Structural modifications in stretch-induced crystallization in PVDF films as measured by small-angle X-ray scattering

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

Contribution to active multi-beam reconfigurable antennas for L and S bands

La presente tesis doctoral con título "Contribution to Active Multi-Beam Reconfigurable Antennas for L and S Bands" ha sido desarrollada por el investigador ingeniero de telecomunicación estudiante de doctorado Javier García-Gasco Trujillo en el Grupo de Radiación del Departamento de Señales, Sistemas y Radiocomunicaciones de la ETSI de Telecomunicación de la Universidad Politécnica de Madrid bajo la dirección de los doctores Manuel Sierra Pérez y José Manuel Fernández González. Durante décadas, el desarrollo de antenas de apuntamiento electrónico ha estado limitado al área militar. Su alto coste y su gran complejidad eran los mayores obstáculos que frenaban la introducción de esta tecnología en aplicaciones comerciales de gran escala. La reciente aparición de componentes de estado sólido prácticos, fiables, y de bajo coste ha roto la barrera del coste y ha reducido la complejidad, haciendo que las antenas reconfigurables de apuntamiento electrónico sean una opción viable en un futuro cercano. De esta manera, las antenas phased array podrían llegar a ser la joya de la corona que permitan alcanzar los futuros retos presentes en los sistemas de comunicaciones tanto civiles como militares. Así pues, ahora es el momento de investigar en el desarrollo de antenas de apuntamiento electrónico de bajo coste, donde los nuevos componentes de estado sólido comerciales forman el núcleo duro de la arquitectura. De esta forma, el estudio e implementación de estos arrays de antenas activas de apuntamiento electrónico capaces de controlar la fase y amplitud de las distintas señales implicadas es uno de los grandes retos de nuestro tiempo. Esta tesis se enfrenta a este desafío, proponiendo novedosas redes de apuntamiento electrónico e innovadores módulos de transmisión/recepción (T/R) utilizando componentes de estado sólido de bajo coste, que podrán integrar asequibles antenas activas reconfigurables multihaz en bandas L y S. En la primera parte de la tesis se realiza una descripción del estado del arte de las antenas phased array, incluyendo su base teórica y sus ventajas competitivas. Debido a que las contribuciones obtenidas en la presente tesis han sido realizadas dentro de distintos proyectos de investigación, donde se han manejada antenas de simple/doble polarización circular y simple/doble banda de trabajo, se describen detenidamente los dos proyectos más relevantes de la investigación: el radar de basura espacial de la Agencia Espacial Europea (ESA), Space Situational Awareness (SSA); y la estación base de seguimiento y control de satélites de órbita baja, GEOdesic Dome Array (GEODA). Sin lugar a dudas, los dispositivos desfasadores son uno de los componentes clave en el diseño de antenas phased arrays. Recientemente se ha observado una gran variación en el precio final de estos dispositivos, llegando en ocasiones a límites inasequibles. Así pues, se han propuesto distintas técnicas de conformación de haz alternativas a la utilización de componentes desfasadores comerciales: el desfasador de líneas conmutadas, la red de haz conmutado, y una novedosa red desfasadora divisora/combinadora de potencia. Para mostrar un uso práctico de las mismas, se ha propuesto el uso de las tres alternativas para el caso práctico del subarray de cinco elementos de la celda GEODA-SARAS. Tras dicho estudio se obtiene que la novedosa red desfasadora divisora/combinadora de potencia propuesta es la que mejor relación comportamiento/coste presenta. Para verificar su correcto funcionamiento se construye y mide los dos bloques principales de los que está compuesta la red total, comprobando que en efecto la red responde según lo esperado. La estructura más simple que permite realizar un barrido plano es el array triangular de tres elementos. Se ha realizado el diseño de una nueva red multihaz que es capaz de proporcionar tres haces ortogonales en un ángulo de elevación _0 y un haz adicional en la dirección broadside utilizando el mencionado array triangular de tres elementos como antena. En primer lugar se realizar una breve introducción al estado del arte de las redes clásicas multihaz. Así mismo se comentan innovadores diseños de redes multihaz sin pérdidas. El estudio da paso a las redes disipativas, de tal forma que se analiza su base matemática y se muestran distintas aplicaciones en arrays triangulares de tres elementos. Finalmente, la novedosa red básica propuesta se presenta, mostrando simulaciones y medidas de la misma para el caso prácticoo de GEODA. También se ha diseñado, construido y medido una red compuesta por dos redes básicas complementarias capaz de proporcionar seis haces cuasi-ortogonales en una dirección _0 con dos haces superpuestos en broadside. La red propuesta queda totalmente validada con la fabricación y medida de estos con prototipos. Las cadenas de RF de los módulos T/R de la nueva antena GEODA-SARAS no son algo trivial. Con el fin de mostrar el desarrollo de una cadena compleja con una gran densidad de componentes de estado sólido, se presenta una descripción detallada de los distintos componentes que integran las cadenas de RF tanto en transmisión como en recepción de la nueva antena GEODA-SARAS. Tras presentar las especificaciones de la antena GEODA-SARA y su diagrama de bloques esquemático se describen los dos bloques principales de las cadenas de RF: la celda de cinco elementos, y el módulo de conversión de panel. De la misma manera también se presentará el módulo de calibración integrado dentro de los dos bloques principales. Para comprobar que el funcionamiento esperado de la placa es el adecuado, se realizará un análisis que tratará entre otros datos: la potencia máxima en la entrada del transmisor (comprobando la saturación de la cadena), señal de recepción mínima y máxima (verificando el rango de sensibilidad requerido), y el factor G/T (cumpliendo la especificación necesaria). Así mismo se mostrará un breve estudio del efecto de la cuantificación de la fase en el conformado de haz de RF. Los estudios muestran que la composición de las cadenas de RF permite el cumplimiento de las especificaciones necesarias. Finalmente la tesis muestra las conclusiones globales del trabajo realizado y las líneas futuras a seguir para continuar con esta línea de investigación. ABSTRACT This PhD thesis named "Contribution to Active Multi-Beam Reconfigurable Antennas for L and S Bands", has been written by the Electrical Engineer MSc. researcher Javier García-Gasco Trujillo in the Grupo de Radiación of the Departamento de Señales, Sistemas y Radiocomunicaciones from the ETSI de Telecomunicación of the Universidad Politécnica de Madrid. For decades, the implementation of electronically steerable phased array antennas was confined to the military area. Their high cost and complexity were the major obstacles to introduce this technology in large scale commercial applications. The recent emergence of new practical, low-cost, and highly reliable solid state devices; breaks the barrier of cost and reduces the complexity, making active phased arrays a viable future option. Thus, phased array antennas could be the crown jewel that allow to meet the future challenges in military and civilian communication systems. Now is time to deploy low-cost phased array antennas, where newly commercial components form the core of the architecture. Therefore, the study and implementation of these novel low-cost and highly efficient solid state phased array blocks capable of controlling signal phase/amplitude accurately is one of the great challenges of our time. This thesis faces this challenge, proposing innovative electronic beam steering networks and transmitter/ receiver (T/R) modules using affordable solid state components, which could integrate fair reconfigurable phased array antennas working in L and S bands. In the first part of the thesis, a description of the state of art of phased array antennas, including their fundamentals and their competitive advantages, is presented. Since thesis contributions have been carried out for different research projects, where antennas with single/double circular polarization and single/double working frequency bands have been examined, frameworks of the two more important projects are detailed: the Space Situational Awareness (SSA) programme from the European Space Agency (ESA), and the GEOdesic Dome Array (GEODA) project from ISDEFE-INSA and the ESA. Undoubtedly, phase shifter devices are one of the key components of phased array antennas. Recent years have witnessed wide fluctuations in commercial phase shifter prices, which sometimes led to unaffordable limit. Several RF steering technique alternatives to the commercial phase shifters are proposed, summarized, and compared: the switched line phase shifter, the switched-beam network, and the novel phase shifter power splitter/combiner network. In order to show a practical use of the three different techniques, the five element GEODA-SARAS subarray is proposed as a real case of study. Finally, a practical study of a newly phase shifter power splitter/combiner network for a subarray of five radiating elements with triangular distribution is shown. Measurements of the two different phase shifter power splitter/combiner prototypes integrating the whole network are also depicted, demonstrating their proper performance. A triangular cell of three radiating elements is the simplest way to obtain a planar scanner. A new multibeam network configuration that provides three orthogonal beams in a desired _0 elevation angle and an extra one in the broadside steering direction for a triangular array of three radiating elements is introduced. Firstly, a short introduction to the state of art of classical multi-beam networks is presented. Lossless network analysis, including original lossless network designs, are also commented. General dissipative network theory as well as applications for array antennas of three radiating elements are depicted. The proposed final basic multi-beam network are simulated, built and measured to the GEODA cell practical case. A combined network that provides six orthogonal beams in a desired _0 elevation angle and a double seventh one in the broadside direction by using two complementary proposed basic networks will be shown. Measurements of the whole system will be also depicted, verifying the expected behavior. GEODA-SARAS T/R module RF chains are not a trivial design. A thorough description of all the components compounding GEODA-SARAS T/R module RF chains is presented. After presenting the general specifications of the GEODA-SARAS antenna and its block diagrams; two main blocks of the RF chains, the five element cell and the panel conversion module, are depicted and analyzed. Calibration module integrated within the two main blocks are also depicted. Signal flow throw the system analyzing critical situations such as maximum transmitted power (testing the chain unsaturation), minimum and maximum receiving signal (verifying sensitivity range), maximum receiver interference signals (assuring a proper reception), and G/T factor (fulfilling the technical specification) are evaluated. Phase quantization error effects are also listed. Finally, the manuscript contains the conclusions drawn of the present research and the future work.

Solid Lipid Nanoparticles For Hydrophilic Biotech Drugs: Optimization And Cell Viability Studies (caco-2 & Hepg-2 Cell Lines).

Insulin was used as model protein to developed innovative Solid Lipid Nanoparticles (SLNs) for the delivery of hydrophilic biotech drugs, with potential use in medicinal chemistry. SLNs were prepared by double emulsion with the purpose of promoting stability and enhancing the protein bioavailability. Softisan(®)100 was selected as solid lipid matrix. The surfactants (Tween(®)80, Span(®)80 and Lipoid(®)S75) and insulin were chosen applying a 2(2) factorial design with triplicate of central point, evaluating the influence of dependents variables as polydispersity index (PI), mean particle size (z-AVE), zeta potential (ZP) and encapsulation efficiency (EE) by factorial design using the ANOVA test. Therefore, thermodynamic stability, polymorphism and matrix crystallinity were checked by Differential Scanning Calorimetry (DSC) and Wide Angle X-ray Diffraction (WAXD), whereas the effect of toxicity of SLNs was check in HepG2 and Caco-2 cells. Results showed a mean particle size (z-AVE) width between 294.6 nm and 627.0 nm, a PI in the range of 0.425-0.750, ZP about -3 mV, and the EE between 38.39% and 81.20%. After tempering the bulk lipid (mimicking the end process of production), the lipid showed amorphous characteristics, with a melting point of ca. 30 °C. The toxicity of SLNs was evaluated in two distinct cell lines (HEPG-2 and Caco-2), showing to be dependent on the concentration of particles in HEPG-2 cells, while no toxicity in was reported in Caco-2 cells. SLNs were stable for 24 h in in vitro human serum albumin (HSA) solution. The resulting SLNs fabricated by double emulsion may provide a promising approach for administration of protein therapeutics and antigens.

SPITZER OBSERVATIONS OF A1763. II. CONSTRAINING THE NATURE OF ACTIVITY IN THE CLUSTER-FEEDING FILAMENT WITH VLA AND XMM-NEWTON DATA

The A1763 superstructure at z = 0.23 contains the first galaxy filament to be directly detected using mid-infrared observations. Our previous work has shown that the frequency of starbursting galaxies, as characterized by 24 mu m emission is much higher within the filament than at either the center of the rich galaxy cluster, or the field surrounding the system. New Very Large Array and XMM-Newton data are presented here. We use the radio and X-ray data to examine the fraction and location of active galaxies, both active galactic nuclei (AGNs) and starbursts (SBs). The radio far-infrared correlation, X-ray point source location, IRAC colors, and quasar positions are all used to gain an understanding of the presence of dominant AGNs. We find very few MIPS-selected galaxies that are clearly dominated by AGN activity. Most radio-selected members within the filament are SBs. Within the supercluster, three of eight spectroscopic members detected both in the radio and in the mid-infrared are radio-bright AGNs. They are found at or near the core of A1763. The five SBs are located further along the filament. We calculate the physical properties of the known wide angle tail (WAT) source which is the brightest cluster galaxy of A1763. A second double lobe source is found along the filament well outside of the virial radius of either cluster. The velocity offset of the WAT from the X-ray centroid and the bend of the WAT in the intracluster medium are both consistent with ram pressure stripping, indicative of streaming motions along the direction of the filament. We consider this as further evidence of the cluster-feeding nature of the galaxy filament.

Progress in high field MRI at the University of Florida

In this article we report on progress in high magnetic field MRI at the University of Florida in support of our new 750MHz wide bore and 11.7T/40cm MR instruments. The primary emphasis is on the associated rf technology required, particularly high frequency volume and phased array coils. Preliminary imaging results at 750MHz are presented. Our results imply that the pursuit of even higher fields seems warranted. (C) 2002 Elsevier Science B.V. All rights reserved.

Effects of residues on the degradation of PHA produced from mixed microbial cultures and processed in extrusion

Thermal degradation upon melting is one of the major drawbacks reported for polyhydroxyalkanoates (PHA). However, the role of residues originating from the fermentation and the extraction steps on the thermal stability of this class of biopolymers still needs to be clarified. In the particular case of PHA produced from mixed microbial cultures (MMC), this topic is even less documented in the literature. Here, two polyhydroxy(butyrate-co-valerate) (PHBV) produced from MMC enriched in PHA accumulating organisms and fed with cheese whey were studied. A micro extrusion line is used to produce filaments and assess the processability and the degradation of processed PHBV. The prototype micro extrusion line allows for studying grams of materials. The two PHBV contain 18 mol% HV. PHBV was recovered with 11 wt% residues, and further submitted to a purification procedure resulting in a second biopolyester containing less than 2 wt% impurities. The thermorheological characterization of the two PHBV is first presented, together with their semicrystalline properties. Then the processing windows of the two biopolyesters are presented. Finally, the properties of extruded filaments are reported and the thermomechanical degradation of PHBV is extensively studied. The structure was assessed by wide angle X-ray diffraction, mechanical and rheological properties are reported, thermal properties are studied with differential scanning calorimetry and thermogravimetric analysis, whereas Fourier Transform Infrared spectroscopy was used to assess the impact of the extrusion on PHBV chemical structure. All results obtained with the two PHBV are compared to assess the effects of residues on both PHBV processability and degradation.

Microinjection molding of polyamide 6/carbon nanotube composites

Microinjection molding of polymer composites with carbon nanotubes (CNT) requires previous production of the nanocomposites, often by melt extrusion. Each processing step has a thermo-mechanical effect on the polymer melt, conveying different properties to the final product. In this work, polyamide 6 and its composites with pristine and functionalized CNT (f-CNT) were processed by a mini twin-screw extrusion, followed by microinjection molding. The morphology induced on the polymer by each process was analyzed by differential scanning calorimetry and wide angle X-ray diffraction. Calorimetric analysis showed a secondary crystallization for the microinjected materials, absent for the extruded materials. The characterization of microinjected polyamide 6 by X-ray diffraction revealed a large contribution of the c phase to the total crystallinity, mainly in the skin region, while the nanocomposites and extruded materials were characterized by a larger contribution of the a phase. Functionalization of CNT did not affect significantly the polymer morphology compared to composites with pristine CNT.

Thermal characterization of polyhydroxyalkanoates and poly(lactic acid) blends obtained by injection molding

In this work we present the thermal characterization of the full scope of polyhydroxyalcanoate and poly(lactic acid) blends obtain by injection molding. Blends of polyhydroxyalcanoate and poly(lactic acid) (PHA/PLA) were prepared in different compositions ranging from 0–100% in steps of 10%. The blends were injection molded and then characterized by differential scanning calorimetry (DSC), scanning electron microscopy (SEM) and wide angle X-ray diffraction (WAXD). The increment of PHA fraction increased the degree of crystallinity of the blend and the miscibility of the base polymers as verified by the Fox model. The WAXD analysis indicates that the presence of PHA hindered the PLA crystallization. The crystallization evolution trough PHA weight fraction (wf) shows a phase inversion around 50-60%. SEM analyses confirmed that the miscibility of PHA/PLA blends increased with the incorporation of PHA and became total for values of PHA higher that 50%.

Comparison of three commercially available radio frequency coils for human brain imaging at 3 Tesla.

OBJECTIVE: To evaluate a transverse electromagnetic (TEM), a circularly polarized (CP) (birdcage), and a 12-channel phased array head coil at the clinical field strength of B0 = 3T in terms of signal-to-noise ratio (SNR), signal homogeneity, and maps of the effective flip angle alpha. MATERIALS AND METHODS: SNR measurements were performed on low flip angle gradient echo images. In addition, flip angle maps were generated for alpha(nominal) = 30 degrees using the double angle method. These evaluation steps were performed on phantom and human brain data acquired with each coil. Moreover, the signal intensity variation was computed for phantom data using five different regions of interest. RESULTS: In terms of SNR, the TEM coil performs slightly better than the CP coil, but is second to the smaller 12-channel coil for human data. As expected, both the TEM and the CP coils show superior image intensity homogeneity than the 12-channel coil, and achieve larger mean effective flip angles than the combination of body and 12-channel coil with reduced radio frequency power deposition. CONCLUSION: At 3T the benefits of TEM coil design over conventional lumped element(s) coil design start to emerge, though the phased array coil retains an advantage with respect to SNR performance.

Pitfalls in colour photography of choroidal tumours.

Colour imaging of fundus tumours has been transformed by the development of digital and confocal scanning laser photography. These advances provide numerous benefits, such as panoramic images, increased contrast, non-contact wide-angle imaging, non-mydriatic photography, and simultaneous angiography. False tumour colour representation can, however, cause serious diagnostic errors. Large choroidal tumours can be totally invisible on angiography. Pseudogrowth can occur because of artefacts caused by different methods of fundus illumination, movement of reference blood vessels, and flattening of Bruch's membrane and sclera when tumour regression occurs. Awareness of these pitfalls should prevent the clinician from misdiagnosing tumours and wrongfully concluding that a tumour has grown.

Melt structure and its transformation by sequential crystallization of the two blocks within poly(L-lactide)-block-poly(epsilon-caprolactone) double crystalline diblock copolymers

Sequential crystallization of poly(L-lactide) (PLLA) followed by poly(epsilon-caprolactone) (PCL) in double crystalline PLLA-b-PCL diblock copolymers is studied by differential scanning calorimetry (DSC), polarized optical microscopy (POM), wide-angle X-ray scattering (WAXS) and small-angle X-ray scattering (SAXS). Three samples with different compositions are studied. The sample with the shortest PLLA block (32 wt.-% PLLA) crystallizes from a homogeneous melt, the other two (with 44 and 60% PLLA) from microphase separated structures. The microphase structure of the melt is changed as PLLA crystallizes at 122 degrees C (a temperature at which the PCL block is molten) forming spherulites regardless of composition, even with 32% PLLA. SAXS indicates that a lamellar structure with a different periodicity than that obtained in the melt forms (for melt segregated samples). Where PCL is the majority block, PCL crystallization at 42 degrees C following PLLA crystallization leads to rearrangement of the lamellar structure, as observed by SAXS, possibly due to local melting at the interphases between domains. POM results showed that PCL crystallizes within previously formed PLLA spherulites. WAXS data indicate that the PLLA unit cell is modified by crystallization of PCL, at least for the two majority PCL samples. The PCL minority sample did not crystallize at 42 degrees C (well below the PCL homopolymer crystallization temperature), pointing to the influence of pre-crystallization of PLLA on PCL crystallization, although it did crystallize at lower temperature. Crystallization kinetics were examined by DSC and WAXS, with good agreement in general. The crystallization rate of PLLA decreased with increase in PCL content in the copolymers. The crystallization rate of PCL decreased with increasing PLLA content. The Avrami exponents were in general depressed for both components in the block copolymers compared to the parent homopolymers. Polarized optical micrographs during isothermal crystalli zation of (a) homo-PLLA, (b) homo-PCL, (c) and (d) block copolymer after 30 min at 122 degrees C and after 15 min at 42 degrees C.

Miscibility studies of the blends of chitosan with some cellulose ethers

The polymeric films have been prepared based on blends of chitosan with two cellulose ethers-hydroxypropylmethylcellulose and methylcellulose by casting from acetic acid solutions. The films were transparent and brittle in a dry state but an immersion of the samples in deionized water for over 24 h leads to their disintegration or partial dissolution. The miscibility of the polymers in the blends has been assessed by infrared spectroscopy, wide-angle X-ray diffraction, scanning electron microscopy and thermal gravimetric analysis. It was shown that although weak hydrogen bonding exists between the polymer functional groups the blends are not fully miscible in a dry state. (c) 2005 Elsevier Ltd. All rights reserved.

Assembly of an injectable noncytotoxic peptide-based hydrogelator for sustained release of drugs

A new synthetic tripeptide-based hydrogel has been discovered at physiological pH and temperature. This hydrogel has been thoroughly characterized using different techniques including field emission scanning electron microscopic (FESEM) and high-resolution transmission electron microscopic (HR-TEM) imaging, small- and wide-angle X-ray diffraction analyses, FT-IR, circular dichroism, and rheometric analyses. Moreover, this gel exhibits thixotropy and injectability. This hydrogel has been used for entrapment and sustained release of an antibiotic vancomycin and vitamin B12 at physiological pH and temperature for about 2 days. Interestingly, MTT assay of these gelator molecules shows almost 100% cell viability of this peptide gelator, indicating its noncytotoxicity.

Polymorphism, crystallinity and hydrophilic-lipophilic balance of stearic acid and stearic acid-capric/caprylic triglyceride matrices for production of stable nanoparticles

There is an increasing interest in lipid nanoparticles because of their suitability for several administration routes. Thus, it becomes even more relevant the physicochemical characterization of lipid materials with respect to their polymorphism, lipid miscibility and stability, as well as the assessment of the effect of surfactant on the type and structure of these nanoparticles. This work focuses on the physicochemical characterization of lipid matrices composed of pure stearic acid or of mixtures of stearic acid-capric/caprylic triglycerides, for drug delivery. The lipids were analyzed by Differential Scanning Calorimetry (DSC), Wide Angle X-ray Diffraction (WAXD), Polarized Light Microscopy (PLM) and hydrophilic-lipophilic balance (HLB) in combination with selected surfactants to determine the best solid-to-liquid ratio. Based on the results obtained by DSC and WAXD, the selected qualitative and quantitative composition contributed for the production of stable nanoparticles, since the melting and the tempering processes provided important information on the thermodynamic stability of solid lipid matrices. The best HLB value obtained for stearic acid-capric/caprylic triglycerides was 13.8, achieved after combining these lipids with accepted surfactants (trioleate sorbitan and polysorbate 80 in the ratio of 10:90). The proposed combinations were shown useful to obtain a stable emulsion to be used as intermediate form for the production of lipid nanoparticles. (C) 2011 Elsevier B.V. All rights reserved.

Melting Regime of the Anionic Phospholipid DMPG: New Lamellar Phase and Porous Bilayer Model

Aqueous dispersions of the anionic phospholipid dimyristoyl phosphatidylglycerol (DMPG) at pH above the apparent pK of DMPG and concentrations in the interval 70-300 mM have been investigated by small (SAXS) and wide-angle X-ray scattering, differential scanning calorimetry, and polarized optical microscopy. The order. disorder transition of the hydrocarbon chains occurs along an interval of about 10 degrees C (between T(m)(on) similar to 20 degrees C and T(m)(off) similar to 30 degrees C). Such melting regime was previously characterized at lower concentrations, up to 70 mM DMPG, when sample transparency was correlated with the presence of pores across the bilayer. At higher concentrations considered here, the melting regime persists but is not transparent. Defined SAXS peaks appear and a new lamellar phase L(p) with pores is proposed to exist above 70 mM DMPG, starting at similar to 23 degrees C (similar to 3 degrees C above T(m)(on)) and losing correlation after T(m)(off). A new model for describing the X-ray scattering of bilayers with pores, presented here, is able to explain the broad band attributed to in-plane correlation between pores. The majority of cell membranes have a net negative charge, and the opening of pores across the membrane tuned by ionic strength, temperature, and lipid composition is likely to have biological relevance.