The behaviour of antioxidants in polyolefins under conditions of U.V. exposure

The effects of antioxidants and stabilizers on the oxidative degradation of polyolefins (low density polyethylene [LDPE] and polypropylene [PPJ have been studied after subjecting to prior high temperature processing treatments. The changes in the both chemical and physical properties of unstabilized polymers occurring during processing were found to be strongly dependent on the amount of oxygen present in the mixer. Subsequent thermal and photo-oxidation showed very similar characteristics and the chromophore primarily responsible for:both thermo and photooxidative degradation of unstabilized polymers was found to be hydroperoxide formed during processing. Removal of hydroperoxide by heat treatment in an inert atmosphere although increasing ketonic carbonyl concentration, markedly decreased the rate of photo-oxidation, introducing an induction period similar to that of an unprocessed sample. It was concluded that hydroperoxides are the most important initiators in normally processed polymers during the early stages of photo-oxidation. Antioxidants such as metal dithiocarbamates which act by destroying peroxides into non-radica1 products were found to be efficient melt stabilizers for polyolefins and effective UV stabilizers during the initial photo-oxidation stage, whilst a phenolic antioxidant, n-octadecyl-3-(3',5'-di-terbutyl 4'hydroxypheny1) propionate (Irganox 1076) retarded photo-oxidation rate in the later stages. A typical 'UV absorber' 2-hydroxy-4-octyloxy-benzophenone (HOBP) has a minor thermal antioxidant action but retarded photo-oxidation at all stages. A substituated piperidine derivative, Bis [2.2.6.6-tetramethylpiperidlnyl-4] sebacate (Tinuvin 770) behaved as an pro-oxidant during thermal oxidation of polyolefins but was an effective stabilizer against UV light. The UV absorber, HOBP synergised effectively with both peroxide decomposing antioxidants (metal dithiocarbamates) and a chain-breaking antioxidant (Irganox 1076) during photo-oxidation of the poymers studed whereas the combined effect was additive during thermal oxidation. By contrast, the peroxide decornposers and chain-breaking antioxidant (Irganox 1076) which were effective synergists during thermal oxidation of LDPE· were antagonistic during photo-oxidation. The mechanisms of these processes are discussed.

Reactive processing of polymers: structural characterization of products by 1H and 13C NMR spectroscopy for glycidyl methacrylate grafting onto EPR in the absence and presence of a reactive comonomer

Grafted GMA on EPR samples were prepared in a Thermo-Haake internal mixer by free radical melt grafting reactions in the absence (conventional system; EPR-g-GMA(CONV)) and presence of the reactive comonomer divinyl benzene, DVB (EPR-g-GMA(DVB)). The GMA-homopolymer (poly-GMA), a major side reaction product in the conventional system, was almost completely absent in the DVB-containing system, the latter also resulted in a much higher level of GMA grafting. A comprehensive microstructure analysis of the formed poly-GMA was performed based on one-dimensional H-1 and C-13 NMR spectroscopy and the complete spectral assignments were supported by two-dimensional NMR techniques based on long range two and three bond order carbon-proton couplings from HMBC (Heteronuclear Multiple Bond Coherence) and that of one bond carbon-proton couplings from HSQC (Heteronuclear Single Quantum Coherence), as well as the use of Distortionless Enhancement by Polarization Transfer (DEPT) NMR spectroscopy. The unambiguous analysis of the stereochemical configuration of poly-GMA was further used to help understand the microstructures of the GMA-grafts obtained in the two different free radical melt grafting reactions, the conventional and comonomer-containing systems. In the grafted GMA, in the conventional system (EPR-g-GMA(CONV)), the methylene protons of the GMA were found to be sensitive to tetrad configurational sequences and the results showed that 56% of the GMA sequence in the graft is in atactic configuration and 42% is in syndiotactic configuration whereas the poly-GMA was predominantly syndiotactic. The differences in the microstructures of the graft in the conventional EPR-g-GMA(CONV) and the DVB-containing (EPR-g-GMA(DVB)) systems is also reported (C) 2009 Elsevier Ltd. All rights reserved.

Reactive processing of polymers:effect of in situ compatibilisation on characteristics of blends of polyethylene terephthalate and ethylene-propylene rubber

Ethylene-propylene rubber (EPR) functionalised with glycidyl methacrylate (GMA) (f-EPR) during melt processing in the presence of a co-monomer, such as trimethylolpropane triacrylate (Tris), was used to promote compatibilisation in blends of polyethylene terephthalate (PET) and f-EPR, and their characteristics were compared with those of PET/f-EPR reactive blends in which the f-EPR was functionalised with GMA via a conventional free radical melt reaction (in the absence of a co-monomer). Binary blends of PETand f-EPR (with two types of f-EPR prepared either in presence or absence of the co-monomer) with various compositions (80/20, 60/40 and 50/50 w/w%) were prepared in an internal mixer. The blends were evaluated by their rheology (from changes in torque during melt processing and blending reflecting melt viscosity, and their melt flow rate), morphology scanning electron microscopy (SEM), dynamic mechanical properties (DMA), Fourier transform infrared (FTIR) analysis, and solubility (Molau) test. The reactive blends (PET/f-EPR) showed a marked increase in their melt viscosities in comparison with the corresponding physical (PET/EPR) blends (higher torque during melt blending), the extent of which depended on the amount of homopolymerised GMA (poly-GMA) present and the level of GMA grafting in the f-EPR. This increase was accounted for by, most probably, the occurrence of a reaction between the epoxy groups of GMA and the hydroxyl/carboxyl end groups of PET. Morphological examination by SEM showed a large improvement of phase dispersion, indicating reduced interfacial tension and compatibilisation, in both reactive blends, but with the Tris-GMA-based blends showing an even finer morphology (these blends are characterised by absence of poly-GMA and presence of higher level of grafted GMA in its f-EPR component by comparison to the conventional GMA-based blends). Examination of the DMA for the reactive blends at different compositions showed that in both cases there was a smaller separation between the glass transition temperatures compared to their position in the corresponding physical blends, which pointed to some interaction or chemical reaction between f-EPR and PET. The DMA results also showed that the shifts in the Tgs of the Tris-GMA-based blends were slightly higher than for the conventional GMA-blends. However, the overall tendency of the Tgs to approach each other in each case was found not to be significantly different (e.g. in a 60/40 ratio the former blend shifted by up to 4.5 °C in each direction whereas in the latter blend the shifts were about 3 °C). These results would suggest that in these blends the SEM and DMA analyses are probing uncorrelatable morphological details. The evidence for the formation of in situ graft copolymer between the f-EPR and PET during reactive blending was clearly illustrated from analysis by FTIR of the separated phases from the Tris-GMA-based reactive blends, and the positive Molau test pointed out to graft copolymerisation in the interface. A mechanism for the formation of the interfacial reaction during the reactive blending process is proposed.

Coupling of Heck and hydrogenation reactions in a continuous compact reactor

A continuous multi-step synthesis of 1,2-diphenylethane was performed sequentially in a structured compact reactor. This process involved a Heck C-C coupling reaction followed by the addition of hydrogen to perform reduction of the intermediate obtained in the first step. Both of the reactions were catalysed by microspherical carbon-supported Pd catalysts. Due to the integration of the micro-heat exchanger, the static mixer and the mesoscale packed-bed reaction channel, the compact reactor was proven to be an intensified tool for promoting the reactions. In comparison with the batch reactor, this flow process in the compact reactor was more efficient as: (i) the reaction time was significantly reduced (ca. 7 min versus several hours), (ii) no additional ligands were used and (iii) the reaction was run at lower operational pressure and temperature. Pd leached in the Heck reaction step was shown to be effectively recovered in the following hydrogenation reaction section and the catalytic activity of the system can be mostly retained by reverse flow operation. © 2009 Elsevier Inc. All rights reserved.

Broadband RF current detector

The problems to be solved in this thesis were 1) development of a broadband RF preamplifier to be used with non-ferrous current probes so that the amplified signal exceeds the errors due to cable pickup, no detection is needed in this application, and 2) development of a self-contained device that amplifies and detects the output from a nonferrous current probe, providing a digital readout of the current. These instruments have been completed and are being tested for use by the National Institutes of Occupational Safety and Health (NIOSH). The self-contained current meter operates at frequencies up to 600 MHz, and detects currents as low as 8 mA . At these current magnitudes, the probe (pick-up coil) will output a voltage of 500μV (-53 dBm on 50Ω) which will have to be raised above 0 dBm. The final circuit uses a RF mixer as a variable attenuator in order to increase the dynamic range, two Monolithic Microwave Integrated Circuits (MMIC) for preamplification, a final broadband amplifier to raise the output compression point, a Schottky diode detector, a sample and hold circuit, and a liquid crystal digital panel meter.

Method to Improve the Linearity of Active Commutating Mixers Using Dynamic Current Injection

A double balanced (DBM) CMOS mixer providing high linearity is presented in this paper. A cross-coupled pair used in the IF stage of the mixer to dynamically inject current into the to mixer provide a high linearity. The proposed DBM was fabricated using a standard 130-nm CMOS process and was tested on-wafer. The double balanced mixer delivers 10 dB conversion gain, 9.5 dBm IIP3, and input P1dB of -2.4 dBm. RF bandwidth of the proposed mixer is 6 GHz, covering 0.5 GHz to 6.5 GHz with IF bandwidth of 300 MHz. RF to IF and LO to IF isolation are also better than 59 dB in the whole frequency band. The circuit uses an area of 0.015 mm2 excluding bonding pads and draw 4.5mW from a 1.2V supply.

Method to Improve the Conversion Gain Flatness of Transformer-Coupled Mixers

A 4-10 GHz, on-chip balun based current commutating mixer is proposed. Tunable resistive feedback is used at the transconductance stage for wideband response, and interlaced stacked transformer is adopted for good balance of the balun. Measurement results show that a conversion gain of 13.5 dB, an IIP3 of 4 dBm and a noise figure of 14 dB are achieved with 5.6 mW power consumption under 1.2 V supply. The simulated amplitude and phase imbalance is within 0.9 dB and ±2◦ over the band.

Energy drinks in Ireland - a review

Energy drinks have risen in popularity in recent years and are now sold in over 165 countries worldwide. On the island of Ireland, energy drinks advertising accounted for 20% of the total soft drinks market advertising in 2014. In the United States, sales increased by 60% between 2008 and 2012, and in 2006, a staggering 500 new brands of energy drinks were released worldwide. In the UK, the energy drinks market is worth £491 million and is growing by 7% year on year. This report has found an eightfold increase in the number of energy drinks available in 2015 compared to 2002. While no standard definition of an energy drink is used in the scientific literature, it is commonly understood to be a non-alcoholic drink that contains caffeine (usually its main ingredient), taurine, vitamins and sometimes a combination of other ingredients (such as guarana and ginseng, among others), and it is marketed for its perceived or actual benefits as a stimulant, for improving performance and for increasing energy. As this report will highlight, there is some confusion amongst the public as to what the term "energy drink" means, as some soft and sports drinks, while containing little or no caffeine, use the term ‘energy’ in the product label, for example, Lucozade. Both the scientific community and the public have raised health concerns about the caffeine and calorie intakes associated with energy drinks and the use of these drinks as a mixer with alcohol. These concerns are disputed by the energy drinks industry.

Mechanochemical solvent-free synthesis of Sn-β Zeolite and Ag2O/TiO2 catalysts

Preparations of heterogeneous catalysts are usually complex processes that involve several procedures as precipitation, crystallization and hydrothermal treatments. This processes are really dependent by the operative conditions such as temperature, pH, concentration etc. Hence the resulting product is extremely affected by any possible variations in these parameters making this synthesis really fragile. With the aim to improve these operations has been decided to exploit a new possible strong environment-respectful process by mechanochemical treatment, which permits to carry out solvent free-solvent synthesis exploiting the Mixer Mill MM400 (Retsch) in order to have reproducible results. Two different systems have been studied in this kind of synthesis: a tin β -zeolite tested in a H-trasnfer reaction of cyclohexanone and a silver on titania catalyst used in the fluorination of 2,2 dimethyl glucaric acid. Each catalyst has been characterized by different techniques in order to understand the transformations involved in the mechanochemical treatment.

Radio over fiber enabling PON fronthaul in a two-tiered cloud

Avec l’avènement des objets connectés, la bande passante nécessaire dépasse la capacité des interconnections électriques et interface sans fils dans les réseaux d’accès mais aussi dans les réseaux coeurs. Des systèmes photoniques haute capacité situés dans les réseaux d’accès utilisant la technologie radio sur fibre systèmes ont été proposés comme solution dans les réseaux sans fil de 5e générations. Afin de maximiser l’utilisation des ressources des serveurs et des ressources réseau, le cloud computing et des services de stockage sont en cours de déploiement. De cette manière, les ressources centralisées pourraient être diffusées de façon dynamique comme l’utilisateur final le souhaite. Chaque échange nécessitant une synchronisation entre le serveur et son infrastructure, une couche physique optique permet au cloud de supporter la virtualisation des réseaux et de les définir de façon logicielle. Les amplificateurs à semi-conducteurs réflectifs (RSOA) sont une technologie clé au niveau des ONU(unité de communications optiques) dans les réseaux d’accès passif (PON) à fibres. Nous examinons ici la possibilité d’utiliser un RSOA et la technologie radio sur fibre pour transporter des signaux sans fil ainsi qu’un signal numérique sur un PON. La radio sur fibres peut être facilement réalisée grâce à l’insensibilité a la longueur d’onde du RSOA. Le choix de la longueur d’onde pour la couche physique est cependant choisi dans les couches 2/3 du modèle OSI. Les interactions entre la couche physique et la commutation de réseaux peuvent être faites par l’ajout d’un contrôleur SDN pour inclure des gestionnaires de couches optiques. La virtualisation réseau pourrait ainsi bénéficier d’une couche optique flexible grâce des ressources réseau dynamique et adaptée. Dans ce mémoire, nous étudions un système disposant d’une couche physique optique basé sur un RSOA. Celle-ci nous permet de façon simultanée un envoi de signaux sans fil et le transport de signaux numérique au format modulation tout ou rien (OOK) dans un système WDM(multiplexage en longueur d’onde)-PON. Le RSOA a été caractérisé pour montrer sa capacité à gérer une plage dynamique élevée du signal sans fil analogique. Ensuite, les signaux RF et IF du système de fibres sont comparés avec ses avantages et ses inconvénients. Finalement, nous réalisons de façon expérimentale une liaison point à point WDM utilisant la transmission en duplex intégral d’un signal wifi analogique ainsi qu’un signal descendant au format OOK. En introduisant deux mélangeurs RF dans la liaison montante, nous avons résolu le problème d’incompatibilité avec le système sans fil basé sur le TDD (multiplexage en temps duplexé).

Microfluidic platforms for the characterization of in meso membrane protein crystallization

Membrane proteins, which reside in the membranes of cells, play a critical role in many important biological processes including cellular signaling, immune response, and material and energy transduction. Because of their key role in maintaining the environment within cells and facilitating intercellular interactions, understanding the function of these proteins is of tremendous medical and biochemical significance. Indeed, the malfunction of membrane proteins has been linked to numerous diseases including diabetes, cirrhosis of the liver, cystic fibrosis, cancer, Alzheimer's disease, hypertension, epilepsy, cataracts, tubulopathy, leukodystrophy, Leigh syndrome, anemia, sensorineural deafness, and hypertrophic cardiomyopathy.1-3 However, the structure of many of these proteins and the changes in their structure that lead to disease-related malfunctions are not well understood. Additionally, at least 60% of the pharmaceuticals currently available are thought to target membrane proteins, despite the fact that their exact mode of operation is not known.4-6 Developing a detailed understanding of the function of a protein is achieved by coupling biochemical experiments with knowledge of the structure of the protein. Currently the most common method for obtaining three-dimensional structure information is X-ray crystallography. However, no a priori methods are currently available to predict crystallization conditions for a given protein.7-14 This limitation is currently overcome by screening a large number of possible combinations of precipitants, buffer, salt, and pH conditions to identify conditions that are conducive to crystal nucleation and growth.7,9,11,15-24 Unfortunately, these screening efforts are often limited by difficulties associated with quantity and purity of available protein samples. While the two most significant bottlenecks for protein structure determination in general are the (i) obtaining sufficient quantities of high quality protein samples and (ii) growing high quality protein crystals that are suitable for X-ray structure determination,7,20,21,23,25-47 membrane proteins present additional challenges. For crystallization it is necessary to extract the membrane proteins from the cellular membrane. However, this process often leads to denaturation. In fact, membrane proteins have proven to be so difficult to crystallize that of the more than 66,000 structures deposited in the Protein Data Bank,48 less than 1% are for membrane proteins, with even fewer present at high resolution (< 2Å)4,6,49 and only a handful are human membrane proteins.49 A variety of strategies including detergent solubilization50-53 and the use of artificial membrane-like environments have been developed to circumvent this challenge.43,53-55 In recent years, the use of a lipidic mesophase as a medium for crystallizing membrane proteins has been demonstrated to increase success for a wide range of membrane proteins, including human receptor proteins.54,56-62 This in meso method for membrane protein crystallization, however, is still by no means routine due to challenges related to sample preparation at sub-microliter volumes and to crystal harvesting and X-ray data collection. This dissertation presents various aspects of the development of a microfluidic platform to enable high throughput in meso membrane protein crystallization at a level beyond the capabilities of current technologies. Microfluidic platforms for protein crystallization and other lab-on-a-chip applications have been well demonstrated.9,63-66 These integrated chips provide fine control over transport phenomena and the ability to perform high throughput analyses via highly integrated fluid networks. However, the development of microfluidic platforms for in meso protein crystallization required the development of strategies to cope with extremely viscous and non-Newtonian fluids. A theoretical treatment of highly viscous fluids in microfluidic devices is presented in Chapter 3, followed by the application of these strategies for the development of a microfluidic mixer capable of preparing a mesophase sample for in meso crystallization at a scale of less than 20 nL in Chapter 4. This approach was validated with the successful on chip in meso crystallization of the membrane protein bacteriorhodopsin. In summary, this is the first report of a microfluidic platform capable of performing in meso crystallization on-chip, representing a 1000x reduction in the scale at which mesophase trials can be prepared. Once protein crystals have formed, they are typically harvested from the droplet they were grown in and mounted for crystallographic analysis. Despite the high throughput automation present in nearly all other aspects of protein structure determination, the harvesting and mounting of crystals is still largely a manual process. Furthermore, during mounting the fragile protein crystals can potentially be damaged, both from physical and environmental shock. To circumvent these challenges an X-ray transparent microfluidic device architecture was developed to couple the benefits of scale, integration, and precise fluid control with the ability to perform in situ X-ray analysis (Chapter 5). This approach was validated successfully by crystallization and subsequent on-chip analysis of the soluble proteins lysozyme, thaumatin, and ribonuclease A and will be extended to microfluidic platforms for in meso membrane protein crystallization. The ability to perform in situ X-ray analysis was shown to provide extremely high quality diffraction data, in part as a result of not being affected by damage due to physical handling of the crystals. As part of the work described in this thesis, a variety of data collection strategies for in situ data analysis were also tested, including merging of small slices of data from a large number of crystals grown on a single chip, to allow for diffraction analysis at biologically relevant temperatures. While such strategies have been applied previously,57,59,61,67 they are potentially challenging when applied via traditional methods due to the need to grow and then mount a large number of crystals with minimal crystal-to-crystal variability. The integrated nature of microfluidic platforms easily enables the generation of a large number of reproducible crystallization trials. This, coupled with in situ analysis capabilities has the potential of being able to acquire high resolution structural data of proteins at biologically relevant conditions for which only small crystals, or crystals which are adversely affected by standard cryocooling techniques, could be obtained (Chapters 5 and 6). While the main focus of protein crystallography is to obtain three-dimensional protein structures, the results of typical experiments provide only a static picture of the protein. The use of polychromatic or Laue X-ray diffraction methods enables the collection of time resolved structural information. These experiments are very sensitive to crystal quality, however, and often suffer from severe radiation damage due to the intense polychromatic X-ray beams. Here, as before, the ability to perform in situ X-ray analysis on many small protein crystals within a microfluidic crystallization platform has the potential to overcome these challenges. An automated method for collecting a "single-shot" of data from a large number of crystals was developed in collaboration with the BioCARS team at the Advanced Photon Source at Argonne National Laboratory (Chapter 6). The work described in this thesis shows that, even more so than for traditional structure determination efforts, the ability to grow and analyze a large number of high quality crystals is critical to enable time resolved structural studies of novel proteins. In addition to enabling X-ray crystallography experiments, the development of X-ray transparent microfluidic platforms also has tremendous potential to answer other scientific questions, such as unraveling the mechanism of in meso crystallization. For instance, the lipidic mesophases utilized during in meso membrane protein crystallization can be characterized by small angle X-ray diffraction analysis. Coupling in situ analysis with microfluidic platforms capable of preparing these difficult mesophase samples at very small volumes has tremendous potential to enable the high throughput analysis of these systems on a scale that is not reasonably achievable using conventional sample preparation strategies (Chapter 7). In collaboration with the LS-CAT team at the Advanced Photon Source, an experimental station for small angle X-ray analysis coupled with the high quality visualization capabilities needed to target specific microfluidic samples on a highly integrated chip is under development. Characterizing the phase behavior of these mesophase systems and the effects of various additives present in crystallization trials is key for developing an understanding of how in meso crystallization occurs. A long term goal of these studies is to enable the rational design of in meso crystallization experiments so as to avoid or limit the need for high throughput screening efforts. In summary, this thesis describes the development of microfluidic platforms for protein crystallization with in situ analysis capabilities. Coupling the ability to perform in situ analysis with the small scale, fine control, and the high throughput nature of microfluidic platforms has tremendous potential to enable a new generation of crystallographic studies and facilitate the structure determination of important biological targets. The development of platforms for in meso membrane protein crystallization is particularly significant because they enable the preparation of highly viscous mixtures at a previously unachievable scale. Work in these areas is ongoing and has tremendous potential to improve not only current the methods of protein crystallization and crystallography, but also to enhance our knowledge of the structure and function of proteins which could have a significant scientific and medical impact on society as a whole. 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Evaluación de las propiedades mecánicas de materiales compuestos elaborados a partir de cenizas volantes y polímeros reciclados

En el presente artículo se evalúan las propiedades mecánicas de los materiales compuestos basados en cenizas volantes de carbón de la central termoeléctrica de Termozipa combinadas con los película extensible (Stretch film), polietilenos de baja densidad lineal de pos-consumo y polímero termoplástico parcialmente cristalino pos- industrial. Se obtuvieron mezclas variando el contenido de cenizas volantes de 0 a 50 % en peso en cada uno de los tres materiales poliméricos, dentro de una máquina mezcladora tipo Brabender. Las propiedades mecánicas evaluadas fueron: resistencia a la tracción, dureza Shore D, y absorción de energía. Los resultados obtenidos indican que en todos los casos a medida que se agrega ceniza volante las propiedades mecánicas aumentan.

Otimização de uma linha de aglomeração de materiais reciclados

Dado a globalização dos negócios e o aumento da competitividade dos produtos, é cada vez mais difícil para as grandes empresas manter a sua posição no mercado. Este processo quer-se rápido, eficaz e com o menor custo possível. Para este efeito, a metodologia Lean tem oferecido respostas bastante interessantes às empresas, com a aplicação de ferramentas da metodologia muito simples mas muito eficientes. Garantir características no produto final que façam á empresa manter ou ganhar cota no mercado é fundamental. Como tal, as empresas tentam ao máximo garantir a qualidade e o aspecto visual do produto. Posto isto, foram efetuados vários trabalhos para fazer frente às situações acima apresentadas e fazer com que o produto continue competitivo, para que possa aumentar a sua margem de lucro, mantendo o seu valor no mercado. Os trabalhos efetuados foram: plano de manutenção autónoma, um estudo do efeito da velocidade do misturador no produto final e um balanceamento à linha de aglomeração. Com a aplicação do Plano de Manutenção Autónoma, foi possível eliminar desperdícios, tornar a linha mais organizada e limpa e instruir os operadores a serem mais responsáveis, organizados e críticos ao seu trabalho. Quanto ao estudo do efeito da velocidade do misturador no produto final, os resultados não foram os esperados, dado que com o ensaio industrial efetuado não foi possível melhorar significativamente o aspeto visual do produto. Apesar de não ter sido possível a sua implementação, com o estudo do Balanceamento da linha, junto com os dados recolhidos foi possível obter um conhecimento mais pormenorizado da linha, foi criada uma possibilidade de proteger a linha de possíveis flutuações do mercado e eliminação de desperdício e uma possibilidade de listagem de tarefas estandartizadas e equilibradas, promovendo um menor esforço aos operadores. Em síntese, com a elaboração destes trabalhos, foi possível provocar um impacto positivo na linha, tornando-a mais organizada, reduzindo desperdício, protegendo de flutuações do mercado e aumentando o conhecimento da mesma.

Desenvolvimento de bioblendas poliméricas a partir de gelatina bovina e de tilápia com amido de milho

The natural raw materials acquired special importance beside the mineral raw materials with the need for using alternative sources to oil, because they can be used to produce biopolymers. Gelatin, produced from the denaturation of collagen, and starch, an abundant polysaccharide in various plants, are examples of biopolymers which have several technological applications, especially in films. The objective of this work is to produce polymeric bioblends with gelatin and corn starch using two types of gelatin: commercial bovine gelatin and gelatin produced from mechanically separated flesh of tilapia (Oreochromis niloticus). For the extraction of tilapia gelatin 3 distinct pretreatments, followed by extraction in distilled water under heating were performed. The properties of gelatin extracted were similar to bovine gelatin, and the differences can be explained by the difference in extraction processes and sources. Blends of commercial gelatin and starch were produced in an internal mixer from a Haake torque rheometer, to study the behavior of the gelatin mixture with starch, thus, the same compositions were processed by twin screw extrusion, to define the mixing parameters. Subsequently, the extrusion of blends of tilapia gelatin and corn starch was carried out in the same twin screw extruder. The physico-chemical, rheological and morphological properties of the blends with thermoplastic starch and gelatin were studied. It was found that various properties vary linearly with increasing concentration of the components. The blends produced are immiscible, and among the two gelatins, tilapia gelatin showed a better interfacial adhesion with the corn starch. Regarding the morphology, gelatins formed the dispersed phase in all compositions studied, even in compositions rich in starch. Can be concluded that the procedure for tilapia gelatin extraction is feasible and advantageous, and the increasing in its scale to a reactor of 30 liters is possible, with a satisfactory yield. The bioblends of bovine gelatin/corn starch and tilapia gelatin/corn starch were successfully produced, and the processing conditions were appropriate

Compósitos de matriz metálica à base níquel com adição de TaC e NbC produzidos via metalurgia do pó

Carbide reinforced metallic alloys potentially improve some important mechanical properties required for the overall use of important engineering materials such as steel and nickel. Nevertheless, improved performance is achieved not only by composition enhancement but also by adequate processing techniques, such as novel sintering methods in the case of powder metallurgy. The method minimizes energy losses in addition to providing uniform heating during sintering. Thus, the general objective of this study was to evaluate the density, hardness, flexural strength, dilatometric behavior and to analyze the microstructure of metal matrix composites based nickel with addition of carbides of tantalum and / or niobium when sintered in a conventional furnace and Plasma assisted debinding and sintering (PADS). Initially, were defineds best parameters of granulation, screening and mixing procedure. After, mixtures of carbonyl Ni and 5%, 10% and 15 wt.% NbC and TaC were prepared in a Y-type mixer under wet conditions during 60 minutes. The mixtures were then dried and granulated using 1.5 wt. % paraffin diluted in hexane. Granulates were cold pressed under 600 MPa. Paraffin was then removed from the pressed pellets during a pre-sintering process carried out in a tubular furnace at 500 °C during 30 min. The heating rate was 3 ºC/min. The pellets were then sintered using either a plasma assisted reactor or a conventional resistive tubular furnace. For both methods, the heating rate was set to 8 ºC/min up to 1150 °C. The holding time was 60 minutes. The microstructure of the sintered samples was evaluated by SEM. Brinell hardness tests were also carried out. The results revealed that higher density and higher hardness values were observed in the plasma-assisted sintered samples. Hardness increased with the concentration of carbides in the Ni-matrix. The flexural strength also increased by adding the carbides. The decline was larger for the sample with addition of 5% 5% TaC and NbC. In general, compositions containing added carbide 10% showed less porous and more uniform distribution of carbides in the nickel matrix microstructural appearance. Thus, both added carbide and plasma sintering improved density, hardness, flexural strength and microstructural appearance of the composites