Singlet Oxygen in Microporous Silica Xerogel:Quantum Yield and Oxidation at the Gas–Solid Interface

The quantum yields of singlet oxygen production and lifetimes at the gas–solid interface in silica gel material are determined. Different photosensitizers (PS) are encapsulated in parallelepipedic xerogel monoliths (PS-SG). PS were chosen according to their known photooxidation properties: 9,10-dicyanoanthracene (DCA), 9,10-anthraquinone (ANT), and a benzophenone derivative, 4-benzoyl benzoic acid (4BB). These experiments are mainly based on time-resolved 1O2 phosphorescence detection, and the obtained FD and tD values are compared with those of a reference sensitizer for production, 1H-phenalen-1- one (PN), included in the same xerogel. The trend between their ability to oxidize organic pollutants in the gas phase and their efficiency for production is investigated through photooxidation experiments of a test pollutant dimethylsulfide (DMS). The FD value is high for DCA-SG relative to the PN reference, whereas it is slightly lower for 4BB-SG and for ANT-SG. FD is related to the production of sulfoxide and sulfone as the main oxidation products for DMS photosensitized oxidation. Additional mechanisms, leading to C!S bond cleaveage, appear to mainly occur for the less efficient singlet oxygen sensitizers 4BB-SG and ANTSG.

Ultrasonic Study Of The Elastic Properties And Phase Transitions In Selected Mixed Sulphate Crystals

The thesis investigated the elastic properties and phase transitions in selected mixed sulphate crystals – Lithium Hydrazinium Sulphate [LiN2H2SO4], Lithium Ammonium Sulphate [LiNH4SO4] and Lithium Potassium Sulphate [LiKSO4] – using ultrasonic technique. The pulse echo overlap technique has been used for measuring ultrasonic velocity and its dependence on temperature along different directions with waves of longitudinal and transverse polarizations. Two major numerical techniques and the corresponding computer programs developed as part of present work are presented in this thesis. All the 9 elastic constants of LHS are determined accurately from ultrasonic measurements and applying misorientation correction refines the constants. Ultrasonic measurements are performed in LAS to determine the elastic constants and to study the low temperature phase transitions. Temperature variation studies of elastic constant of LAS are performed for 6 different modes of propagation for heating and cooling at low temperatures. All the 5 independent elastic constants of LPS is determined using ultrasonic measurements. It is concluded that LPS crystal does not undergo a phase transition near this temperature. A comparison of the three crystals studied shows that LPS has maximum number of phase transitions and LHS has the least number. It is interesting to note that LPS has the simplest formula unit among the three. There is considerable scope for the future work on these crystals and others belonging to the sulphate family.

Ultrasonic measurement of the elastic properties of benzoyl glycine single crystals

Certain organic crystals are found to possess high non- linear optical coefficients,often one to two orders of magnitude higher than those of the well known inorganic non-linear optical materials.Benzoyl glycine is one such crystal whose optical second-harmonic generation efficiency is much higher than that of potassium dihydrogen phosphate. Single crystals of benzoyl glycine are grown by solvent evaporation technique using N,N-dimethyl formamide as the solvent.All the nine second-order elastic stiffness constants of this orthorhombic crystal are determined from ultrasonic wave velocity measurements employing the pulse echo overlap technique.The anisotropy of elastic wave propagation in this crystal is demonstrated by plotting the phase velocity, slowness,Young's modulus and linear compressibility surfaces along symmetry planes.The volume compressibility, bulk modulus and relevant Poisson's ratios are also determined. Variation of the diagonal elastic stiffness constants with temperature over a limited range are measured and reported.

Characterization of Selected Photonic Materials and Systems Using Photoacoustic Technique

The photoacoustic investigations carried out on different photonic materials are presented in this thesis. Photonic materials selected for the investigation are tape cast ceramics, muItilayer dielectric coatings, organic dye doped PVA films and PMMA matrix doped with dye mixtures. The studies are performed by the measurement of photoacoustic signal generated as a result of modulated cw laser irradiation of samples. The gas-microphone scheme is employed for the detection of photoacoustic signal. The different measurements reported here reveal the adaptability and utility of the PA technique for the characterization of photonic materials.Ceramics find applications in the field of microelectronics industry. Tape cast ceramics are the building blocks of many electronic components and certain ceramic tapes are used as thermal barriers. The thermal parameters of these tapes will not be the same as that of thin films of the same materials. Parameters are influenced by the presence of foreign bodies in the matrix and the sample preparation technique. Measurements are done on ceramic tapes of Zirconia, Zirconia-Alumina combination, barium titanate, barium tin titanate, silicon carbide, lead zirconate titanateil'Z'T) and lead magnesium niobate titanate(PMNPT). Various configurations viz. heat reflection geometry and heat transmission geometry of the photoacoustic technique have been used for the evaluation of different thermal parameters of the sample. Heat reflection geometry of the PA cell has been used for the evaluation of thermal effusivity and heat transmission geometry has been made use of in the evaluation of thermal diffusivity. From the thermal diffusivity and thermal effusivity values, thermal conductivity is also calculated. The calculated values are nearly the same as the values reported for pure materials. This shows the feasibility of photoacoustic technique for the thermal characterization of ceramic tapes.Organic dyes find applications as holographic recording medium and as active media for laser operations. Knowledge of the photochemical stability of the material is essential if it has to be used tor any of these applications. Mixing one dye with another can change the properties of the resulting system. Through careful mixing of the dyes in appropriate proportions and incorporating them in polymer matrices, media of required stability can be prepared. Investigations are carried out on Rhodamine 6GRhodamine B mixture doped PMMA samples. Addition of RhB in small amounts is found to stabilize Rh6G against photodegradation and addition of Rh6G into RhB increases the photosensitivity of the latter. The PA technique has been successfully employed for the monitoring of dye mixture doped PMMA sample. The same technique has been used for the monitoring of photodegradation ofa laser dye, cresyl violet doped polyvinyl alcohol also.Another important application of photoacoustic technique is in nondestructive evaluation of layered samples. Depth profiling capability of PA technique has been used for the non-destructive testing of multilayer dielectric films, which are highly reflecting in the wavelength range selected for investigations. Eventhough calculation of thickness of the film is not possible, number of layers present in the system can be found out using PA technique. The phase plot has clear step like discontinuities, the number of which coincides with the number of layers present in the multilayer stack. This shows the sensitivity of PA signal phase to boundaries in a layered structure. This aspect of PA signal can be utilized in non-destructive depth profiling of reflecting samples and for the identification of defects in layered structures.

Fabrication of Electrochemical Sensors for the Determination of Pharmaceuticals

Voltammetric sensors are an important class of electrochemical sensors in which the analytical information is obtained from the measurement of current obtained as a result of electrochemical oxidation/reduction.This current is proportional to the concentration of the analyte.Chemically modified electrodes(CMEs) have great significance as important analytical tools for the electrochemical determination of pharmaceuticals.The modification of electrode results in efficient determination of electro-active biomolecules at very lower potential without its major interferences.The operation mechanism of CMEs depends on the properties of the modifier materials that are used to promote selectivity towards the target analytes.Modified electrodes can be prepared by deposition of various compounds such as organic compounds ,conducting polymers,metal oxides,etc. on the various electrode surfaces.The thesis presents the development ,electrochemical characterization and analytical application studies of eight voltammetric sensors developed for six drugs viz.,Ambroxol,Sulfamethoxazole,PAM Chloride, Lamivudine,Metronidazole and Nimesulide.The modification techniques adopted as part of the present work include Multiwalled Carbon Nanotube(MWCNT) based modification.Electropolymerisation and Gold Nanoparticle (AuNP) based modifications.

The quantum effects in quadratically damped systems

A dynamical system with a damping that is quadratic in velocity is converted into the Hamiltonian format using a nonlinear transformation. Its quantum mechanical behaviour is then analysed by invoking the Gaussian effective potential technique. The method is worked out explicitly for the Duffing oscillator potential.

Studies on equatorial undercurrent in the indian ocean

This thesis is an outcome of the studies, carried out by the author on the Equatorial Undercurrent and the Equatorial Jet, an interesting and unique phenomenon discovered, recently, in the Indian Ocean (wyrtxi, 1973). The main objective of the thesis is to carry out a detailed investigation of the seasonal, latitudinal and longitudinal variation of the Equatorial Undercurrent in the Indian Ocean and also the Equatorial Jet, through mapping the vertical distribution of the oceanographic properties across the equator along various longitudes for all the months of an year, between SON and SOS, utilising the oceanographic data collected during the International Indian Ocean Expedition and subsequently in the equatorial Indian Ocean. As the distribution of the hydrographic properties give only a qualitative identification of the Undercurrent, a novel technique of computing the zonal flux through bivariate distribution of salinity and thermosteric anomaly introduced by Montgomery and Stroup (1962), is adopted in order to have a quantitative variation of the Equatorial Undercurrent and the Equatorial Jet. Finally, an attempt is made to give a plausible explanation of the features observed.

Studies on the propagation of errors in physical oceanographic computations

The results of an investigation on the limits of the random errors contained in the basic data of Physical Oceanography and their propagation through the computational procedures are presented in this thesis. It also suggest a method which increases the reliability of the derived results. The thesis is presented in eight chapters including the introductory chapter. Chapter 2 discusses the general theory of errors that are relevant in the context of the propagation of errors in Physical Oceanographic computations. The error components contained in the independent oceanographic variables namely, temperature, salinity and depth are deliniated and quantified in chapter 3. Chapter 4 discusses and derives the magnitude of errors in the computation of the dependent oceanographic variables, density in situ, gt, specific volume and specific volume anomaly, due to the propagation of errors contained in the independent oceanographic variables. The errors propagated into the computed values of the derived quantities namely, dynamic depth and relative currents, have been estimated and presented chapter 5. Chapter 6 reviews the existing methods for the identification of level of no motion and suggests a method for the identification of a reliable zero reference level. Chapter 7 discusses the available methods for the extension of the zero reference level into shallow regions of the oceans and suggests a new method which is more reliable. A procedure of graphical smoothening of dynamic topographies between the error limits to provide more reliable results is also suggested in this chapter. Chapter 8 deals with the computation of the geostrophic current from these smoothened values of dynamic heights, with reference to the selected zero reference level. The summary and conclusion are also presented in this chapter.

A study on the parameters affecting the compressibility characteristics of Cochin marine clays

There are numerous parameters affecting the compressibility characteristics of soft clays. A few of them such as load increment ratio, type of drainage and thickness of sample were taken up for detailed investigation. However, the main thrust in the present investigations was to develop an insight into the benefits of preloading technique, envolve procedures and establish design charts for preparation of a precompression programme which will substantially reduce the consolidation settlements of the extremely soft deposits of Cochin marine clays.

EVALUATION OF THERMODYNAMIC PARAMETERS OF THE ATMOSPHERE BY A FORTRAN PROGRAM

Thermodynamic parameters of the atmosphere form part of the input to numerical forecasting models. Usually these parameters are evaluated from a thermodynamic diagram. Here, a technique is developed to evaluate these parameters quickly and accurately using a Fortran program. This technique is tested with four sets of randomly selected data and the results are in agreement with the results from the conventional method. This technique is superior to the conventional method in three respects: more accuracy, less computation time, and evaluation of additional parameters. The computation time for all the parameters on a PC AT 286 machine is II sec. This software, with appropriate modifications, can be used, for verifying various lines on a thermodynamic diagram

Structural, magnetic and electrical properties of the sol-gel prepared Li0.5Fe2.5O4 fine particles

Fine particles of lithium ferrite were synthesized by the sol-gel method. By subsequent heat treatment at different temperatures, lithium ferrites of different grain sizes were prepared. A structural characterization of all the samples was conducted by the x-ray diffraction technique. A grain size of around 12 nm was observed for Li0.5Fe2.5O4 obtained through the sol-gel method. Magnetic properties of lithium ferrite nanoparticles with grain size ranging from 12 to 32 nm were studied. Magnetization measurements showed that Li0.5Fe2.5O4 fine particles exhibit a deviation from the predicted magnetic behaviour. The as-prepared sample of lithium ferrite showed a maximum saturation magnetization of 75 emu g−1. Variation of coercivity is attributed to the transition from multi-domain to single domain nature. Dielectric permittivity and ac conductivity of all the samples were evaluated as a function of frequency, temperature and grain size. Variation of permittivity and ac conductivity with frequency reveals that the dispersion is due to the Maxwell–Wagner type interfacial polarization

Piezoresistive cantilevers with an integrated bimorph actuator

Scanning Probe Microscopy (SPM) has become of fundamental importance for research in area of micro and nano-technology. The continuous progress in these fields requires ultra sensitive measurements at high speed. The imaging speed limitation of the conventional Tapping Mode SPM is due to the actuation time constant of piezotube feedback loop that keeps the tapping amplitude constant. In order to avoid this limit a deflection sensor and an actuator have to be integrated into the cantilever. In this work has been demonstrated the possibility of realisation of piezoresistive cantilever with an embedded actuator. Piezoresistive detection provides a good alternative to the usual optical laser beam deflection technique. In frames of this thesis has been investigated and modelled the piezoresistive effect in bulk silicon (3D case) for both n- and p-type silicon. Moving towards ultra-sensitive measurements it is necessary to realize ultra-thin piezoresistors, which are well localized to the surface, where the stress magnitude is maximal. New physical effects such as quantum confinement which arise due to the scaling of the piezoresistor thickness was taken into account in order to model the piezoresistive effect and its modification in case of ultra-thin piezoresistor (2D case). The two-dimension character of the electron gas in n-type piezoresistors lead up to decreasing of the piezoresistive coefficients with increasing the degree of electron localisation. Moreover for p-type piezoresistors the predicted values of the piezoresistive coefficients are higher in case of localised holes. Additionally, to the integration of the piezoresistive sensor, actuator integrated into the cantilever is considered as fundamental for realisation of fast SPM imaging. Actuation of the beam is achieved thermally by relying on differences in the coefficients of thermal expansion between aluminum and silicon. In addition the aluminum layer forms the heating micro-resistor, which is able to accept heating impulses with frequency up to one megahertz. Such direct oscillating thermally driven bimorph actuator was studied also with respect to the bimorph actuator efficiency. Higher eigenmodes of the cantilever are used in order to increase the operating frequencies. As a result the scanning speed has been increased due to the decreasing of the actuation time constant. The fundamental limits to force sensitivity that are imposed by piezoresistive deflection sensing technique have been discussed. For imaging in ambient conditions the force sensitivity is limited by the thermo-mechanical cantilever noise. Additional noise sources, connected with the piezoresistive detection are negligible.

Wechselwirkung von im NANOJET erzeugten Teilchen mit Polymeren und biologischen Objekten

Am Institut für Mikrostrukturtechnologie und Analytik wurde eine neue Technik entwickelt, die neue Anwendungen und Methoden der Mikro- und Nanostrukturierung auf Basis eines neuen Verfahrens erschlossen hat. NANOJET führt über die passive Rastersondenmikroskopie hinaus zu einem vielseitigen, aktiven Bearbeitungswerkzeug auf der Mikro- und Nanometerskala. NANOJET (NANOstructuring Downstream PlasmaJET) ist eine aktive Rasterkraft-Mikroskopie-Sonde. Radikale (chemisch aktive Teilchen, die ein ungepaartes Valenzelektron besitzen) strömen aus dem Ende einer ultradünnen, hohlen Rasterkraftmikroskop-Spitze. Dadurch wird es möglich, über die übliche passive Abtastung einer Probenoberfläche hinausgehend, diese simultan und in-situ durch chemische Reaktionen zu verändern. Die Abtragung von Material wird durch eine chemische Ätzreaktion erreicht. In dieser Arbeit wurde zum größten Teil Photoresist als Substrat für die Ätzexperimente verwendet. Für das Ätzen des Resists wurden die Atome des Fluors und des Sauerstoffs im Grundzustand als verantwortlich identifiziert. Durch Experimente und durch Ergänzung von Literaturdaten wurde die Annahme bestätigt, dass Sauerstoffradikale mit Unterstützung von Fluorradikalen für die hohen erzielten Ätzraten verantwortlich sind. Die Beimischung von Fluor in einem Sauerstoffplasma führt zu einer Verringerung der Aktivierungsenergie für die Ätzreaktion gegenüber Verwendung reinen Sauerstoffs. In weiterer Folge wurde ein Strukturierungsverfahren dargestellt. Hierbei wurden "geformte Kapillaren" (mikrostrukturierte Aperturen) eingesetzt. Die Herstellung der Aperturen erfolgte durch einen elektrochemischen Ätzstop-Prozess. Die typische Größe der unter Verwendung der "geformten Kapillaren" geätzten Strukturen entsprach den Kapillarenöffnungen. Es wurde ein Monte-Carlo Simulationsprogramm entwickelt, welches den Transport der reaktiven Teilchen in der langen Transportröhre simulierte. Es wurde sowohl die Transmission der Teilchen in der Transportröhre und der Kapillare als auch ihre Winkelverteilung nach dem Verlassen der Kapillare berechnet. Das Aspektverhältnis der Röhren hat dabei einen sehr starken Einfluss. Mit einem steigenden Aspektverhältnis nahm die Transmission exponentiell ab. Die geschaffene experimentelle Infrastruktur wurde genutzt, um auch biologische Objekte zu behandeln und zu untersuchen. Hierfür wurde eine neue Methodik entwickelt, die eine dreidimensionale Darstellung des Zellinneren erlaubt. Dies wurde durch die kontrollierte Abtragung von Material aus der Zellmembran durchgeführt. Die Abtragung der Zellmembran erfolgte mittels Sauerstoffradikalen, die durch eine hohle Spitze lokalisiert zum Ort der Reaktion transportiert wurden. Ein piezoresistiver Cantilever diente als Sensor in dem zur Bildgebung eingesetzten RKM. Das entwickelte Verfahren ermöglicht es nun erstmals, schonend Zellen zu öffnen und die innen liegenden Organellen weiter zu untersuchen. Als Nachweis für weitere Verwendungsmöglichkeiten des NANOJET-Verfahrens wurde auch Knochenmaterial behandelt. Die Ergebnisse dieser Experimente zeigen klar, dass das Verfahren für vielfältige biologische Materialien verwendbar ist und somit nun ein weiter Anwendungskreis in der Biologie und Medizin offen steht.

The Effect of Periodic Silane Burst on the Properties of GaN on Si (111) Substrates

The periodic silane burst technique was employed during metalorganic chemical vapor deposition of epitaxial GaN on AlN buffer layers grown on Si (111). Periodic silicon delta doping during growth of both the AlN and GaN layers led to growth of GaN films with decreased tensile stresses and decreased threading dislocation densities, as well as films with improved quality as indicated by x-ray diffraction, micro-Raman spectroscopy, atomic force microscopy, and transmission electron microscopy. The possible mechanism of the reduction of tensile stress and the dislocation density is discussed in the paper.

News from compositions, the R package

The R-package “compositions”is a tool for advanced compositional analysis. Its basic functionality has seen some conceptual improvement, containing now some facilities to work with and represent ilr bases built from balances, and an elaborated subsys- tem for dealing with several kinds of irregular data: (rounded or structural) zeroes, incomplete observations and outliers. The general approach to these irregularities is based on subcompositions: for an irregular datum, one can distinguish a “regular” sub- composition (where all parts are actually observed and the datum behaves typically) and a “problematic” subcomposition (with those unobserved, zero or rounded parts, or else where the datum shows an erratic or atypical behaviour). Systematic classification schemes are proposed for both outliers and missing values (including zeros) focusing on the nature of irregularities in the datum subcomposition(s). To compute statistics with values missing at random and structural zeros, a projection approach is implemented: a given datum contributes to the estimation of the desired parameters only on the subcompositon where it was observed. For data sets with values below the detection limit, two different approaches are provided: the well-known imputation technique, and also the projection approach. To compute statistics in the presence of outliers, robust statistics are adapted to the characteristics of compositional data, based on the minimum covariance determinant approach. The outlier classification is based on four different models of outlier occur- rence and Monte-Carlo-based tests for their characterization. Furthermore the package provides special plots helping to understand the nature of outliers in the dataset. Keywords: coda-dendrogram, lost values, MAR, missing data, MCD estimator, robustness, rounded zeros