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.

Correlação entre as propriedades mecânicas de materiais impermeabilizantes a base de elastômeros de poliuréia e poliuretano com o desempenho do sistema aplicado em lajes estruturais

Dissertação (mestrado)—Universidade de Brasília, Faculdade de Tecnologia, Departamento de Engenharia Civil e Ambiental, Programa de Pós-graduação em Estruturas e Construção Civil, 2015.

Caracterización espectroscópica de impedancia de polímeros para el uso en electrodos de electrocardiogramas

Un estudio comparativo de la impedancia de un polímero tipo poliolefina termoplástica elastómera con un electrodo comercial gelificado universal ha sido hecho con el fin de determinar si el polímero puede ser usado como electrodo seco para la adquisición de señales cardiacas. Los resultados de la espectrometría de impedancia mostraron características muy parecidas y que ambos se comportan como dispositivos resistores, por ejemplo a 120 Hz el polímero registró una resistencia de 6,3 k y el electrodo comercial 7,2 k . Además, se obtuvo una relación lineal de corriente contra voltaje, determinando resistencias de 7 k y 8,2 k para el polímero y electrodo comercial gelificado respectivamente. Finalmente concluimos que es aplicable el uso de este polímero en electrodos secos.

Evaluation of the genotoxicity of cellulose nanofibers

Background: Agricultural products and by products provide the primary materials for a variety of technological applications in diverse industrial sectors. Agro-industrial wastes, such as cotton and curaua fibers, are used to prepare nanofibers for use in thermoplastic films, where they are combined with polymeric matrices, and in biomedical applications such as tissue engineering, amongst other applications. The development of products containing nanofibers offers a promising alternative for the use of agricultural products, adding value to the chains of production. However, the emergence of new nanotechnological products demands that their risks to human health and the environment be evaluated. This has resulted in the creation of the new area of nanotoxicology, which addresses the toxicological aspects of these materials.Purpose and methods: Contributing to these developments, the present work involved a genotoxicological study of different nanofibers, employing chromosomal aberration and comet assays, as well as cytogenetic and molecular analyses, to obtain preliminary information concerning nanofiber safety. The methodology consisted of exposure of Allium cepa roots, and animal cell cultures (lymphocytes and fibroblasts), to different types of nanofibers. Negative controls, without nanofibers present in the medium, were used for comparison.Results: The nanofibers induced different responses according to the cell type used. In plant cells, the most genotoxic nanofibers were those derived from green, white, and brown cotton, and curaua, while genotoxicity in animal cells was observed using nanofibers from brown cotton and curaua. An important finding was that ruby cotton nanofibers did not cause any significant DNA breaks in the cell types employed.Conclusion: This work demonstrates the feasibility of determining the genotoxic potential of nanofibers derived from plant cellulose to obtain information vital both for the future usage of these materials in agribusiness and for an understanding of their environmental impacts.

MICROFLUIDIC ASSAY PERFORMANCE ENHANCEMENT USING POROUS VOLUMETRIC DETECTION ELEMENTS FOR IMPEDEMETRIC AND OPTICAL SENSING

Microfluidic technologies have great potential to help create automated, cost-effective, portable devices for rapid point of care (POC) diagnostics in diverse patient settings. Unfortunately commercialization is currently constrained by the materials, reagents, and instrumentation required and detection element performance. While most microfluidic studies utilize planar detection elements, this dissertation demonstrates the utility of porous volumetric detection elements to improve detection sensitivity and reduce assay times. Impedemetric immunoassays were performed utilizing silver enhanced gold nanoparticle immunoconjugates (AuIgGs) and porous polymer monolith or silica bead bed detection elements within a thermoplastic microchannel. For a direct assay with 10 µm spaced electrodes the detection limit was 0.13 fM AuIgG with a 3 log dynamic range. The same assay was performed with electrode spacing of 15, 40, and 100 µm with no significant difference between configurations. For a sandwich assay the detection limit was10 ng/mL with a 4 log dynamic range. While most impedemetric assays rely on expensive high resolution electrodes to enhance planar senor performance, this study demonstrates the employment of porous volumetric detection elements to achieve similar performance using lower resolution electrodes and shorter incubation times. Optical immunoassays were performed using porous volumetric capture elements perfused with refractive index matching solutions to limit light scattering and enhance signal. First, fluorescence signal enhancement was demonstrated with a porous polymer monolith within a silica capillary. Next, transmission enhancement of a direct assay was demonstrated by infusing aqueous sucrose solutions through silica bead beds with captured silver enhanced AuIgGs yielding a detection limit of 0.1 ng/mL and a 5 log dynamic range. Finally, ex situ functionalized porous silica monolith segments were integrated into thermoplastic channels for a reflectance based sandwich assay yielding a detection limit of 1 ng/mL and a 5 log dynamic range. The simple techniques for optical signal enhancement and ex situ element integration enable development of sensitive, multiplexed microfluidic sensors. Collectively the demonstrated experiments validate the use of porous volumetric detection elements to enhance impedemetric and optical microfluidic assays. The techniques rely on commercial reagents, materials compatible with manufacturing, and measurement instrumentation adaptable to POC diagnostics.

Microfabricated elastomer tactile sensors for robotic fingertip systems

Tactile sensing is an important aspect of robotic systems, and enables safe, dexterous robot-environment interaction. The design and implementation of tactile sensors on robots has been a topic of research over the past 30 years, and current challenges include mechanically flexible “sensing skins”, high dynamic range (DR) sensing (i.e.: high force range and fine force resolution), multi-axis sensing, and integration between the sensors and robot. This dissertation focuses on addressing some of these challenges through a novel manufacturing process that incorporates conductive and dielectric elastomers in a reusable, multilength-scale mold, and new sensor designs for multi-axis sensing that improve force range without sacrificing resolution. A single taxel was integrated into a 1 degree of freedom robotic gripper for closed-loop slip detection. Manufacturing involved casting a composite silicone rubber, polydimethylsiloxane (PDMS) filled with conductive particles such as carbon nanotubes, into a mold to produce microscale flexible features on the order of 10s of microns. Molds were produced via microfabrication of silicon wafers, but were limited in sensing area and were costly. An improved technique was developed that produced molds of acrylic using a computer numerical controlled (CNC) milling machine. This maintained the ability to produce microscale features, and increased the sensing area while reducing costs. New sensing skins had features as small as 20 microns over an area as large as a human hand. Sensor architectures capable of sensing both shear and normal force sensing with high dynamic range were produced. Using this architecture, two sensing modalities were developed: a capacitive approach and a contact resistive approach. The capacitive approach demonstrated better dynamic range, while the contact resistive approach used simpler circuitry. Using the contact resistive approach, normal force range and resolution were 8,000 mN and 1,000 mN, respectively, and shear force range and resolution were 450 mN and 100 mN, respectively. Using the capacitive approach, normal force range and resolution were 10,000 mN and 100 mN, respectively, and shear force range and resolution were 1,500 mN and 50 mN, respectively.

Characterization of a biodegradable starch based film. Application on the preservation of fresh spinach

Mestrado em Engenharia Alimentar - Instituto Superior de Agronomia - UL

Biocompósitos poliméricos obtidos a partir da fração lignocelulósica e amilácea do caroço de manga (mangifera indica), Tommy atkins

This employment has the function the utilization of mango seeds Tommy Atkins, like starch source to obtain biopolymers and fibers source and nanowhiskers cellulose also, that will be use like reinforcing fillers in micro and nanobiocomposites polymeric. The fibers in natura removed from tegument mango seed were characterized, as weel as the treated fibers and nanowhiskers of cellulose extracted from them. The starch extracted from seed s almond showed a good performance (32%) and a high purity. The chemicals analyzes, of crystallinity and morphological of the fibers in natura, treated fibers and nanowhiskers of cellulose confirmed the efficacy of the chemical treatement performed to remove amorphous constituents (hemicellulose and lignina). The thermoplastic starch (TPS) obtained from two sources, corn starch and starchy material mango, was produced in a twin screw extruder with compositon mass of 62,5% of starch, 9,4% of water and 28,1% of glycerol. The starch material mango was the main objective of this work for the production of biodegradable materials, and the starch corn was utilized during the production stage to evaluate the processability of the starch and use as parameter for comparison, according of being a conventional source for obtaining conventional comercial starch. The incorporation of fibers (6% in mass) and nanowhiskers cellulose (1% in mass) in matrix of TPS to obtain composite and nanocomposite, respectively, it was performed in single screw extruder. The biocomposites and bionanocomposites polymeric were obtained and the TPS from starchy material mango presented better results of thermal and mechanicals properties when compared to TPS corn starch. Concludes that the sediment generated of the agroindustrial processing mango used presents potencial to producing of biodegradables materials

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

Drought impact on rainfed common bean production areas in Brazil.

Common bean production in Goiás, Brazil is concentrated in the same geographic area, but spread acrossthree distinct growing seasons, namely, wet, dry and winter. In the wet and dry seasons, common beansare grown under rainfed conditions, whereas the winter sowing is fully irrigated. The conventional breed-ing program performs all varietal selection stages solely in the winter season, with rainfed environmentsbeing incorporated in the breeding scheme only through the multi environment trials (METs) wherebasically only yield is recorded. As yield is the result of many interacting processes, it is challengingto determine the events (abiotic or biotic) associated with yield reduction in the rainfed environments(wet and dry seasons). To improve our understanding of rainfed dry bean production so as to produceinformation that can assist breeders in their efforts to develop stress-tolerant, high-yielding germplasm,we characterized environments by integrating weather, soil, crop and management factors using cropsimulation models. Crop simulations based on two commonly grown cultivars (Pérola and BRS Radi-ante) and statistical analyses of simulated yield suggest that both rainfed seasons, wet and dry, can bedivided in two groups of environments: highly favorable environment and favorable environment. Forthe wet and dry seasons, the highly favorable environment represents 44% and 58% of production area,respectively. Across all rainfed environment groups, terminal and/or reproductive drought stress occursin roughly one fourth of the seasons (23.9% for Pérola and 24.7% for Radiante), with drought being mostlimiting in the favorable environment group in the dry TPE. Based on our results, we argue that eventhough drought-tailoring might not be warranted, the common bean breeding program should adapttheir selection practices to the range of stresses occurring in the rainfed TPEs to select genotypes moresuitable for these environments.

CHARACTERIZATION OF THERMAL AND MECHANICAL PROPERTIES OF POLYPROPYLENE–BASED COMPOSITES FOR FUEL CELL BIPOLAR PLATES AND DEVELOPMENT OF EDUCATIONAL TOOLS IN HYDROGEN AND FUEL CELL TECHNOLOGIES

In this project we developed conductive thermoplastic resins by adding varying amounts of three different carbon fillers: carbon black (CB), synthetic graphite (SG) and multi–walled carbon nanotubes (CNT) to a polypropylene matrix for application as fuel cell bipolar plates. This component of fuel cells provides mechanical support to the stack, circulates the gases that participate in the electrochemical reaction within the fuel cell and allows for removal of the excess heat from the system. The materials fabricated in this work were tested to determine their mechanical and thermal properties. These materials were produced by adding varying amounts of single carbon fillers to a polypropylene matrix (2.5 to 15 wt.% Ketjenblack EC-600 JD carbon black, 10 to 80 wt.% Asbury Carbons’ Thermocarb TC-300 synthetic graphite, and 2.5 to 15 wt.% of Hyperion Catalysis International’s FIBRILTM multi-walled carbon nanotubes) In addition, composite materials containing combinations of these three fillers were produced. The thermal conductivity results showed an increase in both through–plane and in–plane thermal conductivities, with the largest increase observed for synthetic graphite. The Department of Energy (DOE) had previously set a thermal conductivity goal of 20 W/m·K, which was surpassed by formulations containing 75 wt.% and 80 wt.% SG, yielding in–plane thermal conductivity values of 24.4 W/m·K and 33.6 W/m·K, respectively. In addition, composites containing 2.5 wt.% CB, 65 wt.% SG, and 6 wt.% CNT in PP had an in–plane thermal conductivity of 37 W/m·K. Flexural and tensile tests were conducted. All composite formulations exceeded the flexural strength target of 25 MPa set by DOE. The tensile and flexural modulus of the composites increased with higher concentration of carbon fillers. Carbon black and synthetic graphite caused a decrease in the tensile and flexural strengths of the composites. However, carbon nanotubes increased the composite tensile and flexural strengths. Mathematical models were applied to estimate through–plane and in–plane thermal conductivities of single and multiple filler formulations, and tensile modulus of single–filler formulations. For thermal conductivity, Nielsen’s model yielded accurate thermal conductivity values when compared to experimental results obtained through the Flash method. For prediction of tensile modulus Nielsen’s model yielded the smallest error between the predicted and experimental values. The second part of this project consisted of the development of a curriculum in Fuel Cell and Hydrogen Technologies to address different educational barriers identified by the Department of Energy. By the creation of new courses and enterprise programs in the areas of fuel cells and the use of hydrogen as an energy carrier, we introduced engineering students to the new technologies, policies and challenges present with this alternative energy. Feedback provided by students participating in these courses and enterprise programs indicate positive acceptance of the different educational tools. Results obtained from a survey applied to students after participating in these courses showed an increase in the knowledge and awareness of energy fundamentals, which indicates the modules developed in this project are effective in introducing students to alternative energy sources.

Acoustic manipulation and alignment of particles for applications in separation, micro-templating and device fabrication

This dissertation studies the manipulation of particles using acoustic stimulation for applications in microfluidics and templating of devices. The term particle is used here to denote any solid, liquid or gaseous material that has properties, which are distinct from the fluid in which it is suspended. Manipulation means to take over the movements of the particles and to position them in specified locations. ^ Using devices, microfabricated out of silicon, the behavior of particles under the acoustic stimulation was studied with the main purpose of aligning the particles at either low-pressure zones, known as the nodes or high-pressure zones, known as anti-nodes. By aligning particles at the nodes in a flow system, these particles can be focused at the center or walls of a microchannel in order to ultimately separate them. These separations are of high scientific importance, especially in the biomedical domain, since acoustopheresis provides a unique approach to separate based on density and compressibility, unparalleled by other techniques. The study of controlling and aligning the particles in various geometries and configurations was successfully achieved by controlling the acoustic waves. ^ Apart from their use in flow systems, a stationary suspended-particle device was developed to provide controllable light transmittance based on acoustic stimuli. Using a glass compartment and a carbon-particle suspension in an organic solvent, the device responded to acoustic stimulation by aligning the particles. The alignment of light-absorbing carbon particles afforded an increase in visible light transmittance as high as 84.5%, and it was controlled by adjusting the frequency and amplitude of the acoustic wave. The device also demonstrated alignment memory rendering it energy-efficient. A similar device for suspended-particles in a monomer enabled the development of electrically conductive films. These films were based on networks of conductive particles. Elastomers doped with conductive metal particles were rendered surface conductive at particle loadings as low as 1% by weight using acoustic focusing. The resulting films were flexible and had transparencies exceeding 80% in the visible spectrum (400-800 nm) These films had electrical bulk conductivities exceeding 50 S/cm. ^

Optimization of extrusion process to obtain shrimp snacks with rice grits and polished rice grains.

This research studied the effect of thermoplastic extrusion on the expansion index (EI), water absorption index (WAI), water solubility index (WSI), and sensory acceptance (SA) of a snack from rice grits, polished rice grains, and shrimp. A 23 factorial design was used with independent variables, temperature in the third extruder zone (63.2?96.8°C), initial moisture (106.4?173.6 g/kg), and shrimp content (16?184 g/kg), whereas EI, WAI, WSI, and SA were the responses. Through the surface-response methodology, the formulation with 80 g/kg shrimp and 130 g/kg initial moisture processed at 85°C in the third extruder zone was considered optimal. The product had good EI, WAI, and SA, 65.6 g/kg moisture, 24.0 g/kg lipids, 89.5 g/kg proteins, 34.2 kg/kg ashes, 72.4 g/kg fibers, and 714.3 g/kg carbohydrates. The product is an alternative for using rice grit, which has low commercial value, while also fully using the regional shrimp.

Relação entre resistência ao cisalhamento no plano e parâmetros processuais de co-cura de juntas em compósitos auto-reforçados de polietileno de matriz reprocessada

Este estudo investiga a otimização da resistência ao cisalhamento no plano de juntas de sobreposição co-curadas do compósito termoplástico unidirecional auto-reforçado de polietileno de baixa densidade reciclado reforçado por fibras de polietileno de ultra alto peso molecular através da relação desta resistência com os parâmetros processuais de prensagem a quente para a conformação da junta (pressão, temperatura, tempo e comprimento). A matriz teve sua estrutura química analisada para verificar potenciais degradações devidas à sua origem de reciclagem. Matriz e reforço foram caracterizados termicamente para definir a janela de temperatura de processamento de junta a ser estudada. A elaboração das condições de cura dos corpos de prova foi feita de acordo com a metodologia de Projeto de Experimento de Superfície de Resposta e a relação entre a resistência ao cisalhamento das juntas e os respectivos parâmetros de cura foi obtida através de equação de regressão gerada pelo método dos Mínimos Quadrados Ordinários. A caracterização mecânica em tração do material foi analisada micro e macromecanicamente. A análise química da matriz não demonstrou a presença de grupos carboxílicos que evidenciassem degradação por ramificações de cadeia e reticulação advindos da reciclagem do material. As metodologias de ensaio propostas demonstraram ser eficazes, podendo servir como base para a constituição de normas técnicas. Demonstrou-se que é possível obter juntas com resistência ótima ao cisalhamento de 6,88 MPa quando processadas a 1 bar, 115°C, 5 min e com 12 mm. A análise da fratura revelou que a ruptura por cisalhamento das juntas foi precedida por múltiplas fissuras longitudinais induzidas por sucessivos debondings, tanto dentro quanto fora da junta, devido à tensão transversal acumulada na mesma, proporcional a seu comprimento. A temperatura demonstrou ser o parâmetro de processamento mais relevante para a performance da junta, a qual é pouco afetada por variações na pressão e tempo de cura.

Preparation and characterization of multifunctional bio-based polymers exhibiting enhanced properties

Driven by environmental reasons and the expected depletion of crude oil, bio-based polymers are currently undergoing a renaissance in the attempt to replace fossil-based ones. The present work aims at contributing in the development of the steps that start from biomass and move to new polymeric multifunctional materials. The study focuses on two bio-based building blocks (itaconic and vanillic acids) characterized by exploitable functionalities, i.e. a lateral double bond and a substituted aromatic ring respectively, able to confer interesting properties to the final polymers. The lateral double bond of dimethyl itaconate was functionalized via thia-Michael addition reaction obtaining a thermo-stable building block that can undergo polycondensation under classical conditions of reaction. The addition of a long lateral chain allows the polymer to express antimicrobial activity against Staphylococcus aureus making it attractive for packaging and targeting antimicrobial applications. Moreover, the architecture of the homopolymer was modified by means of copolymerization with dimethyl 2,5-furandicarboxylate thus improving the rigidity and obtaining a thermo-processable material. Potential applications as thermoset or thermoplastic material have been discussed. As concerns vanillic acid, the presence of aromatic rings on the polymer backbone imparts high thermal stability, but brittle behaviour in the homopolymer. Therefore, the architecture of the polyester was successfully tuned by means of copolymerization with a flexible bio-based comonomer, i.e. ω-pentadecalactone, providing processable random copolymers. An in depth investigation of water transport mechanism has been undertaken on the synthesized polyesters. Since the copolymers present a succession of aromatic and aliphatic units, as a consequence of the chemical structure water vapor permeability interposes between polyethylene and poly(ethylene terephthalate) proving that the copolyesters are suitable for packaging applications. Moving towards a sustainable model of development, novel sustainable synthetic pathways for the eco-design of new bio-based polymeric structures with high value functionalities and different potential applications have been successfully developed.