic correlations is employed to study the correlated excited states of 1,12-benzoperylene. In chapter 6, we have studied the correlated excited states of coronene and ova-lene within Pariser-Parr-Pople (PPP) model employing symmetry adapted density matrix renormalization group technique. These polynuclear aromatic hydrocar-bons can be considered as graphene nanoflakes and study of their ele ctronic struc-tures will shed light on the electron correlation effects in these finite-size gr aphene analogues. The electron correlation effect usually diminishes on going from one-dimensional to higher-dimensional systems, yet, it is significant within these fin ite-size graphene derivatives where it depends on the molecular topology. We have characterized these low-lying energy states by calculating bond orders, spin den-sities in the lowest triplet state and two-photon absorption cross-sections for low-lying two-photon states. vi

Much study has been carried out to determine the properties of Lamellar Graphite Iron (LGI) or grey iron and their relations to factors such as the cooling rate, the dendrite morphology, the pouring temperature, and so on. However, there hasn’t been much comprehensive study on the properties of LGI outside the generally used and accepted composition, with 1 to 3% Silicon. The scope of this study is to measure and evaluate the thermal conductivity and tensile strength of LGI, for a higher concentration of  Si and different carbon contents. The concentration of Si aimed for was 4% but the concentration obtained after spectroscopy was between 4.1% to 4.15%. There are two hypereutectic, one near-eutectic and three hypoeutectic samples considered and these six chemical compositions were cast under different cooling conditions . The cooling time has been varied by providing different molds of 30mm, 55mm, and 80mm diameter cylinders respectively, for all the six sample compositions. The microstructure analysis carried out studies the segregation of Si, the graphite morphology, primary austenite morphology. These factors are then compared to the thermal and tensile behavior measured in this study. It can be observed that the thermal conductivity studied in the present work has a direct correlation for a higher Si content and tends to be greater than the thermal conductivity values observed from other studies with lower content Of Si. However, the conductivity shows an inverse relation with the cooling rate and is maximum for the samples with the lowest cooling rate. The tensile strength, on the other hand, seems to have a lower value than that observed in previous studies for LGI with 1 to 3% Si, but shows a direct correlation with the cooling rate. The mean area fraction of dendrites obtained and the mean interdendritic hydraulic diameter is also measured and their influence on the properties are also studied. The addition of more Si has greatly favored the thermal behavior positively but has also reduced the tensile strength.