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.

Microstrip antennas for mobile telephone handset with reduced radiation hazards

A novel antenna configuration comprised of two circular micro strip antennas (CMAs) resonating in the TMtt and TM2, modes, producing radiation characteristics suitable for a mobile telephone handset, is presented. The antennas operating at the same frequency are placed back to back with a separation comparable to the thickness of a typical handset. The radiation pattern consists of a region of reduced radiation intensity, which minimizes the radiation hazards to the user

The Steady-State and Transient Characteristic Analysis of Thermal Fixing a Photorefractive Hologram Grating in Lithium Niobate

The transient interaction between a refraction index grating and light beams during simultaneous writing and thermal fixing of a photorefractive hologram is investigated. With a diffusion- and photovoltaic-dominated carrier transport mechanism and carrier thermal activation (temperature dependent) considered in Fe:LiNbO3 crystal, from the standpoint of field-material coupling, the theoretical thermal fixing time and the space-charge field buildup, spatial distribution, and temperature dependence are given numerically by combining the band transport model with mobile ions with the coupled-wave equation

A new microstrip patch antenna for mobile communications and bluetooth applications

compact multihand planar octagonal-shaped microstrip antenna simultaneously suitable for mobile communication and blue tooth application is presented. The antenna provides sufficient isolation benveen the two operating bands and an area reduction of -29 % with respect to a circular patch operating in the same band

Integrated internal PIFA for UMTS operation of clamshell mobile phones

novel design of at internal PIFA integrated with an RF-shielding metal case for application in a clamshell or fielder-tvpe mobile phone is presented. The integrated PIFA has a bent and tapered radiating arm in order to easily fit in the casing of the clamshell mobile phone as an internal antenna. The integrated PlEA can also provide a wide operating bandwidth fir UM7S (1920-2170 MHz) operation. In addition, for the clamshell mobile phone in either the talk or standby condition, only a small effect on the operating bandwidth of the integrated PIFA is obtained. The experimental results of the proposed design are presented

Synthesis, characterization and hydrodesulphurisation activity of CoMo/gama-Al2O3 catalyst prepared through molecular designed dispersion method

CoMo/gama-Al2O3 catalysts for hydrodesulphurisation activity were prepared by making use of the molecular designed dispersion (MDD) method. Molybdenum and cobalt pyrrolidine-N-carbodithioate (Pydtc) complexes were used for the incorporation of metals on the support. The catalysts were characterized by elemental analysis, low temperature oxygen chemisorption, temperature programmed reduction (TPR) and laser Raman spectroscopy. The hydrodesulphurisation activity of all the catalysts were carried out and results were compared with those of the catalysts prepared through the conventional method. Higher molybdenum dispersion, smaller molybdenum clusters, lower reduction temperature of catalyst and better hydrodesulphurisation activity were observed for the catalysts prepared through the MDD method

A Beacon based Localization System for Autonomous Mobile Robots and its Applications in Traffic and Transport Control

ACCURATE sensing of vehicle position and attitude is still a very challenging problem in many mobile robot applications. The mobile robot vehicle applications must have some means of estimating where they are and in which direction they are heading. Many existing indoor positioning systems are limited in workspace and robustness because they require clear lines-of-sight or do not provide absolute, driftfree measurements.The research work presented in this dissertation provides a new approach to position and attitude sensing system designed specifically to meet the challenges of operation in a realistic, cluttered indoor environment, such as that of an office building, hospital, industrial or warehouse. This is accomplished by an innovative assembly of infrared LED source that restricts the spreading of the light intensity distribution confined to a sheet of light and is encoded with localization and traffic information. This Digital Infrared Sheet of Light Beacon (DISLiB) developed for mobile robot is a high resolution absolute localization system which is simple, fast, accurate and robust, without much of computational burden or significant processing. Most of the available beacon's performance in corridors and narrow passages are not satisfactory, whereas the performance of DISLiB is very encouraging in such situations. This research overcomes most of the inherent limitations of existing systems.The work further examines the odometric localization errors caused by over count readings of an optical encoder based odometric system in a mobile robot due to wheel-slippage and terrain irregularities. A simple and efficient method is investigated and realized using an FPGA for reducing the errors. The detection and correction is based on redundant encoder measurements. The method suggested relies on the fact that the wheel slippage or terrain irregularities cause more count readings from the encoder than what corresponds to the actual distance travelled by the vehicle.The application of encoded Digital Infrared Sheet of Light Beacon (DISLiB) system can be extended to intelligent control of the public transportation system. The system is capable of receiving traffic status input through a GSM (Global System Mobile) modem. The vehicles have infrared receivers and processors capable of decoding the information, and generating the audio and video messages to assist the driver. The thesis further examines the usefulness of the technique to assist the movement of differently-able (blind) persons in indoor or outdoor premises of his residence.The work addressed in this thesis suggests a new way forward in the development of autonomous robotics and guidance systems. However, this work can be easily extended to many other challenging domains, as well.

Solitons and their resonances on two-dimensional superfluid films

The dynamics of saturated two-dimensional superfluid4He films is shown to be governed by the Kadomtsev-Petviashvili equation with negative dispersion. It is established that the phenomena of soliton resonance could be observed in such films. Under the lowest order nonlinearity, such resonance would happen only if two dimensional effects are taken into account. The amplitude and velocity of the resonant soliton are obtained.

Energy-Efficient Cluster based Routing Schemes for Static and Mobile Sensor Networks

The theme of the thesis is centred around one important aspect of wireless sensor networks; the energy-efficiency.The limited energy source of the sensor nodes calls for design of energy-efficient routing protocols. The schemes for protocol design should try to minimize the number of communications among the nodes to save energy. Cluster based techniques were found energy-efficient. In this method clusters are formed and data from different nodes are collected under a cluster head belonging to each clusters and then forwarded it to the base station.Appropriate cluster head selection process and generation of desirable distribution of the clusters can reduce energy consumption of the network and prolong the network lifetime. In this work two such schemes were developed for static wireless sensor networks.In the first scheme, the energy wastage due to cluster rebuilding incorporating all the nodes were addressed. A tree based scheme is presented to alleviate this problem by rebuilding only sub clusters of the network. An analytical model of energy consumption of proposed scheme is developed and the scheme is compared with existing cluster based scheme. The simulation study proved the energy savings observed.The second scheme concentrated to build load-balanced energy efficient clusters to prolong the lifetime of the network. A voting based approach to utilise the neighbor node information in the cluster head selection process is proposed. The number of nodes joining a cluster is restricted to have equal sized optimum clusters. Multi-hop communication among the cluster heads is also introduced to reduce the energy consumption. The simulation study has shown that the scheme results in balanced clusters and the network achieves reduction in energy consumption.The main conclusion from the study was the routing scheme should pay attention on successful data delivery from node to base station in addition to the energy-efficiency. The cluster based protocols are extended from static scenario to mobile scenario by various authors. None of the proposals addresses cluster head election appropriately in view of mobility. An elegant scheme for electing cluster heads is presented to meet the challenge of handling cluster durability when all the nodes in the network are moving. The scheme has been simulated and compared with a similar approach.The proliferation of sensor networks enables users with large set of sensor information to utilise them in various applications. The sensor network programming is inherently difficult due to various reasons. There must be an elegant way to collect the data gathered by sensor networks with out worrying about the underlying structure of the network. The final work presented addresses a way to collect data from a sensor network and present it to the users in a flexible way.A service oriented architecture based application is built and data collection task is presented as a web service. This will enable composition of sensor data from different sensor networks to build interesting applications. The main objective of the thesis was to design energy-efficient routing schemes for both static as well as mobile sensor networks. A progressive approach was followed to achieve this goal.

Studies on Spatial and Temporal solitons with varying dispersion,diffraction and nonlinearity

Department of Physics, Cochin University of Science and Technology

Service quality and reliability assessment of mobile communication infrastructure

The service quality of any sector has two major aspects namely technical and functional. Technical quality can be attained by maintaining technical specification as decided by the organization. Functional quality refers to the manner which service is delivered to customer which can be assessed by the customer feed backs. A field survey was conducted based on the management tool SERVQUAL, by designing 28 constructs under 7 dimensions of service quality. Stratified sampling techniques were used to get 336 valid responses and the gap scores of expectations and perceptions are analyzed using statistical techniques to identify the weakest dimension. To assess the technical aspects of availability six months live outage data of base transceiver were collected. The statistical and exploratory techniques were used to model the network performance. The failure patterns have been modeled in competing risk models and probability distribution of service outage and restorations were parameterized. Since the availability of network is a function of the reliability and maintainability of the network elements, any service provider who wishes to keep up their service level agreements on availability should be aware of the variability of these elements and its effects on interactions. The availability variations were studied by designing a discrete time event simulation model with probabilistic input parameters. The probabilistic distribution parameters arrived from live data analysis was used to design experiments to define the availability domain of the network under consideration. The availability domain can be used as a reference for planning and implementing maintenance activities. A new metric is proposed which incorporates a consistency index along with key service parameters that can be used to compare the performance of different service providers. The developed tool can be used for reliability analysis of mobile communication systems and assumes greater significance in the wake of mobile portability facility. It is also possible to have a relative measure of the effectiveness of different service providers.

Design and Development of Compact Coplanar Waveguide Fed Antennas for Wireless Applications

The need of miniaturization in the present day communication industry is challenging. In the present scenario, printed antenna technology is highly suitable for wireless communication due to its low profile and other desirable radiation characteristics. Small monopole type antennas are overruled by compact small antennas for present day mobile communication applications. Coplanar waveguides (CPW) are printed on one side of a dielectric substrate. CPW have attracted the attention of antenna designers due to their excellent properties like ease of integration with ‘MMIC’, low cost, wide bandwidth, flexibility towards multiband operation, low radiation leakage and less dispersion. The requirement of omnidirectional coverage, light weight and low cost made these CPW fed antennas a good candidate for wireless applications. The main focus of the thesis is the study of coplanar waveguide transmission line. Rigorous investigations were performed on both the ground plane and signal strip of a coplanar waveguide transmission line to create effective radiation characteristics. Good amount of works have been done to transform CPW line to antenna suitable for mobile phone applications

Development and Investigations of Mobile Antennas for less Radiation Hazards

Antennas, the key element in wireless communication devices had undergone amazing developments especially in the direction of compactness and safety aspects. In the last two decades, the use of the cellular phones has become the most popular mode of communication across the globe. At the same time, the concerns about the radiation effects have increased in the general public. The main concern of this thesis is to develop a mobile antenna which gives reduced RF interference to the user. The reduction of the power absorbed by the user can tremendously avoid any possible health hazards. The radiation characteristic of a monopole antenna is modified with good radiation characteristics suitable for a mobile handset. The modification is implemented by using different resonating structures which provides reduced radiation along one direction. The direction of less radiation can be changed by modifying the planar antenna structure to a ground folded antenna. This modified structure with excellent radiation characteristic is suitable for modern wireless handheld devices with less user RF interference. Specific Absorption Rate (SAR) is an important parameter for mobile handset. The SAR is estimated for the newly developed antenna for different conditions and discussed in this thesis.

Studies On The Dynamics And Water Quality Of The Muvattupuzha River In Relation To Effluent Discharge

The present study aims at the investigation of the 1ysico—chemical features of a tropical tidal river viz. we Muvattupuzha river. This river is expected to receive Jderate to heavy pollution loads in years to come, from we lone industrial unit, already set up on its bank. ilike other rivers, the geographical disposition of this Lver attains unique importance as regards its dynamics for 3) availability of natural runoff water from catchment :eas, which becomes very heavy during the monsoon season 3) regular steady availability of tail race water from a /dro—electric power station throughout the yearThe study also aims at arriving at the balancing forces of inherent self~purification of the river verses pollution loads from the factory effluents. The investigation period falls ahead of actual pollution occurrence and so the ambient conditions for a period of nearly one-and-a—half years were investigated, the analyses of which providflz to formulate the inter-relations of parameters varying with seasons. Tracer experiments were carried out which revealed the dispersion and dilution characteristics of the river in the vicinity of effluent outfall. The studv covers the trial—cum-capacity production periods of the factory during which effluents of various strength and quantity were discharged into the river; a few computed values arQ’cjmpgrQdl ... with the observed values. The base data along with the profiles of Oxygen sag equation have been utilized fb develop a mathematical model of the river with regard to its water quality