Excitation wavelength dependent fluorescence behaviour of nano colloids of ZnO

In this paper, the fluorescence behaviour of nano colloids of ZnO has been studied as a function of the excitation wavelength. We have found that excitation at the tail of the absorption band gives rise to an emission that shifts with the change of the excitation wavelength. The excitation wavelength dependent shift of the fluorescence maximum is measured to be between 60 and 100 nm. This kind of excitation wavelength dependent fluorescence behaviour, which may appear to be in violation of Kasha’s rule of excitation wavelength independence of the emission spectrum, has been observed for nano ZnO colloids prepared by two different chemical routes and different capping agents. It is shown that the existence of a distribution of energetically different molecules in the ground state coupled with a low rate of the excited state relaxation processes, namely, solvation and energy transfer, are responsible for the excitation wavelength dependent fluorescence behaviour of the systems.

Excitation wavelength dependent fluorescence behaviour of nano colloids of ZnO

In this paper, the fluorescence behaviour of nano colloids of ZnO has been studied as a function of the excitation wavelength. We have found that excitation at the tail of the absorption band gives rise to an emission that shifts with the change of the excitation wavelength. The excitation wavelength dependent shift of the fluorescence maximum is measured to be between 60 and 100 nm. This kind of excitation wavelength dependent fluorescence behaviour, which may appear to be in violation of Kasha’s rule of excitation wavelength independence of the emission spectrum, has been observed for nano ZnO colloids prepared by two different chemical routes and different capping agents. It is shown that the existence of a distribution of energetically different molecules in the ground state coupled with a low rate of the excited state relaxation processes, namely, solvation and energy transfer, are responsible for the excitation wavelength dependent fluorescence behaviour of the systems.

Fabrication and Characterization of Chalcogenide nano composite based materials for Photonic device applications

In this context,in search of new materials based on chalcogenide glasses,we have developed a novel technique for fabrication of chalcogenide nano composites which are presented in this theis.The techniques includes the dissolution of bulk chalcogenide glasses in amine solvent.This solution casting method allows to retain the attractive optical properties of chalcogenide glasses enabling new fabrication routes for realization of large area thick-thin films with less cost. Chalcogenide glass fiber geometry opens new possibilities for a large number of applications in optics,like remote temperature measurements ,CO2 laser power delivery, and optical sensing and single mode propagation of IR light.We have fabricated new optical polymer fibers doped with chalcogenide glasses which can be used for many optical applications.The present thesis also describes the structural,thermal and optical characterization of certain chalocogenide based materials prepared for different methods and its applications.

Anomalous Viscosity Reduction and Hydrodynamic Interactions of Polymeric Nanocolloids in Polymers

One of the central dogmas of fluid physics is the no-slip boundary condition, whose validity has come under scrutiny, especially in the fields of micro and nanofluidics. Although various studies show the violation of the no-slip condition its effect on flow of colloidal particles in viscous media has been rarely explored. Here we report unusually large reduction of effective viscosity experienced by polymeric nano colloids moving through a highly viscous and confined polymer, well above its glass transition temperature. The extent of reduction in effective interface viscosity increases with decreasing temperature and polymer film thickness. Concomitant with the reduction in effective viscosity we also observe apparent divergence of the wave vector dependent hydrodynamic interaction function of these colloids with an anomalous power law exponent of similar to 2 at the lowest temperatures and film thickness studied. Such strong hydrodynamic interactions are not expected for polymeric colloidal motion in polymer melts. We suggest hydrodynamics, especially slip present at the colloid-polymer interface which determines the observed reduction in interface viscosity and presence of strong hydrodynamic interactions.

Spectral and nonlinear optical characterization of ZnO nanocomposites

The spectral and nonlinear optical characteristics of nano ZnO and its composites are investigated. The fluorescence behaviour of nano colloids of ZnO has been studied as a function of the excitation wavelength and there is a red shift in emission peak with excitation wavelength. Apart from the observation of the reported ultra violet and green emissions, our results reveal that additional blue emissions at 420 nm and 490 nm are developed with increasing particle size. Systematic studies on nano ZnO have indicated the presence of luminescence due to excitonic emissions when excited with 255 nm as well as significant contribution from surface defect states when excited with 325 nm. In the weak confinement regime, the third-order optical susceptibility χ(3) increases with increasing particle size (R) and annealing temperature (T) and a R2 and T2.5 dependence of χ(3) is obtained for nano ZnO. ZnO nanocolloids exhibit induced absorption whereas the self assembled films of ZnO exhibit saturable absorption due to saturation of linear absorption of ZnO defect states and electronic effects. ZnO nanocomposites exhibit negative nonlinear index of refraction which can be attributed to two photon absorption followed by weak free carrier absorption. The increase of the third-order nonlinearity in the composites can be attributed to the enhancement of exciton oscillator strength. The nonlinear response of ZnO nanocomposites is wavelength dependent and switching from induced absorption to saturable absorption has been observed at resonant wavelengths. Such a change-over is related to the interplay of plasmon/exciton band bleach and optical limiting mechanisms. This study is important in identifying the spectral range and the composition over which the nonlinear material acts as an optical limiter. ZnO based nanocomposites are potential materials for enhanced and tunable light emission and for the development of nonlinear optical devices with a relatively small optical limiting threshold.

Back scattering from nano-sized ZnO colloids

We report enhanced back scattering in nanometer-sized ZnO colloids prepared in two different media, by different methods. The FWHM of the back scattered cone and hence the mean free path varied with concentration of ZnO as well as particle size. The Lorentzian profile of backscattered cone indicates the presence of coherence.

Enhanced photocatalytic activity of TiO2 nano-structured thin film with a silver hierarchical configuration

TiO2 sol-gels with various Ag/TiO2 molar ratios from 0 to 0.9% were used to fabricate silver-modified nano-structured TiO2 thin films using a layer-by-layer dip-coating (LLDC) technique. This technique allows obtaining TiO2 nano-structured thin films with a silver hierarchical configuration. The coating of pure TiO2 sol-gel and Ag-modified sol-gel was marked as T and A, respectively. According to the coating order and the nature of the TiO2 sol-gel, four types of the TiO2 thin films were constructed, and marked as AT (bottom layer was Ag modified, surface layer was pure TiO,), TA (bottom layer was pure TiO,, surface layer was Ag modified), TT (pure TiO, thin film) and AA (TiO, thin film was uniformly Ag modified). These thin films were characterized by means of linear sweep voltammetry (LSV), X-ray diffraction (XRD), scanning electron microscopy (SEM), electrochemical impedance spectroscopy and transient photocurrent (I-ph). LSV confirmed the existence of Ago state in the TiO, thin film. SEM and XRD experiments indicated that the sizes of the TiO,, nanoparticles of the resulting films were in the order of TT > AT > TA > AA, suggesting the gradient Ag distribution in the films. The SEM and XRD results also confirmed that Ag had an inhibition effect on the size growth of anatase nanoparticles. Photocatalytic activities of the resulting thin films were also evaluated in the photocatalytic degradation process of methyl orange. The preliminary results demonstrated the sequence of the photocatalytic activity of the resulting films was AT > TA > AA > TT. This suggested that the silver hierarchical configuration can be used to improve the photocatalytic activity of TiO2 thin film.

Enhanced affinochromism of polydiacetylene monolayer in response to bacteria by incorporating US nano-crystallites

By incorporating bio-specific receptors, such as p-10,12-pentacosadiyne-1-N-(3,6,9-trioxaundecylamide)-alpha-D-mannopyranoside (MPDA), into 10,12-pentacosadiyonic acid (PDA) monolayer, the MPDA/PDA monolayer underwent affinochromatic transition in response to the bacteria binding to the receptor. Here, we described a new method to study the membrane/macromolececular interaction between Escherichia coli (E coli) and mannose and its relative affinochromism by modifying MPDA/PDA with CdS nano-crystallites (MPDA/PDA-CdS). CdS not only triggered the strong tropism of the bacteria but also reduced the rigidity of the MPDA/PDA backbone, resulting in the enhanced affinochromism. This discovery might be of significance in basic biophysical studies of membrane/macromolececular and designing novel biosensor.

Sol-gel-entrapped nano silver catalysts-correlation between active silver species and catalytic behavior

Silver colloids prepared by reducing AgNO3 in aqueous solution with sodium citrate were embedded in alumina following two different preparation procedures resulting in samples containing 3 and 5 wt.% silver. Characterization of these materials using TEM. XPS, XAES, CP/MAS NMR, XRD, and adsorption-desorption isotherms of nitrogen showed that embedding the pre-prepared silver colloids into the alumina via the sol-gel procedure preserved the particle size of silver. However, as XAES demonstrates, the catalysts prepared in a sol-gel with a lower amount of water led to embedded colloids with a higher population of Ag+ species. The catalytic behaviors of the resultant catalysts were well correlated with the concentration of these species. Thus, the active silver species of the catalysts containing more Ag+ species selectively converts NO to N-2. However, subsequent thermal aging leads to an enhancement of the conversion of NO parallel to slight alteration of the selectivity with the appearance of low amounts of N2O despite an increase of Ag+ species. Accordingly, an optimal surface Ag-0/Ag+ ratio is probably needed, independently of the size of silver particles. It was found that this optimal ratio strongly depends on the operating conditions during the synthesis route. (C) 2010 Elsevier Inc. All rights reserved.

Multiple morphologies of gold nano-plates by high-temperature polyol syntheses

High-temperature polyol methods were used to fabricate micro- or nano-sized gold plates. 1,2propanediol served as both medium and reducing agent. Triangular plates and polygonal plate shapes derived from triangular prisms as well as pentagonal structured gold particles have been synthesized. Poly(vinylpyrrolidone) (PVP) plays an important role, but is not necessary, for the formation of these structures. These gold plates may have applications in the characterisation of adsorbed proteins or peptides. (C) 2008 Elsevier B. V. All rights reserved.

Effect of boiling on deposition of metallic colloids

In this study the relationship between heterogeneous nucleate boiling surfaces and deposition of suspended metallic colloidal particles, popularly known as crud or corrosion products in process industries, on those heterogeneous sites is investigated. Various researchers have reported that hematite is a major constituent of crud which makes it the primary material of interest; however the models developed in this work are irrespective of material choice. Qualitative hypotheses on the deposition process under boiling as proposed by previous researchers have been tested, which fail to provide explanations for several physical mechanisms observed and analyzed. In this study a quantitative model of deposition rate has been developed on the basis of bubble dynamics and colloid-surface interaction potential. Boiling from a heating surface aids in aggregation of the metallic particulates viz. nano-particles, crud particulate, etc. suspended in a liquid, which helps in transporting them to heating surfaces. Consequently, clusters of particles deposit onto the heating surfaces due to various interactive forces, resulting in formation of porous or impervious layers. The deposit layer grows or recedes depending upon variations in interparticle and surface forces, fluid shear, fluid chemistry, etc. This deposit layer in turn affects the rate of bubble generation, formation of porous chimneys, critical heat flux (CHF) of surfaces, activation and deactivation of nucleation sites on the heating surfaces. Several problems are posed due to the effect of boiling on colloidal deposition, which range from research initiatives involving nano-fluids as a heat transfer medium to industrial applications such as light water nuclear reactors. In this study, it is attempted to integrate colloid and surface science with vapor bubble dynamics, boiling heat transfer and evaporation rate. Pool boiling experiments with dilute metallic colloids have been conducted to investigate several parameters impacting the system. The experimental data available in the literature is obtained by flow experiments, which do not help in correlating boiling mechanism with the deposition amount or structure. With the help of experimental evidences and analysis, previously proposed hypothesis for particle transport to the contact line due to hydrophobicity has been challenged. The experimental observations suggest that deposition occurs around the bubble surface contact line and extends underneath area of the bubble microlayer as well. During the evaporation the concentration gradient of a non-volatile species is created, which induces osmotic pressure. The osmotic pressure developed inside the microlayer draws more particles inside the microlayer region or towards contact line. The colloidal escape time is slower than the evaporation time, which leads to the aggregation of particles in the evaporating micro-layer. These aggregated particles deposit onto or are removed from the heating surface, depending upon their total interaction potential. Interaction potential has been computed with the help of surface charge and van der Waals potential for the materials in aqueous solutions. Based upon the interaction-force boundary layer thickness, which is governed by debye radius (or ionic concentration and pH), a simplified quantitative model for the attachment kinetics is proposed. This attachment kinetics model gives reasonable results in predicting attachment rate against data reported by previous researchers. The attachment kinetics study has been done for different pH levels and particle sizes for hematite particles. Quantification of colloidal transport under boiling scenarios is done with the help of overall average evaporation rates because generally waiting times for bubbles at the same position is much larger than growth times. In other words, from a larger measurable scale perspective, frequency of bubbles dictates the rate of collection of particles rather than evaporation rate during micro-layer evaporation of one bubble. The combination of attachment kinetics and colloidal transport kinetics has been used to make a consolidated model for prediction of the amount of deposition and is validated with the help of high fidelity experimental data. In an attempt to understand and explain boiling characteristics, high speed visualization of bubble dynamics from a single artificial large cavity and multiple naturally occurring cavities is conducted. A bubble growth and departure dynamics model is developed for artificial active sites and is validated with the experimental data. The variation of bubble departure diameter with wall temperature is analyzed with experimental results and shows coherence with earlier studies. However, deposit traces after boiling experiments show that bubble contact diameter is essential to predict bubble departure dynamics, which has been ignored previously by various researchers. The relationship between porosity of colloid deposits and bubbles under the influence of Jakob number, sub-cooling and particle size has been developed. This also can be further utilized in variational wettability of the surface. Designing porous surfaces can having vast range of applications varying from high wettability, such as high critical heat flux boilers, to low wettability, such as efficient condensers.

Efficient microwave hydrothermal preparation of nanocrystalline anatase TiO2 colloids

Titanium dioxide nanocrystals are an important commercial product used primarily in white pigments and abrasives, however, more recently the anatase form of TiO2 has become a major component in electrochemical and photoelectrochemical devices. An important property of titanium dioxide nanocrystals for electrical applications is the degree of crystallinity. Numerous preparation methods exist for the production of highly crystalline TiO2 particles. The majority of these processes require long reaction times, high pressures and temperatures (450–1400 °C). Recently, hydrothermal treatment of colloidal TiO2 suspensions has been shown to produce quality crystalline products at low temperatures (<250 °C). In this paper we extend this idea utilising a direct microwave heating source. A comparison between convection and microwave hydrothermal treatment of colloidal TiO2 is presented. The resulting highly crystalline TiO2 colloids were characterised using Raman spectroscopy, XRD, TEM, and electron diffraction. The results show that the microwave treatment of colloidal TiO2 gives comparable increases in crystallinity with respect to normal hydrothermal treatments while requiring significantly less time and energy than the hydrothermal convection treatment.