Investigations on novel polymer nano composites and bio-compatible manganese doped ZnS nanocrystals for photonic and bio-imaging applications

Fluorescence is a powerful tool in biological research, the relevance of which relies greatly on the availability of sensitive and selective fluorescent probes. Nanometer sized fluorescent semiconductor materials have attracted considerable attention in recent years due to the high luminescence intensity, low photobleaching, large Stokes’ shift and high photochemical stability. The optical and spectroscopic features of nanoparticles make them very convincing alternatives to traditional fluorophores in a range of applications. Efficient surface capping agents make these nanocrystals bio-compatible. They can provide a novel platform on which many biomolecules such as DNA, RNA and proteins can be covalently linked. In the second phase of the present work, bio-compatible, fluorescent, manganese doped ZnS (ZnS:Mn) nanocrystals suitable for bioimaging applications have been developed and their cytocompatibility has been assessed. Functionalization of ZnS:Mn nanocrystals by safe materials results in considerable reduction of toxicity and allows conjugation with specific biomolecules. The highly fluorescent, bio-compatible and water- dispersible ZnS:Mn nanocrystals are found to be ideal fluorescent probes for biological labeling

Evaluation of a.c. conductivity of rubber ferrite composites from dielectric measurements

The effect of frequency, composition and temperature on the a.c. electrical conductivity were studied for the ceramic, Ni1–xZnxFe2O4, as well as the filler (Ni1–xZnxFe2O4) incorporated rubber ferrite composites (RFCs). Ni1–xZnxFe2O4 (where x varies from 0 to 1 in steps of 0×2) were prepared by usual ceramic techniques. They were then incorporated into a butyl rubber matrix according to a specific recipe. The a.c. electrical conductivity (sa.c.) calculations were carried out by using the data available from dielectric measurements and by employing a simple relationship. The a.c. conductivity values were found to be of the order of 10–3 S/m. Analysis of the results shows that sa.c. increases with increase of frequency and the change is same for both ceramic Ni1–xZnxFe2O4 and RFCs. sa.c. increases initially with the increase of zinc content and then decreases with increase of zinc. Same behaviour is observed for RFCs too. The dependence of sa.c. on the volume fraction of the magnetic filler was also studied and it was found that the a.c. conductivity of RFCs increases with increase of volume fraction of the magnetic filler. Temperature dependence of conductivity was studied for both ceramic and rubber ferrite composites. Conductivity shows a linear dependence with temperature in the case of ceramic samples

Effect of Carbon Black on the Mechanical and Dielectric Properties of Rubber Ferrite Composites Containing Barium Ferrite

Fine particles of barium ferrite (BaFe12O19) were synthesized by the conventional ceramic technique. These materials were then characterized by the X-ray diffraction method and incorporated in the natural rubber matrix according to a specific receipe for various loadings of ferrite. The rubber ferrite composites (RFC) thus obtained have several applications, and have the advantage of molding into complex shapes. For applications such as microwave absorbers, these composites should have an appropriate dielectric strength with the required mechanical and magnetic properties. The N330 (HAF) carbon black has been added to these RFCs for various loadings to modify the dielectric and mechanical properties. In this article we report the effect of carbon black on the mechanical and dielectric properties of these RFCs. Both the mechanical and dielectric properties can be enhanced by the addition of an appropriate amount of carbon black

Microwave Absorption of Nylon 6,6 Based Polymer Ferrite Composites

Ferrite composites are magnetic composites consisting of fine particles of metal ferrites dispersed in the polymer matrix. These composites have a variety of applications as flexible magnets, pressure/photo sensors and microwave absorbers. Polymers and magnetic materials play a very important role in our day to day life. Both natural and synthetic polymers are today indispensable to mankind. The polymers, which include rubber, plastics and fibers, make life easier and more comfortable.

Butyl rubber- ceramic composites for flexible electronic applications

The first chapter of the thesis gives a general introduction about flexible electronics, dielectrics and composites. The recent developments in flexible electronics also discussed in this chapter. The preparation and characterization techniques used for the butyl rubber ceramic composites are given in chapter 2. The synthesis and characterization of butyl rubber filled with low permittivity ceramic composites are described in chapter 3. The chapter 4 deals with the synthesis and characterization of butyl rubber-high permittivity ceramic composites. The effect of high permittivity ceramic fillers such as TiO2, Sr2Ce2Ti5O15 and SrTiO3 on dielectric, thermal and mechanical properties was studied. The present investigation deals with synthesis, characterization and properties of butyl rubber composites with low, high and very high ceramic fillers and also the effect of particle size on dielectric, thermal and mechanical properties of selected composites.

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.

Simulation of interlaminar and intralaminar damage in polymer-based composites for aeronautical applications under impact loading

La aplicación de materiales compuestos de matriz polimérica reforzados mediante fibras largas (FRP, Fiber Reinforced Plastic), está en gradual crecimiento debido a las buenas propiedades específicas y a la flexibilidad en el diseño. Uno de los mayores consumidores es la industria aeroespacial, dado que la aplicación de estos materiales tiene claros beneficios económicos y medioambientales. Cuando los materiales compuestos se aplican en componentes estructurales, se inicia un programa de diseño donde se combinan ensayos reales y técnicas de análisis. El desarrollo de herramientas de análisis fiables que permiten comprender el comportamiento mecánico de la estructura, así como reemplazar muchos, pero no todos, los ensayos reales, es de claro interés. Susceptibilidad al daño debido a cargas de impacto fuera del plano es uno de los aspectos de más importancia que se tienen en cuenta durante el proceso de diseño de estructuras de material compuesto. La falta de conocimiento de los efectos del impacto en estas estructuras es un factor que limita el uso de estos materiales. Por lo tanto, el desarrollo de modelos de ensayo virtual mecánico para analizar la resistencia a impacto de una estructura es de gran interés, pero aún más, la predicción de la resistencia residual después del impacto. En este sentido, el presente trabajo abarca un amplio rango de análisis de eventos de impacto a baja velocidad en placas laminadas de material compuesto, monolíticas, planas, rectangulares, y con secuencias de apilamiento convencionales. Teniendo en cuenta que el principal objetivo del presente trabajo es la predicción de la resistencia residual a compresión, diferentes tareas se llevan a cabo para favorecer el adecuado análisis del problema. Los temas que se desarrollan son: la descripción analítica del impacto, el diseño y la realización de un plan de ensayos experimentales, la formulación e implementación de modelos constitutivos para la descripción del comportamiento del material, y el desarrollo de ensayos virtuales basados en modelos de elementos finitos en los que se usan los modelos constitutivos implementados.

Infrared actuation in aligned polymer-nanotube composites

Rubber composites containing multiwalled carbon nanotubes have been irradiated with near-infrared light to study their reversible photomechanical actuation response. We demonstrate that the actuation is reproducible across differing polymer systems. The response is directly related to the degree of uniaxial alignment of the nanotubes in the matrix, contracting the samples along the alignment axis. The actuation stroke depends on the specific polymer being tested; however, the general response is universal for all composites tested. We conduct a detailed study of tube alignment induced by stress and propose a model for the reversible actuation behavior based on the orientational averaging of the local response. The single phenomenological parameter of this model describes the response of an individual tube to adsorption of low-energy photons; its experimentally determined value may suggest some ideas about such a response.

Conventional and microwave sintering of CaCu(3)Ti(4)O(12)/CaTiO(3) ceramic composites: non-ohmic and dielectric properties

The non-ohmic and dielectric properties as well as the dependence on the microstructural features of CaCu(3)Ti(4)O(12)/CaTiO(3) ceramic composites obtained by conventional and microwave sintering were investigated. It was demonstrated that the non-ohmic and dielectric properties depend strongly on the sintering conditions. It was found that the non-linear coefficient reaches values of 65 for microwave-sintered samples and 42 for samples sintered in a conventional furnace when a current density interval of 1-10 mA cm(-2) is considered. The non-linear coefficient value of 65 is equivalent to 1500 for samples sintered in the microwave if a current interval of 5-30 mA is considered as is shortly discussed by Chung et al (2004 Nature Mater. 3 774). Due to a high non-linear coefficient and a low leakage current (90 mu A) under both processing conditions, these samples are promising for varistor applications. The conventionally sintered samples exhibit a higher relative dielectric constant at 1 kHz (2960) compared with the samples sintered in the microwave furnace (2100). At high frequencies, the dielectric constant is also larger in the samples sintered in the conventional furnace. Depending on the application, one or another synthesis methodology is recommended, that is, for varistor applications sintered in a microwave furnace and for dielectric application sintered in a conventional furnace.

Dielectric and pyroelectric properties of a composite of ferroelectric ceramic and polyurethane

Flexible piezo- and pyroelectric composite was made in the thin film form by spin coating. Lead Zirconate Titanate (PZT) ceramic powder was dispersed in a castor oil-based polyurethane (PU) matrix, providing a composite with 0-3 connectivity. The dielectric data, measured over a wide range of frequency (10(-5) Hz to 105 Hz), shows a loss peak around 100 Hz related with impurities in the polymer matrix. There is also an evidence of a peak in the range 10(-4) Hz, possibly originating from the glass transition temperature T of the polymer. The pyroelectric coefficient at 34 K is 7.0x10(-5) C(.)m(-2.)K(-1) which is higher than that of P-PVDF (1X10(-5) C(.)m(-2.)K(-1)).

Composites PVDF-TrFE/BT used as bioactive membranes for enhancing bone regeneration

In this paper a piezoelectric composite membranes were developed for charge generator to promoter bone regeneration on defects sites. Is known that the osteogenesis process is induced by interactions between biological mechanisms and electrical phenomena. The membranes were prepared by mixing Barium Titanate (BT) powders and PVDF-TrFE (PVDF:TrFE = 60:40 mol%) on dimethylformamide medium. This precursor solution was dried and crystallized at 100degreesC for 12 hours. Composites membranes were obtained by following methods: solvent casting (SC), spincoating (SP), solvent extraction by water addition (WS) and hot pressing (HP).The microstructural analysis performed by SEM showed connectivity type 3-0 and 3-1 with high homogeneity for samples of ceramic volume fraction major than 0.50. Powder agglomerates within the polymer matrix was evidenced were observed for composites with the BT volume fraction major than 40%. The composite of ceramic fraction of 0.55 presented the best values of remanent polarization (similar to33 muC/cm(2)), but the flexibility of these composites with the larger ceramic fraction was significantly affected.For in vivo evaluation PVDF-TrFE/BT 90/10 membranes with 3cm larger were longitudinally implanted under tibiae of male rabbit. After 21 days the animals were sacrificed. By histological analyses were observed neo formed bone with a high mitotic activity. In the interface bone-membrane was evidenced a pronounced callus formation. These results encourage further applications of these membranes in bone-repair process.

Development of alpha-SiAlON-SiC ceramic composites by liquid phase sintering

In this work, in situ alpha-SiAlON-SiC ceramic composites were obtained,by, liquid phase sintering, using SiC as reinforcement. Different beta-SiC powder contents (0-20 wt.%), were added to Si3N4-AlN-RE2O3. powder mixtures, and compacted by cold isostatic pressing. The samples were sintered at 1950 degrees C for 1 h, in N-2 atmosphere. Sintered: samples were characterized by relative density, weight loss, X-ray diffraction and scanning electron microscopy. Furthermore, mechanical properties such as hardness and fracture toughness were determined by Vickers indentation method. Lattice parameters of the alpha' phase did not considerably change with increase of SiC content. However, morphology, average grain size and aspect ratio of the alpha' phase were considerably changed with increase of the SiC content. These behavior influences significantly the mechanical properties of this hard ceramic composite. (C) 2006 Elsevier Ltd. All rights reserved.

Electric and magnetic properties of polymer electrolyte/carbon black composites

Measurements of 1H Nuclear Magnetic Resonance (NMR) relaxation times, Electron Paramagnetic Resonance (EPR) and AC Impedance Spectroscopy (IS) are reported for composites based on PEO8:LiClO4 and carbon black (CB), prepared by two methods: solvent and fusion processing. Three nuclear relaxation processes were identified for 1H nuclei: (i) belonging to the polymer chains in the amorphous phase, loosely bound to the CB particles, whose dynamics is almost the same as for unfilled polymer, (ii) belonging to the polymer chains which are tightly attached to the CB particles, and (iii) belonging to the crystalline phase in the loose polymer chain. The paramagnetic electronic susceptibility of the composite samples, measured by EPR, was interpreted by assuming a contribution of localized spin states that follow a Curie law, and a Pauli-like contribution of delocalized spins. A significant change of the EPR linewidth was observed at 40 K, which is the temperature where the Curie and Pauli susceptibilities equally contribute to the paramagnetic electronic susceptibility. The electrical properties are very sensitive to the preparation methods of the composites, which conditions the interaction between carbon particle-carbon particle and carbon particle-polymer chain. Classical statistic models to describe the conductivity in these media were not satisfactory. © 1998 Published by Elsevier Science B.V. All rights reserved.

Measurement of Radiant Energy using Pyroelectric Polymer/Ceramic Composite

Monitoring non-ionizing radiant energy is increasingly demanded for many applications such as automobile, biomedical and security system. Thermal type infrared (IR) sensors can operate at room temperature and pyroelectric materials have high sensitivity and accuracy for that application. Working as thermal transducer pyroelectric sensor converts the non-quantified thermal flux into the output measurable quantity of electrical charge, voltage or current. In the present study the composite made of poly(vinylidene fluoride) -PVDF and lead zirconate titanate (PZT) partially recovered with polyaniline (PAni) conductor polymer has been used as sensor element. The pyroelectric coefficient p(T) was obtained by measuring the pyroelectric reversible current, i.e., measuring the thermally stimulated depolarization current (TSDC) after removing all irreversible contribution to the current such as injected charge during polarization of the sample. To analyze the sensing property of the pyroelectric material, the sensor is irradiated by a high power light source (halogen lamp of 250 W) that is chopped providing a modulated radiation. A device assembled in the laboratory is used to change the light intensity sensor, an aluminum strip having openings with diameters ranging from 1 to 10 mm incremented by one millimeter. The sensor element is assembled between two electrodes while its frontal surface is painted black ink to maximize the light absorption. The signal from the sensor is measured by a Lock-In amplifier model SR530 -Stanford Research Systems. The behavior of the output voltage for an input power at several frequencies for PZT-PAni/PVDF (30/ 70 vol%) composite follows the inverse power law (1/ f) and the linearity can be observed in the frequency range used.

Investigation of the dielectric relaxation processes in PbZr0.65Ti0.35O3-BaFe12O19 multiferroic ceramic composites

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)