Synthesis, Characterization and Applications of Hybrid Nanocomposites of TiO2 With Conducting Polymers

A nanocomposite is a multiphase solid material where one of the phases has one, two or three dimensions of less than 100 nanometers (nm), or structures having nano-scale repeat distances between the different phases that make up the material. In the broadest sense this definition can include porous media, colloids, gels and copolymers, but is more usually taken to mean the solid combination of a bulk matrix and nano-dimensional phase(s) differing in properties due to dissimilarities in structure and chemistry. The mechanical, electrical, thermal, optical, electrochemical, catalytic properties of the nanocomposite will differ markedly from that of the component materials. Size limits for these effects have been proposed, <5 nm for catalytic activity, <20 nm for making a hard magnetic material soft, <50 nm for refractive index changes, and <100 nm for achieving superparamagnetism, mechanical strengthening or restricting matrix dislocation movement. Conducting polymers have attracted much attention due to high electrical conductivity, ease of preparation, good environmental stability and wide variety of applications in light-emitting, biosensor chemical sensor, separation membrane and electronic devices. The most widely studied conducting polymers are polypyrrole, polyaniline, polythiophene etc. Conducting polymers provide tremendous scope for tuning of their electrical conductivity from semiconducting to metallic region by way of doping and are organic electro chromic materials with chemically active surface. But they are chemically very sensitive and have poor mechanical properties and thus possessing a processibility problem. Nanomaterial shows the presence of more sites for surface reactivity, they possess good mechanical properties and good dispersant too. Thus nanocomposites formed by combining conducting polymers and inorganic oxide nanoparticles possess the good properties of both the constituents and thus enhanced their utility. The properties of such type of nanocomposite are strongly depending on concentration of nanomaterials to be added. Conducting polymer composites is some suitable composition of a conducting polymer with one or more inorganic nanoparticles so that their desirable properties are combined successfully. The composites of core shell metal oxide particles-conducting polymer combine the electrical properties of the polymer shell and the magnetic, optical, electrical or catalytic characteristics of the metal oxide core, which could greatly widen their applicability in the fields of catalysis, electronics and optics. Moreover nanocomposite material composed of conducting polymers & oxides have open more field of application such as drug delivery, conductive paints, rechargeable batteries, toners in photocopying, smart windows, etc.The present work is mainly focussed on the synthesis, characterization and various application studies of conducting polymer modified TiO2 nanocomposites. The conclusions of the present work are outlined below, Mesoporous TiO2 was prepared by the cationic surfactant P123 assisted hydrothermal synthesis route and conducting polymer modified TiO2 nanocomposites were also prepared via the same technique. All the prepared systems show XRD pattern corresponding to anatase phase of TiO2, which means that there is no phase change occurring even after conducting polymer modification. Raman spectroscopy gives supporting evidence for the XRD results. It also confirms the incorporation of the polymer. The mesoporous nature and surface area of the prepared samples were analysed by N2 adsorption desorption studies and the mesoporous ordering can be confirmed by low angle XRD measurementThe morphology of the prepared samples was obtained from both SEM & TEM. The elemental analysis of the samples was performed by EDX analysisThe hybrid composite formation is confirmed by FT-IR spectroscopy and X-ray photoelectron spectroscopyAll the prepared samples have been used for the photocatalytic degradation of dyes, antibiotic, endocrine disruptors and some other organic pollutants. Photocatalytic antibacterial activity studies were also performed using the prepared systemsAll the prepared samples have been used for the photocatalytic degradation of dyes, antibiotic, endocrine disruptors and some other organic pollutants. Photocatalytic antibacterial activity studies were also performed using the prepared systems Polyaniline modified TiO2 nanocomposite systems were found to have good antibacterial activity. Thermal diffusivity studies of the polyaniline modified systems were carried out using thermal lens technique. It is observed that as the amount of polyaniline in the composite increases the thermal diffusivity also increases. The prepared systems can be used as an excellent coolant in various industrial purposes. Nonlinear optical properties (3rd order nonlinearity) of the polyaniline modified systems were studied using Z scan technique. The prepared materials can be used for optical limiting Applications. Lasing studies of polyaniline modified TiO2 systems were carried out and the studies reveal that TiO2 - Polyaniline composite is a potential dye laser gain medium.

Growth and Melting of Metallic Nanoclusters in Glass: A Review of Recent Investigations

The mechanisms of nucleation and growth and the solid-to-liquid transition of metallic nanoclusters embedded in sodium borate glass were recently studied in situ via small-angle X-ray scattering (SAXS) and wide-an-le X-ray scattering (WAXS). SAXS results indicate that, under isothermal annealing conditions, the formation and growth of Bi or Ag nanoclusters embedded in sodium borate glass occurs through two successive stages after a short incubation period. The first stage is characterized by the nucleation and growth of spherical metal clusters promoted by the diffusion of Bi or Ag atoms through the initially supersaturated glass phase. The second stage is named the coarsening stage and occurs when the (Bi- or Ag-) doping level of the vitreous matrix is close to the equilibrium value. The experimental results demonstrated that, at advanced stages of the growth process, the time dependence of the average radius and density number of the clusters is in agreement with the classical Lifshitz-Slyozov-Waoner (LSW) theory. However, the radius distribution function is better described by a lognormal function than by the function derived from the theoretical LSW model. From the results of SAXS measurements at different temperatures, the activation energies for the diffusion of Ag and Bi through sodium borate glass were determined. In addition, via combination of the results of simultaneous WAXS and SAXS measurements at different temperatures, the crystallographic structure and the dependence of melting temperature T(m) on crystal radius R of Bi nanocrystals were established. The experimental results indicate that T(m) is a linear and decreasing function of nanocrystal reciprocal radius 1/R, in agreement with the Couchman and Jesser theoretical model. Finally, a weak contraction in the lattice parameters of Bi nanocrystals with respect to bulk crystals was established.

Experimental and theoretical investigation of first hyperpolarizability in aminophenols

This work reports theoretical and experimental studies on the first hyperpolarizability (beta) of aminophenols, evaluating the influence of the NH(2) group position relative to the OH group on the hyperpolarizability. A new extension of hyper-Rayleigh scattering technique using picosecond pulse trains was employed to obtain the experimental absolute values of (beta). The theoretical static beta(0) values were calculated using AMI method implemented in the AMPAC program. The theoretical and experimental data show a clear dependence between beta and the relative position of the electron donor (D) and acceptor (A) groups, presenting the 2-aminophenol the higher values. Moreover, calculations show excellent qualitative agreement between theoretical and experimental data, which are improved when the simulations considering the solvated molecule in a combination of discrete solvent molecules interacting with the solute and the application of continuous dielectric model. Besides, the study indicates that the experimental hyperpolarizabilities seem to be a property of the solute-solvation shell system. These facts have affirmed that the theoretical approach employed can be successfully used to foresee the variation in beta due to modifications in the D/A position. Moreover, a theoretical study of the ground state absorption is performed and compared with experimental data. (C) 2008 Elsevier B.V. All rights reserved.

Raman spectroscopy analysis of structural photoinduced changes in GeS(2) + Ga(2)O(3) thin films

Photoexpansion and photobleaching effects have been observed in amorphous GeS(2) + Ga(2)O(3) (GGSO) thin films, when their surfaces were exposed to UV light. The photoinduced changes on the surface of the samples are indications that the structure has been changed as a result of photoexcitation. In this paper, micro-Raman, energy dispersive X-ray analysis (EDX) and backscattering electrons (BSE) microscopy were the techniques used to identify the origin of these effects. Raman spectra revealed that these phenomena are a consequence of the Ge-S bonds` breakdown and the formation of new Ge-O bonds, with an increase of the modes associated with Ge-O-Ge bonds and mixed oxysulphide tetrahedral units (S-Ge-O). The chemical composition measured by EDX and BSE microscopy images indicated that the irradiated area is oxygen rich. So, the present paper provides fundamental insights into the influence of the oxygen within the glass matrix on the considered photoinduced effects. (C) 2010 Elsevier B.V. All rights reserved.

Electrooptic proprieties of layer-by-layer films of a azobenzene containing copolymer

The methacrylic copolymer functionalized with the azo chromophore 4-[N-ethyl-N-(2-hydroxiethyl)]-amino-2′-chloro-4-nitroazobenzene (MMADR13), in its polyelectrolyte form, can be used to fabricate thin films by the layer-by-layer (LbL) technique just if one alternates this anionic polyelectrolyte with a cationic polyelectrolyte such as poly(allylamine hydrochloride) (PAH). Since PAH does not present any particular optical functionality, the main final film feature will came from the side chain DR13 azo-chromophore group due to its large nonlinear optical properties and photoisomerization capabilities. This work reports the electrooptic activity of MMADR13/DR13 LBL films, which arises from the high hiperpolarizability about the azo side chain group.

Condutividade elétrica e polarização térmica de vidros soda-cal-sílica contendo diferentes cátions tetravalentes

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

Study of singlet excited state absorption spectrum of lutetium bisphthalocyanine using the femtosecond Z-scan technique

In this study we investigate the singlet excited state absorption of lutetium bisphthalocyanine (LuPc2) over a wide spectral range. It was observed distinct nonlinear absorption behaviors; saturable (SA) and reverse saturable absorption (RSA). The RSA effect was observed below 640 and above 680 nm, while SA occurs around the Q-band region, located around 660 nm. To describe the main singlet-singlet transitions, we employed the rate equation model considering the simplified three-energy level diagram. Our results reveal a ratio between excited and ground state absorption smaller than 0.05 at the Q-band region, and of approximately 4 for the other regions. (C) 2012 Elsevier B.V. All rights reserved.

Application of Artificial Intelligence Methods to Computer Design of Inorganic Compounds

In this paper the main problems for computer design of materials, which would have predefined properties, with the use of artificial intelligence methods are presented. The DB on inorganic compound properties and the system of DBs on materials for electronics with completely assessed information: phase diagram DB of material systems with semiconducting phases and DB on acousto-optical, electro-optical, and nonlinear optical properties are considered. These DBs are a source of information for data analysis. Using the DBs and artificial intelligence methods we have predicted thousands of new compounds in ternary, quaternary and more complicated chemical systems and estimated some of their properties (crystal structure type, melting point, homogeneity region etc.). The comparison of our predictions with experimental data, obtained later, showed that the average reliability of predicted inorganic compounds exceeds 80%. The perspectives of computational material design with the use of artificial intelligence methods are considered.

Structure and properties of amorphous thin film for optical data storage

In this paper the magnetic and magneto-optical properties of amorphous rare earth-transition metal (RE-TM) alloys as well as the magnetic coupling in the multi-layer thin films for high density optical data storage are presented. Using magnetic effect in scanning tunneling microscopy the clusters structure of amorphous RE-TM thin films has been observed and the perpendicular magnetic anisotropy in amorphous RE-TM thin films has been interpreted. Experimental results of quick phase transformation under short pulse laser irradiation of amorphous semiconductor and metallic alloy thin films for phase change optical recording are reported. A step-by-step phase transformation process through metastable states has been observed. The waveform of crystallization propagation in micro-size spot during laser recording in amorphous semiconductor thin films is characterized and quick recording and erasing mechanism for optical data storage with high performance are discussed. The nonlinear optical effects in amorphous alloy thin films have been studied. By photo-thermal effect or third order optical nonlinearity, the optical self-focusing is observed in amorphous mask thin films. The application of amorphous thin films with super-resolution near field structure for high-density optical data storage is performed. (c) 2007 Elsevier B.V. All rights reserved.

Mode field diameter and nonlinear properties of air-core nanowires

Exact solutions of Maxwell's equations describing the lightwave through 3-layer-structured cylindrical waveguide are obtained and the mode field diameter and nonlinear coefficient of air-core nanowires (ACNWs) are numerically calculated. The simulation results show that ACNWs offer some unique optical properties, such as tight field confining ability and extremely high nonlinearity. At a certain wavelength and air core radius, we optimize the waveguide design to maximize the nonlinear coefficient and minimize the mode field diameter. Our results show that the ACNWs may be powerful potential tools for novel micro-photonic devices in the near future.

Studies on two coordination polymers [M(mu(4)-pz25dc)](n) (M = Cd or Zn, pz25dc=pyrazine-2,5-dicarboxylato) with three-dimensional pillared-layer three-nodal framework: Synthesis, structural characterization, strong optical non-linearities and optical limiting properties

Two isomorphous new candidates [M(mu(4)-pz25dc)](n) (M = Cd, 1; Zn, 2; pz25dc = pyrazine-2,5-dicarboxylato)for nonlinear optical (NLO) materials have been synthesized hydrothermally and characterized crystallographically as pillared-layer three-nodal frameworks with one four-connected metal nodes and two crystallographically different four-connected ligand nodes. Their optical non-linearities are measured by the Z-Scan technique with an 8 ns pulsed laser at 532 nm. These two coordination polymers both exhibit strong NLO absorptive abilities [alpha(2) = (63 +/- 6) x 10 (12) mW (1) 1, ( 46 +/- 6) x 10 (11) mW (1) 2] and effective self-focusing performance [n(2) = (67 +/- 5) x 10 (18) 1, (13 +/- 3) x 10 (18) m(2) W (1) 2] in 1.02 x 10 (4) 1 and 1.05 x 10 (4) mol dm (3) 2 DMF solution separately. The values of the limiting threshold are also measured from the optical limiting experimental data. The heavy atom effect plays important role in the enhancement of optical non-linearities and optical limiting properties. (C) 2009 Elsevier B. V. All rights reserved.

Investigations on Nonlinear and Radiative Properties of Certain Phatonic Materials

Light in its physical and philosophical sense has captured the imagination of human mind right from the dawn of civilization. The invention of lasers in the 60’s caused a renaissance in the field of optics. This intense, monochromatic, highly directional radiation created new frontiers in science and technology. The strong oscillating electric field of laser radiation creates a. polarisation response that is nonlinear in character in the medium through which it passes and the medium acts as a new source of optical field with alternate properties. It was in this context, that the field of optoelectronics which encompasses the generation, modulation, transmission etc. of optical radiation has gained tremendous importance. Organic molecules and polymeric systems have emerged as a class of promising materials of optoelectronics because they offer the flexibility, both at the molecular and bulk levels, to optimize the nonlinearity and other suitable properties for device applications. Organic nonlinear optical media, which yield large third-order nonlinearities, have been widely studied to develop optical devices like high speed switches, optical limiters etc. Transparent polymeric materials have found one of their most promising applicationsin lasers, in which they can be used as active elements with suitable laser dyes doped in it. The solid-matrix dye lasers make possible combination of the advantages of solid state lasers with the possibility of tuning the radiation over a broad spectral range. The polymeric matrices impregnated with organic dyes have not yet widely used because of the low resistance of the polymeric matrices to laser damage, their low dye photostability, and low dye stability over longer time of operation and storage. In this thesis we investigate the nonlinear and radiative properties of certain organic materials and doped polymeric matrix and their possible role in device development

The synthesis of high coercivity cobalt-in-carbon nanotube hybrid structures and their optical limiting properties

Magnetic heterostructures with carbon nanotubes having multiple functionalities are fascinating materials which can be manipulated by means of an external magnetic field. In this paper we report our investigations on the synthesis and optical limiting properties of pristine cobalt nanotubes and high coercivity cobalt-in-carbon nanotubes (a new nanosystem where carbon nanotubes are filled with cobalt nanotubes). A general mobility assisted growth mechanism for the formation of one-dimensional nanostructures inside nanopores is verified in the case of carbon nanotubes. The open-aperture z-scan technique is employed for the optical limiting measurements in which nanosecond laser pulses at 532 nm have been used for optical excitation. Compared to the benchmark pristine carbon nanotubes these materials show an enhanced nonlinear optical absorption, and the nonlinear optical parameters calculated from the data show that these materials are efficient optical limiters. To the best of our knowledge this is the first report where the optical limiting properties of metal nanotubes are compared to those of carbon nanotubes

Nonlinear and magneto-optical transmission studies on magnetic nanofluids of non-interacting metallic nickel nanoparticles

Oxide free stable metallic nanofluids have the potential for various applications such as in thermal management and inkjet printing apart from being a candidate system for fundamental studies. A stable suspension of nickel nanoparticles of ∼5 nm size has been realized by a modified two-step synthesis route. Structural characterization by x-ray diffraction and transmission electron microscopy shows that the nanoparticles are metallic and are phase pure. The nanoparticles exhibited superparamagnetic properties. The magneto-optical transmission properties of the nickel nanofluid (Ni-F) were investigated by linear optical dichroism measurements. The magnetic field dependent light transmission studies exhibited a polarization dependent optical absorption, known as optical dichroism, indicating that the nanoparticles suspended in the fluid are non-interacting and superparamagnetic in nature. The nonlinear optical limiting properties of Ni-F under high input optical fluence were then analyzed by an open aperture z-scan technique. The Ni-F exhibits a saturable absorption at moderate laser intensities while effective two-photon absorption is evident at higher intensities. The Ni-F appears to be a unique material for various optical devices such as field modulated gratings and optical switches which can be controlled by an external magnetic field