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.

Protease Production by haloarchaea Natrinema sp. BTSH10 isolated from salt pan of South India

The present study led to the recognition of Natrinema sp. BTSH 10 isolated from saltern ponds, as an ideal candidate species for production of gelatinase, which was noted as a halozyme capable of showing enzyme activity in the presence of 15% NaCl. Results obtained during the course of the present study indicated potential for application of this enzyme in industrial catalysis that are performed in the presence of high concentrations of salt. The enzyme characteristics noted with this gelatinase also indicate the scope for probable applications in leather industry, meat tenderization, production of fish sauce and soy sauce. Since halophilic proteases are tolerant to organic solvents, they could be used in antifouling coating preparations used to prevent biofouling of submarine equipments. The gelatinase from haloarchaea could be considered as a probable candidate for peptide synthesis. However, further studies are warranted on this haloarcheal gelatinase particularly on structure elucidation and enzyme engineering to suit a wide range of applications. There is immense scope for developing this halozyme as an industrial enzyme once thorough biochemistry of this gelatinase is studied and a pilot scale study is conducted towards industrial production of this enzyme under fermentation is facilitated. Based on the present study it is concluded that haloarchaea Natrinema sp. that inhabit solar saltern ponds are ideal source for deriving industrially important halozymes and molecular studies on enzymes are prerequisite for their probable industrial applications. This is the first time this species of archaea is recognized as a source of gelatinase enzyme that has potential for industrial applications.

Preparation and Study of Optical Properties of CdS, CdS-TiO2 and CdS-Au Nanocomposites for Photonic Applications

Nanophotonics can be regarded as a fusion of nanotechnology and photonics and it is an emerging field providing researchers opportunities in fundamental science and new technologies. In recent times many new methodsand techniques have been developed to prepare materials at nanoscale dimensions. Most of these materials exhibit unique and interesting optical properties and behavior. Many of these have been found to be very useful to develop new devices and systems such as tracers in biological systems, optical limiters, light emitters and energy harvesters. This thesis presents a summary of the work done by the author in the field by choosing a few semiconductor systems to prepare nanomaterials and nanocomposites. Results of the study of linear and nonlinear optical properties of materials thus synthesized are also presented in the various chapters of this thesis. CdS is the material chosen here and the methods and the studies of the detailed investigation are presented in this thesis related to the optical properties of CdS nanoparticles and its composites. Preparation and characterization methods and experimental techniques adopted for the investigations were illustrated in chapter 2 of this thesis. Chapter 3 discusses the preparation of CdS, TiO2 and Au nanoparticles. We observed that the fluorescence behaviour of the CdS nanoparticles, prepared by precipitation technique, depends on excitation wavelength. It was found that the peak emission wavelength can be shifted by as much as 147nm by varyingthe excitation wavelengths and the reason for this phenomenon is the selective excitation of the surface states in the nanoparticles. This provided certain amount of tunability for the emission which results from surface states.TiO2 nanoparticle colloids were prepared by hydrothermal method. The optical absorption study showed a blue shift of absorption edge, indicating quantum confinement effect. The large spectral range investigated allows observing simultaneously direct and indirect band gap optical recombination. The emission studies carried out show four peaks, which are found to be generated from excitonic as well as surface state transitions. It was found that the emission wavelengths of these colloidal nanoparticles and annealed nanoparticles showed two category of surface state emission in addition to the excitonic emission. Au nanoparticles prepared by Turkevich method showed nanoparticles of size below 5nm using plasmonic absorption calculation. It was also found that there was almost no variation in size as the concentration of precursor was changed from 0.2mM to 0.4mM.We have observed SHG from CdS nanostructured thin film prepared onglass substrate by chemical bath deposition technique. The results point out that studied sample has in-plane isotropy. The relative values of tensor components of the second-order susceptibility were determined to be 1, zzz 0.14, xxz and 0.07. zxx These values suggest that the nanocrystals are oriented along the normal direction. However, the origin of such orientation remains unknown at present. Thus CdS is a promising nonlinear optical material for photonic applications, particularly for integrated photonic devices. CdS Au nanocomposite particles were prepared by mixing CdS nanoparticles with Au colloidal nanoparticles. Optical absorption study of these nanoparticles in PVA solution suggests that absorption tail was red shifted compared to CdS nanoparticles. TEM and EDS analysis suggested that the amount of Au nanoparticles present on CdS nanoparticles is very small. Fluorescence emission is unaffected indicating the presence of low level of Au nanoparticles. CdS:Au PVA and CdS PVA nanocomposite films were fabricated and optically characterized. The results showed a red-shift for CdS:Au PVA film for absorption tail compared to CdS PVA film. Nonlinear optical analysis showed a huge nonlinear optical absorption for CdS:Au PVA nanocomposite and CdS:PVA films. Also an enhancement in nonlinear optical absorption is found for CdS:Au PVA thin film compared to the CdS PVA thin film. This enhancement is due to the combined effect of plasmonic as well as excitonic contribution at high input intensity. Samples of CdS doped with TiO2 were also prepared and the linear optical absorption spectra of these nanocompositeparticles clearly indicated the influence of TiO2 nanoparticles. TEM and EDS studies have confirmed the presence of TiO2 on CdS nanoparticles. Fluorescence studies showed that there is an increase in emission peak around 532nm for CdS nanoparticles. Nonlinear optical analysis of CdS:TiO2 PVA nanocomposite films indicated a large nonlinear optical absorption compared to that of CdS:PVA nanocomposite film. The values of nonlinear optical absorption suggests that these nanocomposite particles can be employed for optical limiting applications. CdSe-CdS and CdSe-ZnS core-shell QDs with varying shell size were characterized using UV–VIS spectroscopy. Optical absorption and TEM analysis of these QDs suggested a particle size around 5 nm. It is clearly shown that the surface coating influences the optical properties of QDs in terms of their size. Fluorescence studies reveal the presence of trap states in CdSe-CdS and CdSe- ZnS QDs. Trap states showed an increase as a shell for CdS is introduced and increasing the shell size of CdS beyond a certain value leads to a decrease in the trap state emission. There is no sizeable nonlinear optical absorption observed. In the case of CdSe- ZnS QDs, the trap state emission gets enhanced with the increase in ZnS shell thickness. The enhancement of emission from trap states transition due to the increase in thickness of ZnS shell gives a clear indication of distortion occurring in the spherical symmetry of CdSe quantum dots. Consequently the nonlinear optical absorption of CdSe-ZnS QDs gets increased and the optical limiting threshold is decreased as the shell thickness is increased in respect of CdSe QDs. In comparison with CdSe-CdS QDs, CdSe-ZnS QDs possess much better optical properties and thereby CdSe-ZnS is a strong candidate for nonlinear as well as linear optical applications.

Differential induction, isolation, physicochemical and molecular characterization of temperate phages of environmental Vibrio cholerae as evidence of phage mediated Horizontal Gene Transfer

The resurgence of the enteric pathogen Vibrio cholerae, the causative organism of epidemic cholera, remains a major health problem in many developing countries like India. The southern Indian state of Kerala is endemic to cholera. The outbreaks of cholera follow a seasonal pattern in regions of endemicity. Marine aquaculture settings and mangrove environments of Kerala serve as reservoirs for V. cholerae. The non-O1/non-O139 environmental isolates of V. cholerae with incomplete ‘virulence casette’ are to be dealt with caution as they constitute a major reservoir of diverse virulence genes in the marine environment and play a crucial role in pathogenicity and horizontal gene transfer. The genes coding cholera toxin are borne on, and can be infectiously transmitted by CTXΦ, a filamentous lysogenic vibriophages. Temperate phages can provide crucial virulence and fitness factors affecting cell metabolism, bacterial adhesion, colonization, immunity, antibiotic resistance and serum resistance. The present study was an attempt to screen the marine environments like aquafarms and mangroves of coastal areas of Alappuzha and Cochin, Kerala for the presence of lysogenic V. cholerae, to study their pathogenicity and also gene transfer potential. Phenotypic and molecular methods were used for identification of isolates as V. cholerae. The thirty one isolates which were Gram negative, oxidase positive, fermentative, with or without gas production on MOF media and which showed yellow coloured colonies on TCBS (Thiosulfate Citrate Bile salt Sucrose) agar were segregated as vibrios. Twenty two environmental V. cholerae strains of both O1 and non- O1/non-O139 serogroups on induction with mitomycin C showed the presence of lysogenic phages. They produced characteristic turbid plaques in double agar overlay assay using the indicator strain V. cholerae El Tor MAK 757. PCR based molecular typing with primers targeting specific conserved sequences in the bacterial genome, demonstrated genetic diversity among these lysogen containing non-O1 V. cholerae . Polymerase chain reaction was also employed as a rapid screening method to verify the presence of 9 virulence genes namely, ctxA, ctxB, ace, hlyA, toxR, zot,tcpA, ninT and nanH, using gene specific primers. The presence of tcpA gene in ALPVC3 was alarming, as it indicates the possibility of an epidemic by accepting the cholera. Differential induction studies used ΦALPVC3, ΦALPVC11, ΦALPVC12 and ΦEKM14, underlining the possibility of prophage induction in natural ecosystems, due to abiotic factors like antibiotics, pollutants, temperature and UV. The efficiency of induction of prophages varied considerably in response to the different induction agents. The growth curve of lysogenic V. cholerae used in the study drastically varied in the presence of strong prophage inducers like antibiotics and UV. Bacterial cell lysis was directly proportional to increase in phage number due to induction. Morphological characterization of vibriophages by Transmission Electron Microscopy revealed hexagonal heads for all the four phages. Vibriophage ΦALPVC3 exhibited isometric and contractile tails characteristic of family Myoviridae, while phages ΦALPVC11 and ΦALPVC12 demonstrated the typical hexagonal head and non-contractile tail of family Siphoviridae. ΦEKM14, the podophage was distinguished by short non-contractile tail and icosahedral head. This work demonstrated that environmental parameters can influence the viability and cell adsorption rates of V. cholerae phages. Adsorption studies showed 100% adsorption of ΦALPVC3 ΦALPVC11, ΦALPVC12 and ΦEKM14 after 25, 30, 40 and 35 minutes respectively. Exposure to high temperatures ranging from 50ºC to 100ºC drastically reduced phage viability. The optimum concentration of NaCl required for survival of vibriophages except ΦEKM14 was 0.5 M and that for ΦEKM14 was 1M NaCl. Survival of phage particles was maximum at pH 7-8. V. cholerae is assumed to have existed long before their human host and so the pathogenic clones may have evolved from aquatic forms which later colonized the human intestine by progressive acquisition of genes. This is supported by the fact that the vast majority of V. cholerae strains are still part of the natural aquatic environment. CTXΦ has played a critical role in the evolution of the pathogenicity of V. cholerae as it can transmit the ctxAB gene. The unusual transformation of V. cholerae strains associated with epidemics and the emergence of V. cholera O139 demonstrates the evolutionary success of the organism in attaining greater fitness. Genetic changes in pathogenic V. cholerae constitute a natural process for developing immunity within an endemically infected population. The alternative hosts and lysogenic environmental V. cholerae strains may potentially act as cofactors in promoting cholera phage ‘‘blooms’’ within aquatic environments, thereby influencing transmission of phage sensitive, pathogenic V. cholerae strains by aquatic vehicles. Differential induction of the phages is a clear indication of the impact of environmental pollution and global changes on phage induction. The development of molecular biology techniques offered an accessible gateway for investigating the molecular events leading to genetic diversity in the marine environment. Using nucleic acids as targets, the methods of fingerprinting like ERIC PCR and BOX PCR, revealed that the marine environment harbours potentially pathogenic group of bacteria with genetic diversity. The distribution of virulence associated genes in the environmental isolates of V. cholerae provides tangible material for further investigation. Nucleotide and protein sequence analysis alongwith protein structure prediction aids in better understanding of the variation inalleles of same gene in different ecological niche and its impact on the protein structure for attaining greater fitness of pathogens. The evidences of the co-evolution of virulence genes in toxigenic V. cholerae O1 from different lineages of environmental non-O1 strains is alarming. Transduction studies would indicate that the phenomenon of acquisition of these virulence genes by lateral gene transfer, although rare, is not quite uncommon amongst non-O1/non-O139 V. cholerae and it has a key role in diversification. All these considerations justify the need for an integrated approach towards the development of an effective surveillance system to monitor evolution of V. cholerae strains with epidemic potential. Results presented in this study, if considered together with the mechanism proposed as above, would strongly suggest that the bacteriophage also intervenes as a variable in shaping the cholera bacterium, which cannot be ignored and hinting at imminent future epidemics.

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.

Spontane Strukturbildung in Mehrschichtsystemen unter Verwendung Molekularer Gläser

Den Schwerpunkt dieser Dissertation bildet zum einen die Entwicklung eines theoretischen Modells zur Beschreibung des Strukturbildungsprozesses in organisch/anorganischen Doppelschichtsystemen und zum anderen die Untersuchung der Übertragbarkeit dieser theoretisch gewonnenen Ergebnisse auf reale Systeme. Hierzu dienen systematische experimentelle Untersuchungen dieses Phänomens an einem Testsystem. Der Bereich der selbstorganisierenden Systeme ist von hohem wissenschaftlichen Interesse, erlaubt er doch die Realisierung von Strukturen, die nicht den Begrenzungen heutiger Techniken unterliegen, wie etwa der Beugung bei lithographischen Verfahren. Darüber hinaus liefert ein vertieftes Verständnis des Strukturbildungsprozesses auch eine Möglichkeit, im Falle entsprechender technischer Anwendungen Instabilitäten innerhalb der Schichtsysteme zu verhindern und somit einer Degradation der Bauteile entgegenzuwirken. Im theoretischen Teil der Arbeit konnte ein Modell im Rahmen der klassischen Elastizitätstheorie entwickelt werden, mit dessen Hilfe sich die Entstehung der Strukturen in Doppelschichtsystemen verstehen läßt. Der hier gefundene funktionale Zusammenhang zwischen der Periode der Strukturen und dem Verhältnis der Schichtdicken von organischer und anorganischer Schicht, wird durch die experimentellen Ergebnisse sehr gut bestätigt. Die Ergebnisse zeigen, daß es technologisch möglich ist, über die Vorgabe der Schichtdicke in einem Materialsystem die Periodizität der entstehenden Strukturen vorzugeben. Darüber hinaus liefert das vorgestellte Modell eine Stabilitätsbedingung für die Schichtsysteme, die es ermöglicht, zu jedem Zeitpunkt die dominierende Mode zu identifizieren. Ein Schwerpunkt der experimentellen Untersuchungen dieser Arbeit liegt auf der Strukturbildung innerhalb der Schichtsysteme. Das Testsystem wurde durch Aufbringen einer organischen Schicht - eines sog. Molekularen Glases - auf ein Glassubstrat realisiert, als Deckschicht diente eine Siliziumnitrid-Schicht. Es wurden Proben mit variierenden Schichtdicken kontrolliert erwärmt. Sobald die Temperatur des Schichtsystems in der Größenordnung der Glasübergangstemperatur des jeweiligen organischen Materials lag, fand spontan eine Strukturbildung auf Grund einer Spannungsrelaxation statt. Es ließen sich durch die Wahl einer entsprechenden Heizquelle unterschiedliche Strukturen realisieren. Bei Verwendung eines gepulsten Lasers, also einer kreisförmigen Wärmequelle, ordneten sich die Strukturen konzentrisch an, wohingegen sich ihre Ausrichtung bei Verwendung einer flächenhaften Heizplatte statistisch verteilte. Auffällig bei allen Strukturen war eine starke Modulation der Oberfläche. Ferner konnte in der Arbeit gezeigt werden, daß sich durch eine gezielte Veränderung der Spannungsverteilung innerhalb der Schichtsysteme die Ausrichtung der Strukturen (gezielt) manipulieren ließen. Unabhängig davon erlaubte die Variation der Schichtdicken die Realisierung von Strukturen mit einer Periodizität im Bereich von einigen µm bis hinunter zu etwa 200 nm. Die Kontrolle über die Ausrichtung und die Periodizität ist Grundvoraussetzung für eine zukünftige technologische Nutzung des Effektes zur kontrollierten Herstellung von Mikro- bzw. Nanostrukturen. Darüber hinaus konnte ein zunächst von der Strukturbildung unabhängiges Konzept eines aktiven Sensors für die optische Raster-Nahfeld-Mikroskopie vorgestellt werden, das das oben beschriebene System, bestehend aus einem fluoreszierenden Molekularen Glas und einer Siliziumnitrid-Deckschicht, verwendet. Erste theoretische und experimentelle Ergebnisse zeigen das technologische Potential dieses Sensortyps.

Rissbildung und Zugtragverhalten von mit Stabstahl und Fasern bewehrtem Ultrahochfesten Beton (UHPC)

Ultrahochfester Beton (UHPC) ist ein sehr gefügedichter zementgebundener Werkstoff, der sich nicht nur durch eine hohe Druckfestigkeit, sondern auch durch einen hohen Widerstand gegen jede Form physikalischen oder chemischen Angriffs auszeichnet. Duktiles Nachbruchverhalten bei Druckversagen wird meist durch die Zugabe dünner kurzer Fasern erreicht. In Kombination mit konventioneller Betonstahl- oder Spannbewehrung ermöglicht UHPC die Ausführung sehr schlanker, weitgespannter Konstruktionen und eröffnet zugleich neue Anwendungsgebiete, wie zum Beispiel die flächenhafte Beschichtung von Brückendecks. Durch das Zusammenwirken kontinuierlicher Bewehrungselemente und diskontinuierlich verteilter kurzer Fasern ergeben sich unter Zugbeanspruchung Unterschiede gegenüber dem bekannten Stahl- und Spannbeton. In der vorliegenden Arbeit wird hierzu ein Modell entwickelt und durch eine umfangreiche Versuchsreihe abgesichert. Ausgangspunkt sind experimentelle und theoretische Untersuchungen zum Verbundverhalten von Stabstählen in einer UHPC-Matrix und zum Einfluss einer Faserzugabe auf das Reiß- und Zugtragverhalten von UHPC. Die Modellbildung für UHPC-Zugelemente mit gemischter Bewehrung aus Stabstahl und Fasern erfolgt auf der Grundlage der Vorgänge am diskreten Riss, die daher sehr ausführlich behandelt werden. Für den elastischen Verformungsbereich der Stabbewehrung (Gebrauchslastbereich) kann damit das Last-Verformungs-Verhalten für kombiniert bewehrte Bauteile mechanisch konsistent unter Berücksichtigung des bei UHPC bedeutsamen hohen Schwindmaßes abgebildet werden. Für die praktische Anwendung wird durch Vereinfachungen ein Näherungsverfahren abgeleitet. Sowohl die theoretischen als auch die experimentellen Untersuchungen bestätigen, dass der faserbewehrte UHPC bei Kombination mit kontinuierlichen Bewehrungselementen selbst kein verfestigendes Verhalten aufweisen muss, um insgesamt verfestigendes Verhalten und damit eine verteilte Rissbildung mit sehr keinen Rissbreiten und Rissabständen zu erzielen. Diese Beobachtungen können mit Hilfe der bisher zur Verfügung stehenden Modelle, die im Wesentlichen eine Superposition isoliert ermittelter Spannungs-Dehnungs-Beziehungen des Faserbetons und des reinen Stahls vorsehen, nicht nachvollzogen werden. Wie die eigenen Untersuchungen zeigen, kann durch ausreichend dimensionierte Stabstahlbewehrung zielgerichtet und ohne unwirtschaftlich hohe Fasergehalte ein gutmütiges Verhalten von UHPC auf Zug erreicht werden. Die sichere Begrenzung der Rissbreiten auf deutlich unter 0,1 mm gewährleistet zugleich die Dauerhaftigkeit auch bei ungünstigen Umgebungsbedingungen. Durch die Minimierung des Material- und Energieeinsatzes und die zu erwartende lange Nutzungsdauer lassen sich so im Sinne der Nachhaltigkeit optimierte Bauteile realisieren.

Textiles - Screen Printing Training

Training on techniques needed to use the textile screen printing facilities at WSA. Please note that watching these videos does not mean you are authorised to use these machines, this is for reference after a formal in person induction.

The pattern of fall of serum bilirubin after operative relief of obstructive jaundice. A preliminary report

This is the beginning of a prospective study on patients who have obstructive jaundice to see how the serum bilirubin falls after operative relief of the obstruction. Seven of such patients have been studied; four had carcinoma of the head of the pancreas while the other three had choledocholithiasis. The patients with carcinoma had relief of the jaundice through a biliary-enteric anastomosis and those with common bile duct stones had choledochotomy with stone extraction which was completed with insertion of a T-tube. Serial bilirubin estimations were then performed post-operatively to chart the pattern and rate of descent of this in each patient. Our observations suggest that the pattern of fall of serum bilirubin after successful decompression of the extra-hepatic biliary tree exhibit a distinct pattern regardless of the surgical procedure performed for the relief of the obstruction.

Eficacia de la limpieza corporal con clorhexidina en prevenir la sepsis neonatal en cuidado intensivo revisión sistemática

ANTECEDENTES. La mortalidad neonatal se debe principalmente a procesos infecciosos y a prematurez. Se ha sugerido que el lavado corporal total con clorhexidina podría reducir la mortalidad neonatal relacionada con infección. No existen revisiones sistemáticas que exploren la eficacia de esta intervención. Objetivo. Evaluar la eficacia y seguridad de la limpieza corporal total con clorhexidina en la prevención de las infecciones asociadas al cuidado de la salud en neonatos de alto riesgo hospitalizados en cuidado intensivo neonatal. Metodología. Se realizó una revisión sistemática de la literatura. La búsqueda se hizo a través de las bases de datos Medline, Embase, LilaCS, Cochrane library y el registro de ensayos clínicos del Instituto Nacional de Salud de Estados Unidos. Se incluyeron ensayos clínicos publicados en los últimos 15 años hasta el 30 de enero del 2015. Las variables cualitativas se estimaron mediante OR o RR con sus IC95%. Las variables cuantitativas mediante diferencias de promedios o diferencias estandarizadas de promedios con sus IC95%. Resultados: Se incluyeron 3 estudios en el análisis cualitativo y cuantitativo. No se encontró evidencia concluyente que permita recomendar el uso de la limpieza corporal total con clorhexidina en los recién nacidos hospitalizados en cuidado intensivo neonatal. Conclusión: No existe evidencia que permita concluir que la limpieza corporal total con clorhexidina al 0.25% es mejor respecto a otras intervenciones en la prevención de sepsis neonatal asociada al cuidado de la salud . Es una intervención segura sin efectos adversos significativos.

Jardins Verticais : um contributo para os espaços verdes urbanos e oportunidade na reabilitação do edificado

O Homem tem privilegiado a vida no meio urbano, em detrimento do rural, por mais oportunidade de emprego e melhores condições de vida. As cidades cresceram de forma acelerada, sobretudo depois da Revolução Industrial do século XVIII, crescimento sem controlo, repercutindo-se num desajustado planeamento urbano, ambiental, humano, social e económico. De uma forma, as paisagens verdes e naturais, foram substituídas por densas manchas cinzentas de construção, criando afastamento crescente do Homem com a Natureza. Os Jardins Verticais poderão ter um papel fundamental revestindo de forma verde e natural as fachadas dos edifícios, numa tentativa de colmatar o afastamento entre ambos. Para além destes aspectos, os Jardins Verticais proporcionam inúmeras vantagens para o edifício, de que se destacam a eficiência energética e acústica, a protecção da estrutura do edificado ou a melhoria da qualidade do ar interior. Estes também importantes para a envolvente, como na redução do efeito ilha de calor, no aumento da biodiversidade, na melhoria da qualidade do ar exterior, mas sobretudo porque proporcionam ao Homem uma sensação de saúde e conforto, exclusivo da Natureza. Tendo em conta o estado de degradação do edificado nas grandes cidades, e tomando como exemplo particular a cidade do Porto, o recurso aos Jardins Verticais poderá ser uma solução viável para a reabilitação urbana, mudando a imagem de degradação, propondo uma imagem mais “verde” e contribuindo para o nível de sustentabilidade. Partindo deste pressuposto, propõe-se como aplicação do conhecimento adquirido no estudo desenvolvido e aqui apresentado, o recurso a Jardins Verticais como estratégia de reabilitação de edifícios da cidade do Porto. Inspirado na técnica e mestria de Patrick Blanc, resultou um “pormenor-tipo”, como base para a aplicação de Jardins Verticais no edificado social da cidade, experimentado em 10 estudos práticos, tirando-se partido das vantagens supra-mencionadas.

Common black coatings - reflectance and ageing characteristics in the 0.32-14.3 mu m wavelength range

The diffuse and regular reflectances of five optically absorbing coatings frequently used in optical systems, were measured over the 0.32-14.3 mu m wavelength range, before and after exposure to heat and intense optical radiation. The measured coatings included Nextel Velvet Black, an anodised coating and NPL Super Black. The anodised coating exhibited substantial variations in its diffuse and regular reflectance values after thermal and simulated solar ageing. Solar and thermal ageing of the Nextel Velvet Black resulted in increases of its reflectance. However, thermal ageing tended to decrease the reflectance of the other paint samples examined. Thermal and solar ageing of the NPL Super Black resulted in only minor changes in its reflectance characteristics. All measurements are traceable to the UK National Standards.

Cooled Infrared Dichroic Beamsplitters and Filters for the MIRI Spectrometer and Imager (5-29µm)

The spectral design and fabrication of cooled (7K) mid-infrared dichroic beamsplitters and bandpass filter coatings for the MIRI spectrometer and imager are described. Design methods to achieve the spectral performance and coating materials are discussed.

The effect of flow field & geometry on the dynamic contact angle

A number of recent experiments suggest that, at a given wetting speed, the dynamic contact angle formed by an advancing liquid-gas interface with a solid substrate depends on the flow field and geometry near the moving contact line. In the present work, this effect is investigated in the framework of an earlier developed theory that was based on the fact that dynamic wetting is, by its very name, a process of formation of a new liquid-solid interface (newly “wetted” solid surface) and hence should be considered not as a singular problem but as a particular case from a general class of flows with forming or/and disappearing interfaces. The results demonstrate that, in the flow configuration of curtain coating, where a liquid sheet (“curtain”) impinges onto a moving solid substrate, the actual dynamic contact angle indeed depends not only on the wetting speed and material constants of the contacting media, as in the so-called slip models, but also on the inlet velocity of the curtain, its height, and the angle between the falling curtain and the solid surface. In other words, for the same wetting speed the dynamic contact angle can be varied by manipulating the flow field and geometry near the moving contact line. The obtained results have important experimental implications: given that the dynamic contact angle is determined by the values of the surface tensions at the contact line and hence depends on the distributions of the surface parameters along the interfaces, which can be influenced by the flow field, one can use the overall flow conditions and the contact angle as a macroscopic multiparametric signal-response pair that probes the dynamics of the liquid-solid interface. This approach would allow one to investigate experimentally such properties of the interface as, for example, its equation of state and the rheological properties involved in the interface’s response to an external torque, and would help to measure its parameters, such as the coefficient of sliding friction, the surface-tension relaxation time, and so on.

A combined BIE-FE method for the Stokes equations

A numerical algorithm for the biharmonic equation in domains with piecewise smooth boundaries is presented. It is intended for problems describing the Stokes flow in the situations where one has corners or cusps formed by parts of the domain boundary and, due to the nature of the boundary conditions on these parts of the boundary, these regions have a global effect on the shape of the whole domain and hence have to be resolved with sufficient accuracy. The algorithm combines the boundary integral equation method for the main part of the flow domain and the finite-element method which is used to resolve the corner/cusp regions. Two parts of the solution are matched along a numerical ‘internal interface’ or, as a variant, two interfaces, and they are determined simultaneously by inverting a combined matrix in the course of iterations. The algorithm is illustrated by considering the flow configuration of ‘curtain coating’, a flow where a sheet of liquid impinges onto a moving solid substrate, which is particularly sensitive to what happens in the corner region formed, physically, by the free surface and the solid boundary. The ‘moving contact line problem’ is addressed in the framework of an earlier developed interface formation model which treats the dynamic contact angle as part of the solution, as opposed to it being a prescribed function of the contact line speed, as in the so-called ‘slip models’. Keywords: Dynamic contact angle; finite elements; free surface flows; hybrid numerical technique; Stokes equations.