Control by ATR-FTIR of surface treatment of cork stoppers and its effect on their mechanical performance

Fourier transform infrared (FTIR) spectroscopy was applied to determine the type of surface treatment and dose used on cork stoppers and to predict the friction between stopper and bottleneck. Agglomerated cork stoppers were finished with two different doses and using two surface treatments: P (paraffin and silicone), 15 and 25 mg/stopper, and S (only silicone), 10 and 15 mg/stopper. FTIR spectra were recorded at five points for each stopper by attenuated total reflectance (ATR). Absorbances at 1,010, 2,916, and 2,963 cm -1 were obtained in each spectrum. Discriminant analysis techniques allowed the treatment, and dose applied to each stopper to be identified from the absorbance values. 91.2% success rates were obtained from individual values and 96.0% from the mean values of each stopper. Spectrometric data also allowed treatment homogeneity to be determined on the stopper surface, and a multiple regression model was used to predict the friction index (If = Fe/Fc) (R 2 = 0.93)

Diseño preliminar térmico y estructural del instrumento NOMAD de ExoMars

El vehículo espacial ExoMarsOrbiter, llamado Exomars Trace Gas Orbiter (EMTGO), se encuadra en una misión de la ESA/NASA, contribuyendo a las ambiciones europeas de misiones de exploración futura, según lo establecido en la declaración Aurora. Los objetivos del programa ExoMars dan continuidad a los esfuerzos de cooperación con la NASA para enviar una misión de retorno de una muestra de Marte en las siguientes décadas. Están prevista s dos misiones dentro del programa ExoMars, una para 2016 y otra para 2018. NOMAD (solar occultation in the infra red and Nadir and Occultation for MArs Discovery) es un espectrómetro de alta resolución en el infrarrojo - visible - ultravioleta, observando en las franjas de 0.2 - 0.65 y 2.3 - 4.2 μm, para la inspección de la atmósfera de Marte. Dispone de tres canales (LNO, SO y UVIS) que operarán según tres modos distintos (ocultación solar, limbo y nadir). NOMAD es un instrumento con una masa de 29.9 kg que está montado sobre la bandeja superior exterior, en la cara fría del vehículo, y debe estar fuertemente desacoplado del mismo desde un punto de vista térmico (con una conductancia total máxima de 0.02 W/K). Este desacoplamiento dificulta el diseño estructural de la unión con el vehículo. El diseño térmico debe estar capacitado además para evacuar el calor disipado internamente y las cargas exteriores, utilizando únicamente métodos de control térmico pasivos. Un requisito térmico adicional es el que impone e l espectrómetro del canal LNO, que es una caja interior a NOMAD que debe ser enfriada a - 100º C. Con el objeto de cumplir estos requisitos, se disponen dos radiadores: un radiador ‘general’ para mantener al conjunto del instrumento a una temperatura semejante a la ambiente terrestre, y un radiador multietapa en “V” para enfriar la sección del LNO a - 100º C. Éste último consiste en 4 etapas con placas delgadas, que disponen de una combinación de regiones de alta emisividad y otras de alta reflectividad, para evacuar el calor entre etapas. Además, se ha de alcanzar un compromiso entre la rigidez del radiador y la masa del mismo para disminuir la masa del radiador, las placas delgadas deben ser rigidizadas estructuralmente. Tanto su diseño térmico como el estructural representan un reto tecnológico, debido a su escasa presencia en misiones anteriores. El modelo geométrico y los modelos matemáticos térmico s y estructural es se han construido siguiendo los estándares de la ESA. Esto es, la metodología utilizada ha sido la de efectuar primero un diseño conceptual preliminar, para posteriormente desarrollar un modelo térmico y otro estructural a nivel instrumento, con el software ESATAN y NASTRAN, ambos indicados por la ESA. Los resultados muestran la viabilidad de NOMAD desde un punto de vista térmico y estructural.

Intermediate Band to Conduction Band optical absorption in ZnTe:O

ZnTe doped with high concentrations of oxygen has been proposed in previous works as intermediate band (IB) material for photovoltaic applications. The existence of extra optical transitions related to the presence of an IB has already been demonstrated in this material and it has been possible to measure the absorption coefficient of the transitions from the valence band (VB) to the IB. In this work we present the first measurement of the absorption coefficient associated to transitions from the IB to the conduction band (CB) in ZnTe:O. The samples used are 4 ?m thick ZnTe layers with or without O in a concentration ~ 1019 cm-3, which have been grown on semi-insulating GaAs substrates by molecular beam epitaxy (MBE). The IB-CB absorption coefficient peaks for photon energies ~ 0.4 eV. It is extracted from reflectance and transmittance spectra measured using Fourier Transform Infrared (FTIR) spectroscopy. Under typical FTIR measurement conditions (low light intensity, broadband spectrum) the absorption coefficient in IB-to-CB transitions reaches 700 cm-1. This is much weaker than the one observed for VB-IB absorption. This result is consistent with the fact that the IB is expected to be nearly empty of electrons under equilibrium conditions in ZnTe(:O). The absorption for VB to IB transitions is also observed in the same samples through reflectance measurements performed in the visible range using a monochromator. These measurements are compared with the quantum efficiency (QE) from solar cells fabricated under similar conditions.

Intermediate band to conduction band optical absorption in ZnTeO

ZnTe doped with high concentrations of oxygen has been proposed in previous works as an intermediate band (IB) material for photovoltaic applications. The existence of extra optical transitions related to the presence of an IB has already been demonstrated in this material and it has been possible to measure the absorption coefficient of the transitions from the valence band (VB) to the IB. In this study, we present the first measurement of the absorption coefficient associated with transitions from the IB to the conduction band (CB) in ZnTeO. The samples used are 4-mum-thick ZnTe layers with or without O in a concentration ~10 19 cm -3, which have been grown on semiinsulating GaAs substrates by molecular beam epitaxy (MBE). The IB-CB absorption coefficient peaks for photon energies ~0.4 eV. It is extracted from reflectance and transmittance spectra measured using Fourier transform infrared (FTIR) spectroscopy. Under typical FTIR measurement conditions (low light intensity, broadband spectrum), the absorption coefficient in IB-to-CB transitions reaches 700 cm -1. This is much weaker than the one observed for VB-IB absorption. This result is consistent with the fact that the IB is expected to be nearly empty of electrons under equilibrium conditions in ZnTe(O).

Al Este del Retiro

La zona de Madrid al Este del Retiro ha estado indefectiblemente condicionada en su tardío desarrollo urbano por su posición a espaldas del Real Sitio. La construcción hacia 1640 de las tapias que rodeaban los reales jardines transformó la red de caminos que partían hacia oriente, aisló los terrenos ubicados más al Este de la ciudad, con la que ya sólo se podrían comunicar por las carreteras de Aragón y Valencia, y condenó las expectativas de desarrollo urbano reduciendo los precios de las propiedades, lo cual determinó durante décadas los usos y la arquitectura de la zona. El Anteproyecto de Ensanche de Carlos María de Castro constituye el germen a partir del cual, durante un lento proceso de casi cien años, fue configurándose la ciudad que hoy conocemos. La identificación en el Archivo de Villa del primer plano general del Ensanche trazado por Castro, del cual anteriores trabajos advirtieron de su existencia aunque se desconocía su localización, es la principal aportación de esta investigación. Por un lado, este primer plano general del Ensanche manuscrito es, por sí mismo, un documento de indudable importancia en la historia del urbanismo madrileño. En segundo lugar, el análisis de su contenido arroja nueva luz sobre la propuesta original de Castro, parcialmente censurada por la Dirección General de Obras Públicas antes de la aprobación del plan en 1860. Especialmente en lo referente a la zona de Madrid al Este del Retiro, proyectada como barrio obrero del Ensanche, este documento ha aportado un enfoque desconocido hasta ahora sobre el paisaje urbano concebido por Castro para la más ambiciosa propuesta planteada en mucho tiempo al problema de la vivienda obrera. Finalmente, el análisis de la factura del plano revela la superposición de varias capas de dibujo, evidenciando que durante un tiempo fue un documento vivo, utilizado como plano de trabajo por el equipo de Castro durante aproximadamente diez años, hasta la destitución del ingeniero en 1868. Posteriores análisis del plano sobre otros ámbitos de la ciudad arrojarán sin duda nuevos datos sobre el proceso proyectual del conjunto del Ensanche. Pero la dinámica de lo real, sintetizable en múltiples factores de índole social, económica y legislativa, transformó durante las primeras décadas de andadura del Ensanche la ciudad proyectada por Castro al Este del Retiro. El dibujo de la ciudad, entendido como herramienta de análisis y empleado con éxito en trabajos de investigación realizados por otros autores en la misma línea, ha permitido deducir la reconstitución gráfica del estado de la ciudad en diferentes momentos singulares del desarrollo urbanístico de la zona, así como de la propuesta original de barrio obrero de Castro. No hay que olvidar que, a pesar del escaso interés que suscitaba entre los inversores inmobiliarios el ámbito geográfico de estudio de esta tesis, fue objeto, durante casi un siglo, de numerosas propuestas de ordenación y urbanización que, aunque no llegaron a materializarse, fueron configurando una suerte de desarrollo virtual de la ciudad paralelo al devenir de la realidad. De esta forma, el dibujo se constituye en esta tesis como fuente de información, herramienta de pensamiento y resultado de la investigación en sí mismo, ilustrando y contribuyendo al mejor conocimiento de la forma urbana. ABSTRACT The area of Madrid to the East of the Retiro has been inevitably conditioned in its late urban development by its position behind the Royal Site. The construction of the walls surrounding the royal gardens around 1640 transformed the network of roads departing eastward, isolated land located to the East of the city, with which already only could communicate by roads of Aragon and Valencia, condemned the expectations of urban development by reducing the prices of the properties, and determined for decades uses and architecture of the area. The Carlos María de Castro preliminary design of City Expansion is the germ from which, during a slow process of almost one hundred years, the city which we know today was setting up. The discovery in the City Archive of the City Expansion first drawing traced by Castro, which previous investigations warned of its existence although its location was unknown, is the main contribution of this research. Firstly, this hand drawn general plan of the city expansion is by itself a document of undoubted importance in the history of Madrid urbanism. Secondly, the analysis of its content sheds new light on Castro´s original proposal, partially censored by the Dirección General de Obras Públicas before the approval of the plan in 1860. Especially concerning the area of Madrid to the East of the Retiro, projected as a workingclass district of the City Expansion, this document has provided an unknown up to now approach on the urban landscape designed by Castro for the more ambitious proposal put forward in a long time to the problem of worker housing. Finally, analysis of hand drawn plan reveals the superposition of several layers of drawing, demonstrating that for a time it was a living document, used as a work plan by the Castro team for approximately ten years, until the dismissal of the engineer in 1868. Subsequent analysis of the drawing on other areas of the city will have no doubt new data on the design process of the whole City Expansion. But the dynamics of reality, synthesizable on multiple factors in social, economic and legislative, transformed during the first decades of existence of the City Expansion designed by Castro to the East of the Retiro. Drawing of the city, understood as a tool of analysis and used successfully in research works done by other authors on the same line, has allowed to deduct graphic reconstitution of the city status in different and singular moments in the urban development of the area, as well as the original Castro´s proposal of working-class district. It should not be forgotten that, despite the lack of interest which raised among investors the geographic scope of this thesis study, it was the object, for nearly a century, of numerous proposals for urbanization which, although they didn´t materialize, were setting up a sort of virtual development of the city parallel to the becoming of the reality. In this way, drawing is used in the thesis as a source of information, tool of thought and outcome of the research itself, illustrating and contributing to a better understanding of urban form.

Determination of chromite composition from multispectral reflectance measurements (400-1000 nm)

The relationship between the chemical composition and the multispectral reflectance values of chromite in the VNIR (Visible and Near-Infra-Red) realm is tested and mathematically analysed. Statisticaltools as Pearson's correlation coefficients, linear stepwise regression analysis and least-square adjustments are applied to two populations of data obtained from 14 selected samples 01 chromite multielemental microprobe analysis and multispectral reflectance values (400-1 000 nm). Results show that both data sets correlate, and suggest that the VNIR reflectance spectra can be used as a tool to determine the chemical composition of chromites.

Efficient exchange of the primary quinone acceptor QA in isolated reaction centers of Rhodopseudomonas viridis

A key step in the conversion of solar energy into chemical energy by photosynthetic reaction centers (RCs) occurs at the level of the two quinones, QA and QB, where electron transfer couples to proton transfer. A great deal of our understanding of the mechanisms of these coupled reactions relies on the seminal work of Okamura et al. [Okamura, M. Y., Isaacson, R. A., & Feher, G. (1975) Proc. Natl. Acad. Sci. USA 88, 3491–3495], who were able to extract with detergents the firmly bound ubiquinone QA from the RC of Rhodobacter sphaeroides and reconstitute the site with extraneous quinones. Up to now a comparable protocol was lacking for the RC of Rhodopseudomonas viridis despite the fact that its QA site, which contains 2-methyl-3-nonaprenyl-1,4-naphthoquinone (menaquinone-9), has provided the best x-ray structure available. Fourier transform infrared difference spectroscopy, together with the use of isotopically labeled quinones, can probe the interaction of QA with the RC protein. We establish that a simple incubation procedure of isolated RCs of Rp. viridis with an excess of extraneous quinone allows the menaquinone-9 in the QA site to be almost quantitatively replaced either by vitamin K1, a close analogue of menaquinone-9, or by ubiquinone. To our knowledge, this is the first report of quinone exchange in bacterial photosynthesis. The Fourier transform infrared data on the quinone and semiquinone vibrations show a close similarity in the bonding interactions of vitamin K1 with the protein at the QA site of Rp. viridis and Rb. sphaeroides, whereas for ubiquinone these interactions are significantly different. The results are interpreted in terms of slightly inequivalent quinone–protein interactions by comparison with the crystallographic data available for the QA site of the two RCs.

Emprego do ultra-som modo B e com efeito Doppler, termômetro infravermelho e medidas antropométricas na avaliação de uma formulação cosmética anticelulítica contendo extrato hidroglicólico de Trichilia catigua e Ptychopetalum olacoides Bentham

Hidrolipodistrofia ginóide (H.L.D.G.), a celulite, é comumente tratada com cosméticos contendo extratos vegetais. O estudo realizado foi: ultra-sonografia na avaliação da espessura da hipoderme e a microcirculação cutânea; uso de termômetro infravermelho na medida da temperatura e análise das medidas antropométricas da uma formulação cosmética anticelulítica contendo extrato hidroglicólico de Trichilia catigua e Ptychopetalum olacoides Bentham (catuaba e marapuama). Foram realizadas medidas iniciais e após aplicação da formulação. Os resultados apresentaram alterações estatisticamente significativas para a temperatura cutânea e medidas antropométricas. Não houve diferenças estatisticamente significativas nas medidas da hipoderme e microcirculação. Considerando os resultados, a formulação avaliada possui potencial ação coadjuvante na redução da hidrolipodistrofia ginóide. As técnicas podem ser associadas em conjunto com a avaliação sensorial e apreciabilidade cosmética. Os requisitos chaves para a reprodutibilidade das técnicas incluem ambiente controlado, monitoramento e climatização dos voluntários, procedimentos de medidas padronizados, protocolos de aplicação realístico e operadores qualificados.

Kinetic study of the decompositions involved in the thermal degradation of commercial azodicarbonamide

The transitions and reactions involved in the thermal treatment of several commercial azodicarbonamides (ADC) in an inert atmosphere have been studied by dynamic thermogravimetry analysis (TGA), mass spectrometry and Fourier transform infrared (FTIR) spectroscopy. A pseudo-mechanistic model, involving several competitive and non-competitive reactions, has been suggested and applied to the correlation of the weight loss data. The model applied is capable of accurately representing the different processes involved, and can be of great interest in the understanding and quantification of such phenomena, including the simulation of the instantaneous amount of gases evolved in a foaming process. In addition, a brief discussion on the methodology related to the mathematical modeling of TGA data is presented, taking into account the complex thermal behaviour of the ADC.

Characterization and electrochemical properties of conducting nanocomposites synthesized from p-anisidine and aniline with titanium carbide by chemical oxidative method

A novel polymer/TiC nanocomposites “PPA/TiC, poly(PA-co-ANI)/TiC and PANI/TiC” was successfully synthesized by chemical oxidation polymerization at room temperature using p-anisidine and/or aniline monomers and titanium carbide (TiC) in the presence of hydrochloric acid as a dopant with ammonium persulfate as oxidant. These nanocomposites obtained were characterized by Fourier transform infrared (FTIR) spectroscopy, X-ray diffraction (XRD), transmission electron microscopy (TEM), energy dispersive spectroscopy (EDS), and thermogravimetric analysis (TGA). XRD indicated the presence of interactions between polymers and TiC nanoparticle and the TGA revealed that the TiC nanoparticles improve the thermal stability of the polymers. The electrical conductivity of nanocomposites is in the range of 0.079–0.91 S cm−1. The electrochemical behavior of the polymers extracted from the nanocomposites has been analyzed by cyclic voltammetry. Good electrochemical response has been observed for polymer films; the observed redox processes indicate that the polymerisation on TiC nanoparticles produces electroactive polymers. These nanocomposite microspheres can potentially used in commercial applications as fillers for antistatic and anticorrosion coatings.

Use of space by domestic chicks housed in complex aviaries.

To improve the understanding of the development of locomotor capacity in layer hens, we measured how female laying hen chicks (n=120) of four different strains (LSL-lite, Hyline Brown, Dekalb White, Lohmann Brown; 3 groups of 10 chicks per line) utilized the ground, the air, elevated horizontal (platforms and perches) and inclined surfaces (ramps and ladders) in an aviary until 9 weeks of age. We used infra-red video recordings to perform all-occurrences sampling of locomotive behavioural and perching events that occurred on the ground—where bedding material, food and water were provided, in the air, and on elevated horizontal and inclined surfaces within weekly 30-min sampling periods. Chicks preferred level ground during the first week of life compared to weeks 5–9 (P<0.0001) and performed 52% of all behavioural events in this section. Elevated surface use began at 2 weeks of age and increased over time (P=0.003), where most behaviour was performed in S2 (45% of all events). Chicks preferred horizontal to inclined surfaces, which were used from weeks 2–5 with maximum use occurring during weeks 2 and 3. Lohmann LSL chicks used the space above the ground most frequently (P=0.05) and performed more aerial ascent/descent behaviour than other lines (P<0.0001). Overall activity levels declined with age (P<0.0001). In summary layer chicks almost exclusively locomoted on the ground but utilized elevated horizontal surfaces (perch, first platform) as early as 2 weeks. These results provide information for improving space use in rearing aviaries by introducing lower perches, platforms and ramps/ladders to accommodate age-dependent locomotor abilities.

Assessment of relationships between precipitation and satellite derived vegetation condition in South Australia

The normalised difference vegetation index (NDVI) has evolved as a primary tool for monitoring continental-scale vegetation changes and interpreting the impact of short to long-term climatic events on the biosphere. The objective of this research was to assess the nature of relationships between precipitation and vegetation condition, as measured by the satellite-derived NDVI within South Australia. The correlation, timing and magnitude of the NDVI response to precipitation were examined for different vegetation formations within the State (forest, scrubland, shrubland, woodland and grassland). Results from this study indicate that there are strong relationships between precipitation and NDVI both spatially and temporally within South Australia. Differences in the timing of the NDVI response to precipitation were evident among the five vegetation formations. The most significant relationship between rainfall and NDVI was within the forest formation. Negative correlations between NDVI and precipitation events indicated that vegetation green-up is a result of seasonal patterns in precipitation. Spatial patterns in the average NDVI over the study period closely resembled the boundaries of the five classified vegetation formations within South Australia. Spatial variability within the NDVI data set over the study period differed greatly between and within the vegetation formations examined depending on the location within the state. ACRONYMS AVHRR Advanced Very High Resolution Radiometer ENVSAEnvironments of South Australia EOS Terra-Earth Observing System EVIEnhanced Vegetation Index MODIS Moderate Resolution Imaging Spectro-radiometer MVC Maximum Value Composite NDVINormalised Difference Vegetation Index NIRNear Infra-Red NOAANational Oceanic and Atmospheric Administration SPOT Systeme Pour l’Observation de la Terre. [ABSTRACT FROM AUTHOR]

Immobilization of aluminum chloride on MCM-41 as a new catalyst system for liquid-phase isopropylation of naphthalene

A great deal of effort has been made at searching for alternative catalysts to replace conventional Lewis acid catalyst aluminum trichloride (AlCl3). In this paper, immobilization of AlCl3 on mesoporous MCM-41 silica with and without modification was carried out. The catalytic properties of the immobilized catalyst systems for liquid-phase isopropylation of naphthalene were studied and compared with those of H/MCM-41 and H/mordenite. The structures of the surface-immobilized aluminum chloride catalysts were studied and identified by using solid-state magic angle spinning nuclear magnetic resonance (MAS NMR), Fourier transform infrared (FTIR) spectroscopy, X-ray photoelectron spectroscopy (XPS), nitrogen adsorption, and X-ray diffraction (XRD) techniques. The catalytic activity of the immobilized catalysts was found to be similar to that of acidic mordenite zeolite. A significant enhancement in the selectivity of 2,6-diisopropylnaphthalene (2,6-DIPN) was observed over the immobilized aluminum chloride catalysts. Immobilization of aluminum chloride on mesoporous silica coupled with surface silylation is a promising way of developing alternative catalyst system for liquid-phase Friedel-Crafts alkylation reactions. (C) 2002 Elsevier Science B.V. All rights reserved.

Poly(hydroxyether of phenolphthalein) and its blends with poly(ethylene oxid)

Poly(hydroxyether of phenolphthalein) (PPH) was synthesized through the polycondensation of phenolphthalein with epichlorohydrin. It was characterized by Fourier transform infrared (FTIR) spectroscopy, NMR spectroscopy, and differential scanning calorimetry (DSC). The miscibility of the blends of PPH with poly(ethylene oxide) (PEO) was established on the basis of the thermal analysis results. DSC showed that the PPH/PEO blends prepared via casting from N,N-dimethylformamide possessed single, composition-dependent glass-transition temperatures. Therefore, the blends were miscible in the amorphous state for all compositions. FTIR studies indicated that there were competitive hydrogen-bonding interactions with the addition of PEO to the system, which were involved with (OHO)-O-. . .=C

Synthesis of soluble phosphate polymers by RAFT and their in vitro mineralization

Soluble linear (non-cross-linked) poly(monoacryloxyethyl phosphate) (PMAEP) and poly(2-(methacryloyloxy)ethyl phosphate) (PMOEP) were successfully synthesized through reversible addition-fragmentation chain transfer (RAFT)-mediated polymerization and by keeping the molecular weight below 20 K. Above this molecular weight, insoluble (cross-linked) polymers were observed, postulated to be due to residual diene (cross-linkable) monomers formed during purification of the monomers, MOEP and MAEP. Block copolymers consisting of PMAEP or PMOEP and poly(2-(acetoacetoxy) ethyl methacrylate) (PAAEMA) were successfully prepared and were immobilized on aminated slides. Simulated body fluid studies revealed that calcium phosphate (CaP) minerals formed on both the soluble polymers and the cross-linked gels were very similar. Both the PMAEP polymers and the PMOEP gel showed a CaP layer most probably brushite or monetite based on the Ca/P ratios. A secondary CaP mineral growth with a typical hydroxyapatite (HAP) globular morphology was found on the PMOEP gel. The soluble PMOEP film formed carbonated HAP according to Fourier transform infrared (FTIR) spectroscopy. Block copolymers attached to aminated slides showed only patchy mineralization, possibly due to the ionic interaction of negatively charged phosphate groups and protonated amines.