Atmospheric pressure photoionization mass spectrometry as a tool for the investigation of the hydrolysis reaction mechanisms of phosphite antioxidants

The hydrolysis reaction mechanism of phosphite antioxidants is investigated by liquid chromatography-mass spectrometry (LC/MS). The phosphites were chosen because they differed in chemical structure and phosphorus content. Dopant assisted-atmospheric pressure photoionization (DA-APPI) is chosen as the ion source for (lie ionization of the compounds. [it our previous work, DA-APPI was shown to offer an attractive alternative to atmospheric pressure chemical ionization (APCI) since it provided background-ion free mass spectra and higher sensitivity [M. Papanastasiou, et al., Polymer Degradation and Stability 91 (11) (2006) 2675-2682]. In positive ion mode, the molecules are generally detected in their protonated form. In negative ion mode, the phosphites are unstable and only fragment ions are observed: these however, are characteristic of each phosphite and may be used for the identification of the analytes in complex mixtures. The analytes under investigation are exposed to accelerated humid ageing conditions and their hydrolytic pathway and stability is investigated. Different substituents around the phosphorus atom are shown to have a significant effect on the stability of the phosphites, with phenol substituents producing very hydrolytically stable structures. Alkanox P24 and PEP-36 follow a similar hydrolytic pathway via the scission of the first and then the second P-O-phenol bonds, eventually leading to the formation of phenol, Phosphorous acid and pentaerythritol as end products. HP-10 exhibits a rather different Structure and the products detected suggest scission of either the P-O-hydrocarbon or one of the P-O-phenol bonds. A phenomenon similar to that of autocatalysis is observed for all phosphites and is attributed to the formation of dialkyl phosphites as intermediate products. (C) 2008 Elsevier B.V. All rights reserved.

Parameterization Of Turbulence Models Using 3DVAR Data Assimilation

In this research the 3DVAR data assimilation scheme is implemented in the numerical model DIVAST in order to optimize the performance of the numerical model by selecting an appropriate turbulence scheme and tuning its parameters. Two turbulence closure schemes: the Prandtl mixing length model and the two-equation k-ε model were incorporated into DIVAST and examined with respect to their universality of application, complexity of solutions, computational efficiency and numerical stability. A square harbour with one symmetrical entrance subject to tide-induced flows was selected to investigate the structure of turbulent flows. The experimental part of the research was conducted in a tidal basin. A significant advantage of such laboratory experiment is a fully controlled environment where domain setup and forcing are user-defined. The research shows that the Prandtl mixing length model and the two-equation k-ε model, with default parameterization predefined according to literature recommendations, overestimate eddy viscosity which in turn results in a significant underestimation of velocity magnitudes in the harbour. The data assimilation of the model-predicted velocity and laboratory observations significantly improves model predictions for both turbulence models by adjusting modelled flows in the harbour to match de-errored observations. 3DVAR allows also to identify and quantify shortcomings of the numerical model. Such comprehensive analysis gives an optimal solution based on which numerical model parameters can be estimated. The process of turbulence model optimization by reparameterization and tuning towards optimal state led to new constants that may be potentially applied to complex turbulent flows, such as rapidly developing flows or recirculating flows.

Temperature Dynamics Investigation At Small And Shallow Lakes Using Hydrodynamic Model

A three-dimensional time-dependent hydrodynamic and heat transport model of Lake Binaba, a shallow and small dam reservoir in Ghana, emphasizing the simulation of dynamics and thermal structure has been developed. Most numerical studies of temperature dynamics in reservoirs are based on one- or two-dimensional models. These models are not applicable for reservoirs characterized with complex flow pattern and unsteady heat exchange between the atmosphere and water surface. Continuity, momentum and temperature transport equations have been solved. Proper assignment of boundary conditions, especially surface heat fluxes, has been found crucial in simulating the lake’s hydrothermal dynamics. This model is based on the Reynolds Average Navier-Stokes equations, using a Boussinesq approach, with a standard k − ε turbulence closure to solve the flow field. The thermal model includes a heat source term, which takes into account the short wave radiation and also heat convection at the free surface, which is function of air temperatures, wind velocity and stability conditions of atmospheric boundary layer over the water surface. The governing equations of the model have been solved by OpenFOAM; an open source, freely available CFD toolbox. As its core, OpenFOAM has a set of efficient C++ modules that are used to build solvers. It uses collocated, polyhedral numerics that can be applied on unstructured meshes and can be easily extended to run in parallel. A new solver has been developed to solve the hydrothermal model of lake. The simulated temperature was compared against a 15 days field data set. Simulated and measured temperature profiles in the probe locations show reasonable agreement. The model might be able to compute total heat storage of water bodies to estimate evaporation from water surface.

Supply chain turbulence: the impact of a mid-range event in multi-tier, multi-dimension supply chains

Nota: A autora agradece à Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP) pela concessão de bolsa de estudos para o desenvolvimento deste projeto de pesquisa.

De touch: extending service channels in an airport through touch technologies

This project aimed to create a communication and interaction channel between Madeira Airport and its passengers. We used the pre-existent touch enabled screens at the terminal since their potential was not being utilised to their full capacity. To achieve our goal, we have followed an agile strategy to create a testable prototype and take advantages of its results. The developed prototype is based on a plugin architecture turning it into a maintainable and highly customisable system. The collected usage data suggests that we have achieved the initially defined goals. There is no doubt that this new interaction channel is an improvement regarding the provided services and, supported by the usage data, there is an opportunity to explore additional developments to the channel.

Retrievals of a size parameter for phytoplankton and spectral light absorption by colored detrital matter from water-leaving radiances at SeaWiFS channels in a continental shelf region off Brazil

Many efforts are currently oriented toward extracting more information from ocean color than the chlorophyll a concentration. Among biological parameters potentially accessible from space, estimates of phytoplankton cell size and light absorption by colored detrital matter (CDM) would lead to an indirect assessment of major components of the organic carbon pool in the ocean, which would benefit oceanic carbon budget models. We present here 2 procedures to retrieve simultaneously from ocean color measurements in a limited number of bands, magnitudes, and spectral shapes for both light absorption by CDM and phytoplankton, along with a size parameter for phytoplankton. The performance of the 2 procedures was evaluated using different data sets that correspond to increasing uncertainties: ( 1) measured absorption coefficients of phytoplankton, particulate detritus, and colored dissolved organic matter ( CDOM) and measured chlorophyll a concentrations and ( 2) SeaWiFS upwelling radiance measurements and chlorophyll a concentrations estimated from global algorithms. In situ data were acquired during 3 cruises, differing by their relative proportions in CDM and phytoplankton, over a continental shelf off Brazil. No local information was introduced in either procedure, to make them more generally applicable. Over the study area, the absorption coefficient of CDM at 443 nm was retrieved from SeaWiFS radiances with a relative root mean square error (RMSE) of 33%, and phytoplankton light absorption coefficients in SeaWiFS bands ( from 412 to 510 nm) were retrieved with RMSEs between 28% and 33%. These results are comparable to or better than those obtained by 3 published models. In addition, a size parameter of phytoplankton and the spectral slope of CDM absorption were retrieved with RMSEs of 17% and 22%, respectively. If these methods are applied at a regional scale, the performances could be substantially improved by locally tuning some empirical relationships.

Observational Characterization of the Downward Atmospheric Longwave Radiation at the Surface in the City of São Paulo

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Atmospheric Models Applied to DGPS and RTK Network in Brazil: Preliminary Results

Several positioning techniques have been developed to explore the GPS capability to provide precise coordinates in real time. However, a significant problem to all techniques is the ionosphere effect and the troposphere refraction. Recent researches in Brazil, at São Paulo State University (UNESP), have been trying to tackle these problems. In relation to the ionosphere effects it has been developed a model named Mod_Ion. Concerning tropospheric refraction, a model of Numerical Weather Prediction(NWP) has been used to compute the zenithal tropospheric delay (ZTD). These two models have been integrated with two positioning methods: DGPS (Differential GPS) and network RTK (Real Time Kinematic). These two positioning techniques are being investigated at São Paulo State University (UNESP), Brazil. The in-house DGPS software was already finalized and has provided very good results. The network RTK software is still under development. Therefore, only preliminary results from this method using the VRS (Virtual Reference Station) concept are presented.

GPS/VRS positioning using atmospheric modeling

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Artificial neural networks applied in study of atmospheric parameters to high voltage substations concerning lightning

This gaper demonstrates that artificial neural networks can be used effectively for estimation of parameters related to study of atmospheric conditions to high voltage substations design. Specifically, the neural networks are used to compute the variation of electrical field intensity and critical disruptive voltage in substations taking into account several atmospheric factors, such as pressure, temperature, humidity, so on. Examples of simulation of tests are presented to validate the proposed approach. The results that were obtained by experimental evidences and numerical simulations allowed the verification of the influence of the atmospheric conditions on design of substations concerning lightning.

Treatment of PET and PU polymers by atmospheric pressure plasma generated in dielectric barrier discharge in air

Plasma treatments are frequently employed to modify surface properties of materials such as adhesivity, hydrophobicity, oleophobicity etc. Present work deals with surface modification of common commercial polymers such as polyethylene terephthalate (PET) and polyurethane (PU) by an air dielectric barrier discharge (DBD) at atmospheric pressure. The DBD treatment was performed in a plain reactor in wire-duct geometry (non-uniform field reactor), which was driven by a 60 Hz power supply. Material characterization was carried out by water contact angle measurements, atomic force microscopy (AFM) and X-ray photoelectron spectroscopy (XPS). The plasma-induced modifications are associated with incorporation of polar oxygen and nitrogen containing groups on the polymer surface. The AFM analysis reveals that the plasma treatment roughens the material surface. Due to these structural and morphological changes the surface of DBD-treated polymers becomes more hydrophilic resulting in enhanced adhesion properties. (C) 2010 Elsevier B.V. All rights reserved.

Surface modification of siloxane containing polyurethane polymer by dielectric barrier discharge at atmospheric pressure

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Modification of polyethylene terephthalate by atmospheric pressure dielectric barrier discharge (DBD) in view of improving the polymer wetting properties

Surface treatment of polymers by discharge plasmas has increasingly found industrial applications due to its capability of modifying uniformly the surface without changing the material bulk properties. This work deals with surface modification of polyethylene terephthalate (PET) by a dielectric barrier discharge (DBD) at atmospheric pressure. The treatments were conducted in air, nitrogen or argon plasma. The polymer surface was characterized by contact angle measurement, X-ray photoelectron spectroscopy (XPS) and atomic force microscopy (AFM). The results show that the plasma treatment introduces oxygen-and nitrogen-related polar groups on the polymer surface and promotes the surface roughening. Both plasma-induced surface modifications contribute to the enhancement of the polymer wettability.

Biased Atmospheric, Sub-Atmospheric, and Low-Pressure Air Plasmas for Material Surface Improvements

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Surface Modification of Polycarbonate by Atmospheric-Pressure Plasma Jets

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)