Fluorometric fiber optic drop sensor for atmospheric hydrogen sulfide

A fluorometric technique based on a liquid drop excited from its interior by an optical fiber is described for the measurement of low concentrations of atmospheric hydrogen sulfide (H2S). A drop of alkaline fluorescein mercuric acetate (FMA) solution is suspended in a flowing air sample stream and serves as a renewable sensor. An optical fiber contained within the conduit that forms the drop, brings in the excitation beam; the fluorescence emission is measured by an inexpensive photodiode positioned close to the drop. As H2S in the sample is collected by the alkaline drop, it reacts rapidly with FMA resulting in a significant decrease in fluorescence intensity, proportional to the concentration of H2S sampled. The chemistry of this uniquely selective reaction has been well established for many years, the present technique permits a simple fast inexpensive near real-time measurement with very little reagent consumption. Even without prolonged sampling/preconcentration steps, limits of detection (LODs) in the double digit ppbv range is readily attainable. (C) 1997 Elsevier B.V. B.V.

Construction and performance of a drop cell for the nephelometric determination of sulfur dioxide

A nephelometric technique based on a liquid drop is described for the measurement of atmospheric sulfur dioxide. A 40-mul drop of barium chloride and hydrogen peroxide solution is suspended in a flowing-air sampling stream. The sulfur (IV) collected is oxidized to sulfur (VI) and finally precipitated as barium sulfate. Nephelometric detection of drop is achieved by an appropriate arrangement consisting of an optical fiber contacting the drop and a photodiode placed at 90degrees relative to the fiber. The design and characteristics of this drop-based gas sensor system are described. The analytical response, as photocurrent, is proportional to the product of the sampling period and the sulfur dioxide concentration. The detection limit is ca. 1.1 mg m(-3) for a 10-min sampling time. The present technique is fairly rapid and simple, uses a small amount of reagent and is set up with low-cost equipment, making this system economically viable. (C) 2002 Elsevier B.V. B.V. All rights reserved.

Controlled wetting on silica-based nano- and microstructured surfaces

Der Fokus dieser Doktorarbeit liegt auf der kontrollierten Benetzung von festen Oberflächen, die in vielen Bereichen, wie zum Beispiel in der Mikrofluidik, für Beschichtungen und in biologischen Studien von Zellen oder Bakterien, von großer Bedeutung ist.rnDer erste Teil dieser Arbeit widmet sich der Frage, wie Nanorauigkeit das Benetzungsverhalten, d.h. die Kontaktwinkel und die Pinningstärke, von hydrophoben und superhydrophoben Beschichtungen beeinflusst. Hierfür wird eine neue Methode entwickelt, um eine nanoraue Silika-Beschichtung über die Gasphase auf eine superhydrophobe Oberfläche, die aus rauen Polystyrol-Silika-Kern-Schale-Partikeln besteht, aufzubringen. Es wird gezeigt, dass die Topographie und Dichte der Nanorauigkeiten bestimmt, ob sich die Superhydrophobizität verringert oder erhöht, d.h. ob sich ein Flüssigkeitstropfen im Nano-Wenzel- oder Nano-Cassie-Zustand befindet. Das verstärkte Pinning im Nano-Wenzel-Zustand beruht auf dem Eindringen von Flüssigkeitsmolekülen in die Nanoporen der Beschichtung. Im Nano-Cassie-Zustand dagegen sitzt der Tropfen auf den Nanorauigkeiten, was das Pinning vermindert. Die experimentellen Ergebnisse werden mit molekulardynamischen Simulationen in Bezug gesetzt, die den Einfluss der Oberflächenbeschichtungsdichte und der Länge von fluorinierten Silanen auf die Hydrophobizität einer Oberfläche untersuchen. rnEs wurden bereits verschiedenste Techniken zur Herstellung von transparenten superhydrophoben, d.h. extrem flüssigkeitsabweisenden, Oberflächen entwickelt. Eine aktuelle Herausforderung liegt darin, Funktionalitäten einzuführen, ohne die superhydrophoben Eigenschaften einer Oberfläche zu verändern. Dies ist extrem anspruchsvoll, da funktionelle Gruppen in der Regel hydrophil sind. In dieser Arbeit wird eine innovative Methode zur Herstellung von transparenten superhydrophoben Oberflächen aus Janus-Mikrosäulen mit variierenden Dimensionen und Topographien entwickelt. Die Janus-Säulen haben hydrophobe Seitenwände und hydrophile Silika-Oberseiten, die anschließend selektiv und ohne Verlust der superhydrophoben Eigenschaften der Oberfläche funktionalisiert werden können. Diese selektive Oberflächenfunktionalisierung wird mittels konfokaler Mikroskopie und durch das chemische Anbinden von fluoreszenten Molekülen an die Säulenoberseiten sichtbar gemacht. Außerdem wird gezeigt, dass das Benetzungsverhalten durch Wechselwirkungen zwischen Flüssigkeit und Festkörper in der Nähe der Benetzungslinie bestimmt wird. Diese Beobachtung widerlegt das allgemein akzeptierte Modell von Cassie und Baxter und beinhaltet, dass hydrophile Flächen, die durch mechanischen Abrieb freigelegt werden, nicht zu einem Verlust der Superhydrophobizität führen müssen, wie allgemein angenommen.rnBenetzung kann auch durch eine räumliche Beschränkung von Flüssigkeiten kontrolliert werden, z.B. in mikrofluidischen Systemen. Hier wird eine modifizierte Stöber-Synthese verwendet, um künstliche und natürliche Faser-Template mit einer Silika-Schicht zu ummanteln. Nach der thermischen Zersetzung des organischen Templat-Materials entstehen wohldefinierte Silika-Kanäle und Kanalkreuzungen mit gleichmäßigen Durchmessern im Nano- und Mikrometerbereich. Auf Grund ihrer Transparenz, mechanischen Stabilität und des großen Länge-zu-Durchmesser-Verhältnisses sind die Kanäle sehr gut geeignet, um die Füllgeschwindigkeiten von Flüssigkeiten mit variierenden Oberflächenspannungen und Viskositäten zu untersuchen. Konfokale Mikroskopie ermöglicht es hierbei, die Füllgeschwindigkeiten über eine Länge von mehreren Millimetern, sowie direkt am Kanaleingang zu messen. Das späte Füllstadium kann sehr gut mit der Lucas-Washburn-Gleichung beschrieben werden. Die anfänglichen Füllgeschwindigkeiten sind jedoch niedriger als theoretisch vorhergesagt. Wohingegen die vorhergehenden Abschnitte dieser Arbeit sich mit der quasistatischen Benetzung beschäftigen, spielt hier die Dynamik der Benetzung eine wichtige Rolle. Tatsächlich lassen sich die beobachteten Abweichungen durch einen geschwindigkeitsabhängigen Fortschreitkontaktwinkel erklären und durch dynamische Benetzungstheorien modellieren. Somit löst diese Arbeit das seit langem diskutierte Problem der Abweichungen von der Lucas-Washburn-Gleichung bei kleinen Füllgeschwindigkeiten.

Mechanisms of secondary dispersions separation in particulate beds

The mechanisms by which drops of secondary liquid dispersion ie. <100μ m, are collected, coalesced and transferred have been studied in particulate beds of different sizes and heights of glass ballotini. The apparatus facilitated different coalescer cell arrangements. The liquid-liquid system was toluene/de-ionised water. The inlet drop size distribution was measured by microscopy and using the Malvern Particle Size analyser; the outlet dispersion was sized by photography. The effect of packed height and packing size upon critical velocity, pressure drop and coalescence efficiency have been investigated. Single and two phase flow pressure drops across the packing were correlated by modified Blake-Kozeny equations. Two phase pressure drop was correlated by two equations, one for large ballotini sizes (267μm - 367μm), the other for small ballotini sizes (93μm- 147.5μm). The packings were efficient coalescers up to critical velocities of 3 x 10-2 m/s to 5 x 10-2 m/s. The saturation was measured across the bed using relative permeability and a mathematical model developed which related this profile to measured pressure drops. Filter coefficients for the range of packing studied were found to be accurately predicted from a modified queueing drop model. 

Evolution of stress deficit and changing rates of seismicity in cellular automaton models of earthquake faults

We investigate the internal dynamics of two cellular automaton models with heterogeneous strength fields and differing nearest neighbour laws. One model is a crack-like automaton, transferring ail stress from a rupture zone to the surroundings. The other automaton is a partial stress drop automaton, transferring only a fraction of the stress within a rupture zone to the surroundings. To study evolution of stress, the mean spectral density. f(k(r)) of a stress deficit held is: examined prior to, and immediately following ruptures in both models. Both models display a power-law relationship between f(k(r)) and spatial wavenumber (k(r)) of the form f(k(r)) similar tok(r)(-beta). In the crack model, the evolution of stress deficit is consistent with cyclic approach to, and retreat from a critical state in which large events occur. The approach to criticality is driven by tectonic loading. Short-range stress transfer in the model does not affect the approach to criticality of broad regions in the model. The evolution of stress deficit in the partial stress drop model is consistent with small fluctuations about a mean state of high stress, behaviour indicative of a self-organised critical system. Despite statistics similar to natural earthquakes these simplified models lack a physical basis. physically motivated models of earthquakes also display dynamical complexity similar to that of a critical point system. Studies of dynamical complexity in physical models of earthquakes may lead to advancement towards a physical theory for earthquakes.

Modeling of columnar-to-equiaxed transition in solidified Al-Si alloys

A Cellular-Automaton Finite-Volume-Method (CAFVM) algorithm has been developed, coupling with macroscopic model for heat transfer calculation and microscopic models for nucleation and growth. The solution equations have been solved to determine the time-dependent constitutional undercooling and interface retardation during solidification. The constitutional undercooling is then coupled into the CAFVM algorithm to investigate both the effects of thermal and constitutional undercooling on columnar growth and crystal selection in the columnar zone, and formation of equiaxed crystals in the bulk liquid. The model cannot only simulate microstructures of alloys but also investigates nucleation mechanisms and growth kinetics of alloys solidified with various solute concentrations and solidification morphologies.

Computational evaluation of hydraulic system behaviour with entrapped air under rapid pressurization

The pressurization of hydraulic systems containing entrapped air is considered a critical condition for the infrastructure's security due to transient pressure variations often occurred. The objective of the present study is the computational evaluation of trends observed in variation of maximum surge pressure resulting from rapid pressurizations. The comparison of the results with those obtained in previous studies is also undertaken. A brief state of art in this domain is presented. This research work is applied to an experimental system having entrapped air in the top of a vertical pipe section. The evaluation is developed through the elastic model based on the method of characteristics, considering a moving liquid boundary, with the results being compared with those achieved with the rigid liquid column model.

Computational evaluation of hydraulic system behaviour with entrapped air under rapid pressurization

The pressurization of hydraulic systems containing entrapped air is considered a critical condition for the infrastructure's security due to transient pressure variations often occurred. The objective of the present study is the computational evaluation of trends observed in variation of maximum surge pressure resulting from rapid pressurizations. The comparison of the results with those obtained in previous studies is also undertaken. A brief state of art in this domain is presented. This research work is applied to an experimental system having entrapped air in the top of a vertical pipe section. The evaluation is developed through the elastic model based on the method of characteristics, considering a moving liquid boundary, with the results being compared with those achieved with the rigid liquid column model.

Pinning of quantized vortices in helium drops by dopant atoms and molecules

Using a density functional method, we investigate the properties of liquid 4He droplets doped with atoms (Ne and Xe) and molecules ( SF6 and hydrogen cyanide). We consider the case of droplets having a quantized vortex pinned to the dopant. A liquid-drop formula is proposed that accurately describes the total energy of the complex and allows one to extrapolate the density functional results to large N. For a given impurity, we find that the formation of a dopant+vortex+4HeN complex is energetically favored below a critical size Ncr. Our results support the possibility to observe quantized vortices in helium droplets by means of spectroscopic techniques.

Microscopic-macroscopic approach for binding energies with the Wigner-Kirkwood method

The semiclassical Wigner-Kirkwood ̄h expansion method is used to calculate shell corrections for spherical and deformed nuclei. The expansion is carried out up to fourth order in ̄h. A systematic study of Wigner-Kirkwood averaged energies is presented as a function of the deformation degrees of freedom. The shell corrections, along with the pairing energies obtained by using the Lipkin-Nogami scheme, are used in the microscopic-macroscopic approach to calculate binding energies. The macroscopic part is obtained from a liquid drop formula with six adjustable parameters. Considering a set of 367 spherical nuclei, the liquid drop parameters are adjusted to reproduce the experimental binding energies, which yields a root mean square (rms) deviation of 630 keV. It is shown that the proposed approach is indeed promising for the prediction of nuclear masses.

Estudo da adsorção de brometo de etídeo em resina XAD-7

The adsorption of ethidium bromide on XAD-7 resin was studied. The Freundlich model was the most representative isotherm model to describe the sorption behavior. A solid-liquid equilibrium model was proposed to explain the resin mass influence on the sorption. The equilibrium constant value estimated was 2.31. The results showed an ethidium bromide ion-pair physical adsorption, with adsorption enthalpy equals to -19.33 kJ/mol. A pK2 value equals to 4.69 ± 0.01 was estimated by two distinct methods. The results will be applied to the ethidium bromide preconcentration aiming its decomposition.

O amor em tempos de internet: as expectativas amorosas na rede social Badoo

This research aims to examine the phenomenon of sexual relations by observing the Social Network Badoo. As a means to achieve this objective, qualitative in-depth interviews were conducted online. The main question is to understand how the amorous expectations in the liquid modernity are configured. Added to that, there is as analysis categories the insight about relationships and the love experiences provided by the use of the Social Network Badoo. There are three initial hypotheses: 1) a time of transition is experienced, in which the liquid love in the proposed terms by Bauman (2004) was gaining ground and, as consequence, the relationships would be presenting themselves shorter, more open and with another interactive proposals for the relations. 2) The consuming practices of the liquid modernity can interpellate the relational practices molding them according to your logic. 3) It is assumed that the reasoning, inherent to the market, of the use followed by the disposal settles itself in the social behavior and this practice is accentuated by technology, through the use of the internet for the establishment of romantic relationships.the empirical analysis shows that both the vision on relationships as the amorous expectations in liquid modernity have as references the model of solid loving relationship, inherent to the traditional modernity. However it also demonstrates that the romantic experiences and practices refer to the liquid relationship model. Therefore, from these statements it is argued that there is in liquid modernity the cohabitation of the liquid and solid models of romantic relationships. In summary, this research aims to understand the contemporary love relationships across the spectrum of relationships that develop on the Internet Social Network: Badoo

Flow cell within an LED: a proposal for an optical absorption detector

Droplets formed at the tip of a tube under the same conditions possess extreme uniformity of form, volume and weight. These properties of liquid drop formation have been known for a long time and consequently many applications for the drop have been found in instrumentation and chemical analysis methods. In the present paper, we report on the analytical use of a dynamic LED-based flow-through optical absorption detector with optical path length controlled by continuous dropping of a solution. This arrangement consists of a flow cell built within a high-intensity red LED (lambda (max)=630 nm). The feasibility of the detector is demonstrated by colorimetric determination of methylene blue, and ammonium by Berthelot's reaction, in a flow-injection system. For ammonium, the reaction forms a blue dye (indophenol) with a maximum absorption at 630-650 nm. The detection limit, considered as 3 times the signal of the blank, is better than 125 mu g l(-1). The small flow cell represents a good combination of optical path length, low volume and fast washout. This detector can be used advantageously in automated methods and can represent a solution to problems of optical detection involving gas bubbles and precipitation of particles in turbidimetric applications.

Optical, mechanical and surface properties of amorphous carbonaceous thin films obtained by plasma enhanced chemical vapor deposition and plasma immersion ion implantation and deposition

Diverse amorphous hydrogenated carbon-based films (a-C:H, a-C:H:F, a-C:H:N, a-C:H:Cl and a-C:H:Si:O) were obtained by radiofrequency plasma enhanced chemical vapor deposition (PECVD) and plasma immersion ion implantation and deposition (PIIID). The same precursors were used in the production of each pair of each type of film, such as a-C:H, using both PECVD and PIIID. Optical properties, namely the refractive index, n, absorption coefficient, α, and optical gap, ETauc, of these films were obtained via transmission spectra in the ultraviolet-visible near-infrared range (wavelengths from 300 to 3300 nm). Film hardness, elastic modulus and stiffness were obtained as a function of depth using nano-indentation. Surface energy values were calculated from liquid drop contact angle data. Film roughness and morphology were assessed using atomic force microscopy (AFM). The PIIID films were usually thinner and possessed higher refractive indices than the PECVD films. Determined refractive indices are consistent with literature values for similar types of films. Values of ETauc were increased in the PIIID films compared to the PECVD films. An exception was the a-C:H:Si:O films, for which that obtained by PIIID was thicker and exhibited a decreased ETauc. The mechanical properties - hardness, elastic modulus and stiffness - of films produced by PECVD and PIIID generally present small differences. An interesting effect is the increase in the hardness of a-C:H:Cl films from 1.0 to 3.0 GPa when ion implantation is employed. Surface energy correlates well with surface roughness. The implanted films are usually smoother than those obtained by PECVD. ©2013 Elsevier B.V. All rights reserved.

Modeling of diesel particulate filter filtration and regeneration for transient driving schedules

Due to their high thermal efficiency, diesel engines have excellent fuel economy and have been widely used as a power source for many vehicles. Diesel engines emit less greenhouse gases (carbon dioxide) compared with gasoline engines. However, diesel engines emit large amounts of particulate matter (PM) which can imperil human health. The best way to reduce the particulate matter is by using the Diesel Particulate Filter (DPF) system which consists of a wall-flow monolith which can trap particulates, and the DPF can be periodically regenerated to remove the collected particulates. The estimation of the PM mass accumulated in the DPF and total pressure drop across the filter are very important in order to determine when to carry out the active regeneration for the DPF. In this project, by developing a filtration model and a pressure drop model, we can estimate the PM mass and the total pressure drop, then, these two models can be linked with a regeneration model which has been developed previously to predict when to regenerate the filter. There results of this project were: 1 Reproduce a filtration model and simulate the processes of filtration. By studying the deep bed filtration and cake filtration, stages and quantity of mass accumulated in the DPF can be estimated. It was found that the filtration efficiency increases faster during the deep-bed filtration than that during the cake filtration. A “unit collector” theory was used in our filtration model which can explain the mechanism of the filtration very well. 2 Perform a parametric study on the pressure drop model for changes in engine exhaust flow rate, deposit layer thickness, and inlet temperature. It was found that there are five primary variables impacting the pressure drop in the DPF which are temperature gradient along the channel, deposit layer thickness, deposit layer permeability, wall thickness, and wall permeability. 3 Link the filtration model and the pressure drop model with the regeneration model to determine the time to carry out the regeneration of the DPF. It was found that the regeneration should be initiated when the cake layer is at a certain thickness, since a cake layer with either too big or too small an amount of particulates will need more thermal energy to reach a higher regeneration efficiency. 4 Formulate diesel particulate trap regeneration strategies for real world driving conditions to find out the best desirable conditions for DPF regeneration. It was found that the regeneration should be initiated when the vehicle’s speed is high and during which there should not be any stops from the vehicle. Moreover, the regeneration duration is about 120 seconds and the inlet temperature for the regeneration is 710K.