Preparação e caracterização da casca de banana prata particulada para aplicação com reforço em compósito de matriz de PEAD

The waste, exaggerated and incorrect disposal of biomass are common practices in modern times where everything is disposable. However the growing concern with the nature and the environment compel man to give nobler destinations for these products through sustainability and recycling of waste. Banana peel is a residual biomass, which is not consumed. It generates tons of waste per week in São Paulo city. This trash is disposed in dumps and landfills, which could be reduced by using it as reinforcement in natural composites. The high density polyethylene (HDPE) is a polymer derived from the ethylene polymerization and is easily recycled. Which makes it a sustainable material. In the present work characteristics of the natural composite composed with banana peel and high-density polyethylene were studied. It was noted that removing the lignin present in the banana peel, the fiber introduces a significant improvement in thermal resistance. The preparation of composite was made with a ratio of 5% and 10% of reinforcement in comparison with polymeric matrix mass. Composites were thermally, mechanically and microscopically characterized. The addition of fiber in the polymer increased the mechanical strength of the composite. The fiber surface treatment with distilled water removed the amorphous material present in the fibers, improving significantly thermal stability and increasing crystallinity of the celullose. The addition of 5% fiber in mass to the polymer increased significantly the tensile strength and elasticity modulus for the composite. With 10% of fiber addiction there were also an improvement when compared with pure HDPE, but when compared with 5% composite the mechanical properties are slightly lower. This may be due to the fiber particle size, which are small and eventually become a hub of tension ... (Complete abstract click electronic access below)

Estudo da superfície de fibras de carbono após tratamento de implantação iônica por imersão em plasma (3IP)

In this work, plasma immersion ion implantation (PIII) treatments of carbon fibers (CFs) were performed in order to induce modifications of chemical and physical properties of the CF surface aimed to improve the performance of thermoplastic composite. The samples to be treated were immersed in nitrogen or air glow discharge plasma and pulsed at −3.0 kV for 2.0, 5.0, 10.0, and 15.0 min. After PIII processing, the specimens were characterized by atomic force microscopy (AFM), scanning electron microscopy, Raman spectroscopy, and X-ray photoelectron spectroscopy (XPS). After CFs treatments, the CF/Polypropylene (PP) composites were produced by hot pressing method. Surface morphology of as-received CFs exhibited some scratches aligned along the fibers due to the fiber manufacturing process. After both treatments, these features became deeper, and also, a number of small particles nonuniformly distributed on the fiber surface can be observed. These particles are product of CF surface sputtering during the PIII treatment, which removes the epoxy layer that covers as-received samples. AFM analyses of CF samples treated with nitrogen depicted a large increase of the surface roughness (Rrms value approximately six times higher than that of the untreated sample). The increase of the roughness was also observed for samples treated by air PIII. Raman spectra of all samples presented the characteristic D- and G-bands at approximately 1355 and 1582 cm−1, respectively. Analysis of the surface chemical composition provided by the XPS showed that nitrogen and oxygen were incorporated onto the surface. The polar radicals formed on the surface lead to increasing of the CF surface energy. Both the modification of surface roughness and the surface oxidation contributed for the enhancement of CF adhesion to the polymeric matrix. These features were confirmed ... (Complete abstract click electronic access below)

Estudo da modificação superficial de fibras de carbono por meio de tratamentos a plasma para o aumento da adesão na interface de compósitos fibra de carbono/PPS

Pós-graduação em Engenharia Mecânica - FEG

Avaliação térmica e estrutural do bagaço de cana de açúcar pré-tratado com ozônio, ultrassom e micro-ondas para produção de etanol celulósico por hidrólise enzimática

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

Estudo do efeito da cristalinidade nas propriedades mecânicas de compósitos termoplásticos com aplicações aeronáuticas

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

Electrospun Polymeric Scaffolds with Enhanced Biomimetic Properties for Tissue Engineering Applications

This PhD Thesis is focused on the development of fibrous polymeric scaffolds for tissue engineering applications and on the improvement of scaffold biomimetic properties. Scaffolds were fabricated by electrospinning, which allows to obtain scaffolds made of polymeric micro or nanofibers. Biomimetism was enhanced by following two approaches: (1) the use of natural biopolymers, and (2) the modification of the fibers surface chemistry. Gelatin was chosen for its bioactive properties and cellular affinity, however it lacks in mechanical properties. This problem was overcome by adding poly(lactic acid) to the scaffold through co-electrospinning and mechanical properties of the composite constructs were assessed. Gelatin effectively improves cell growth and viability and worth noting, composite scaffolds of gelatin and poly(lactic acid) were more effective than a plain gelatin scaffold. Scaffolds made of pure collagen fibers were fabricated. Modification of collagen triple helix structure in electrospun collagen fibers was studied. Mechanical properties were evaluated before and after crosslinking. The crosslinking procedure was developed and optimized by using - for the first time on electrospun collagen fibers - the crosslinking reactant 1,4-butanediol diglycidyl ether, with good results in terms of fibers stabilization. Cell culture experiments showed good results in term of cell adhesion and morphology. The fiber surface chemistry of electrospun poly(lactic acid) scaffold was modified by plasma treatment. Plasma did not affect thermal and mechanical properties of the scaffold, while it greatly increased its hydrophilicity by the introduction of carboxyl groups at the fiber surface. This fiber functionalization enhanced the fibroblast cell viability and spreading. Surface modifications by chemical reactions were conducted on electrospun scaffolds made of a polysophorolipid. The aim was to introduce a biomolecule at the fiber surface. By developing a series of chemical reactions, one oligopeptide every three repeating units of polysophorolipid was grafted at the surface of electrospun fibers.

Nanofiber-based spectroscopy of organic molecules

This thesis reports on the experimental realization of nanofiber-based spectroscopy of organic molecules. The light guided by subwavelength diameter optical nanfibers exhibits a pronounced evanescent field surrounding the fiber which yields high excitation and emission collection efficiencies for molecules on or near the fiber surface.rnThe optical nanofibers used for the experiments presented in this thesis are realized as thernsub-wavelength diameter waist of a tapered optical fiber (TOF). The efficient transfer of thernlight from the nanofiber waist to the unprocessed part of the TOF depends critically on therngeometric shape of the TOF transitions which represent a nonuniformity of the TOF. Thisrnnonuniformity can cause losses due to coupling of the fundamental guided mode to otherrnmodes which are not guided by the taper over its whole length. In order to quantify the lossrnfrom the fundamental mode due to tapering, I have solved the coupled local mode equationsrnin the approximation of weak guidance for the three layer system consisting of fiber core andrncladding as well as the surrounding vacuum or air, assuming the taper shape of the TOFsrnused for the experiments presented in this thesis. Moreover, I have empirically studied therninfluence of the TOF geometry on its transmission spectra and, based on the results, I haverndesigned a nanofiber-waist TOF with broadband transmission for experiments with organicrnmolecules.rnAs an experimental demonstration of the high sensitivity of nanofiber-based surface spectroscopy, I have performed various absorption and fluorescence spectroscopy measurements on the model system 3,4,9,10-perylene-tetracarboxylic dianhydride (PTCDA). The measured homogeneous and inhomogeneous broadening of the spectra due to the interaction of the dielectric surface of the nanofiber with the surface-adsorbed molecules agrees well with the values theoretically expected and typical for molecules on surfaces. Furthermore, the self-absorption effects due to reasorption of the emitted fluorescence light by circumjacent surface-adsorbed molecules distributed along the fiber waist have been analyzed and quantified. With time-resolved measurements, the reorganization of PTCDA molecules to crystalline films and excimers can be observed and shown to be strongly catalyzed by the presence of water on the nanofiber surface. Moreover, the formation of charge-transfer complexes due to the interaction with localized surface defects has been studied. The collection efficiency of the molecular emission by the guided fiber mode has been determined by interlaced measurements of absorption and fluorescence spectra to be about 10% in one direction of the fiber.rnThe high emission collection efficiency makes optical nanofibers a well-suited tool for experiments with dye molecules embedded in small organic crystals. As a first experimental realization of this approach, terrylene-doped para-terphenyl crystals attached to the nanofiber-waist of a TOF have been studied at cryogenic temperatures via fluorescence and fluorescence excitation spectroscopy. The statistical fine structure of the fluorescence excitation spectrum for a specific sample has been observed and used to give an estimate of down to 9 molecules with center frequencies within one homogeneous width of the laser wavelength on average for large detunings from resonance. The homogeneous linewidth of the transition could be estimated to be about 190MHz at 4.5K.

A membrane-associated form of sucrose synthase and its potential role in synthesis of cellulose and callose in plants.

Sucrose synthase (SuSy; EC 2.4.1.13; sucrose + UDP reversible UDPglucose + fructose) has always been studied as a cytoplasmic enzyme in plant cells where it serves to degrade sucrose and provide carbon for respiration and synthesis of cell wall polysaccharides and starch. We report here that at least half of the total SuSy of developing cotton fibers (Gossypium hirsutum) is tightly associated with the plasma membrane. Therefore, this form of SuSy might serve to channel carbon directly from sucrose to cellulose and/or callose synthases in the plasma membrane. By using detached and permeabilized cotton fibers, we show that carbon from sucrose can be converted at high rates to both cellulose and callose. Synthesis of cellulose or callose is favored by addition of EGTA or calcium and cellobiose, respectively. These findings contrast with the traditional observation that when UDPglucose is used as substrate in vitro, callose is the major product synthesized. Immunolocalization studies show that SuSy can be localized at the fiber surface in patterns consistent with the deposition of cellulose or callose. Thus, these results support a model in which SuSy exists in a complex with the beta-glucan synthases and serves to channel carbon from sucrose to glucan.

EDC-mediated oligonucleotide immobilization on a long period grating optical biosensor

We present the development and simplification of label-free fiber optic biosensors based on immobilization of oligonucleotides on dual-peak long period gratings (dLPGs). This improvement is the result of a simplification of biofunctionalization methodology. A one-step 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide (EDC)-mediated reaction has been developed for the straightforward immobilization of unmodified oligonucleotides on the glass fiber surface along the grating region, leading to covalent attachment of a 5´-phosphorylated probe oligonucleotide to the amino-derivatized fiber grating surface. Immobilization is achieved via a 5´phosphate-specific linkage, leaving the remainder of the oligonucleotide accessible for binding reactions. The dLPG has been tested in different external media to demonstrate its inherent ultrahigh sensitivity to the surrounding-medium refractive index (RI) achieving 50- fold improvement in RI sensitivity over the previously-published LPG sensor in media with RI’s relevant to biological assays. After functionalization, the dLPG biosensor was used to monitor the hybridization of complementary oligonucleotides showing a detectable oligonucleotide concentration of 4 nM. The proposed one-step EDC reaction approach can be further extended to develop fiber optic biosensors for disease analysis and medical diagnosis with the advances of label-free, real-time, multiplex, high sensitivity and specificity.

Nanobump microresonator

We introduce a whispering gallery-mode (WGM) nanobump microresonator (NBMR) and develop its theory. This microresonator is formed by an asymmetric nanoscale-high deformation of the translationally symmetric optical fiber surface, which is employed in fabrication of surface nanoscale axial photonics (SNAP) structures. It is shown that an NBMR causes strong localization of WGMs near a closed ray (geodesic) at the fiber surface, provided that this ray is stable. Our theory explains and describes the experimentally observed localization of WGMs by NBMRs and is useful for the design and fabrication of SNAP devices.

Permanent matching of coupled optical bottle resonators with better than 0.16 GHz precision

The fabrication precision is one of the most critical challenges to the creation of practical photonic circuits composed of coupled high Q-factor microresonators. While very accurate transient tuning of microresonators based on local heating has been reported, the record precision of permanent resonance positioning achieved by post-processing is still within 1 and 5 GHz. Here we demonstrate two coupled bottle microresonators fabricated at the fiber surface with resonances that are matched with a better than 0.16 GHz precision. This corresponds to a better than 0.17 Å precision in the effective fiber radius variation. The achieved fabrication precision is only limited by the resolution of our optical spectrum analyzer and can be potentially improved by an order of magnitude.

MOLECULAR MODELING OF EPON 862-DETDA / CARBON COMPOSITES

The thermoset epoxy resin EPON 862, coupled with the DETDA hardening agent, are utilized as the polymer matrix component in many graphite (carbon fiber) composites. Because it is difficult to experimentally characterize the interfacial region, computational molecular modeling is a necessary tool for understanding the influence of the interfacial molecular structure on bulk-level material properties. The purpose of this research is to investigate the many possible variables that may influence the interfacial structure and the effect they will have on the mechanical behavior of the bulk level composite. Molecular models are established for EPON 862-DETDA polymer in the presence of a graphite surface. Material characteristics such as polymer mass-density, residual stresses, and molecular potential energy are investigated near the polymer/fiber interface. Because the exact degree of crosslinking in these thermoset systems is not known, many different crosslink densities (degrees of curing) are investigated. It is determined that a region exists near the carbon fiber surface in which the polymer mass density is different than that of the bulk mass density. These surface effects extend ~10 Å into the polymer from the center of the outermost graphite layer. Early simulations predict polymer residual stress levels to be higher near the graphite surface. It is also seen that the molecular potential energy in polymer atoms decreases with increasing crosslink density. New models are then established in order to investigate the interface between EPON 862-DETDA polymer and graphene nanoplatelets (GNPs) of various atomic thicknesses. Mechanical properties are extracted from the models using Molecular Dynamics techniques. These properties are then implemented into micromechanics software that utilizes the generalized method of cells to create representations of macro-scale composites. Micromechanics models are created representing GNP doped epoxy with varying number of graphene layers and interfacial polymer crosslink densities. The initial micromechanics results for the GNP doped epoxy are then taken to represent the matrix component and are re-run through the micromechanics software with the addition of a carbon fiber to simulate a GNP doped epoxy/carbon fiber composite. Micromechanics results agree well with experimental data, and indicate GNPs of 1 to 2 atomic layers to be highly favorable. The effect of oxygen bonded to the surface of the GNPs is lastly investigated. Molecular Models are created for systems with varying graphene atomic thickness, along with different amounts of oxygen species attached to them. Models are created for graphene containing hydroxyl groups only, epoxide groups only, and a combination of epoxide and hydroxyl groups. Results show models of oxidized graphene to decrease in both tensile and shear modulus. Attaching only epoxide groups gives the best results for mechanical properties, though pristine graphene is still favored.

Coupling of composite resin cements to quartz fiber posts: A comparison of industrial and ""chairside"" treatments of the post surface

Purpose: To evaluate the influence of surface treatments on microtensile bond strength of luting resin cements to fiber posts. Materials and Methods: Forty-two quartz fiber posts (Light Post, RTD) were divided into 7 groups (n = 6) according to the surface treatment. I and 11: experimental patented industrial treatment consisting of zirconium oxide coating and silanization (RTD); III: industrial treatment followed by adhesive application (XPBond, Dentsply Caulk); IV: adhesive (XPBond); V: adhesive (Prime&Bond NT, Dentsply Caulk); VI: silane (Calibra Silane, Dentsply Caulk); VII: no treatment. Adhesives were used in the self-curing mode. Two cements (Sealbond, RTD - group 1, and Calibra, Dentsply Caulk - groups 11 to VII) were applied on the posts to produce cylindrical specimens. Post/cement interfaces were evaluated under SEM. The surface of the industrially coated posts was examined using energy dispersive analysis by x-ray. Cylinders were cut to obtain microtensile sticks that were loaded in tension at a crosshead speed of 0.5 mm/min until failure. Statistical analysis was performed using Kruskal-Wallis analysis of variance followed by Dunn`s multiple range test for post-hoc comparisons (p < 0.05). Weibull analysis was also performed. Results: The post/cement bond strength was significantly higher on fiber posts treated industrially (I: 23.14 +/- 8.05 MPa; II: 21.56 +/- 7.07 MPa; III: 22.37 +/- 7.00 MPa) or treated with XPBond adhesive (IV: 21.03 +/- 5.34 MPa) when compared to Prime&Bond NT application (V: 14.05 +/- 5.06 MPa), silanization (VI: 6.31 +/- 4.60 MPa) or no treatment (VII: 4.62 +/- 4.31) of conventional fiber posts (p < 0.001). Conclusion: The experimental industrial surface treatment and the adhesive application enhanced fiber post to resin cement interfacial strength. Industrial pretreatment may simplify the clinical luting procedure.

Enzymatic treatments to improve mechanical properties and surface hydrophobicity of jute fiber membranes

Fiber membranes prepared from jute fragments can be valuable, low cost, and renewable. They have broad application prospects in packing bags, geotextiles, filters, and composite reinforcements. Traditionally, chemical adhesives have been used to improve the properties of jute fiber membranes. A series of new laccase, laccase/mediator systems, and multi-enzyme synergisms were attempted. After the laccase treatment of jute fragments, the mechanical properties and surface hydrophobicity of the produced fiber membranes increased because of the cross-coupling of lignins with ether bonds mediated by laccase. The optimum conditions were a buffer pH of 4.5 and an incubation temperature of 60 °C with 0.92 U/mL laccase for 3 h. Laccase/guaiacol and laccase/alkali lignin treatments resulted in remarkable increases in the mechanical properties; in contrast, the laccase/2,2-azino-bis-(3-ethylthiazoline-6-sulfonate) (ABTS) and laccase/2,6-dimethoxyphenol treatments led to a decrease. The laccase/ guaiacol system was favorable to the surface hydrophobicity of jute fiber membranes. However, the laccase/alkali lignin system had the opposite effect. Xylanase/laccase and cellulase/laccase combined treatments were able to enhance both the mechanical properties and the surface hydrophobicity of jute fiber membranes. Among these, cellulase/laccase treatment performed better; compared to mechanical properties, the surface hydrophobicity of the jute fiber membranes showed only a slight increase after the enzymatic multi-step processes.

Surface transformation hardening of carbon steel with high power fiber laser

This study investigated the surface hardening of steels via experimental tests using a multi-kilowatt fiber laser as the laser source. The influence of laser power and laser power density on the hardening effect was investigated. The microhardness analysis of various laser hardened steels was done. A thermodynamic model was developed to evaluate the thermal process of the surface treatment of a wide thin steel plate with a Gaussian laser beam. The effect of laser linear oscillation hardening (LLOS) of steel was examined. An as-rolled ferritic-pearlitic steel and a tempered martensitic steel with 0.37 wt% C content were hardened under various laser power levels and laser power densities. The optimum power density that produced the maximum hardness was found to be dependent on the laser power. The effect of laser power density on the produced hardness was revealed. The surface hardness, hardened depth and required laser power density were compared between the samples. Fiber laser was briefly compared with high power diode laser in hardening medium-carbon steel. Microhardness (HV0.01) test was done on seven different laser hardened steels, including rolled steel, quenched and tempered steel, soft annealed alloyed steel and conventionally through-hardened steel consisting of different carbon and alloy contents. The surface hardness and hardened depth were compared among the samples. The effect of grain size on surface hardness of ferritic-pearlitic steel and pearlitic-cementite steel was evaluated. In-grain indentation was done to measure the hardness of pearlitic and cementite structures. The macrohardness of the base material was found to be related to the microhardness of the softer phase structure. The measured microhardness values were compared with the conventional macrohardness (HV5) results. A thermodynamic model was developed to calculate the temperature cycle, Ac1 and Ac3 boundaries, homogenization time and cooling rate. The equations were numerically solved with an error of less than 10-8. The temperature distributions for various thicknesses were compared under different laser traverse speed. The lag of the was verified by experiments done on six different steels. The calculated thermal cycle and hardened depth were compared with measured data. Correction coefficients were applied to the model for AISI 4340 steel. AISI 4340 steel was hardened by laser linear oscillation hardening (LLOS). Equations were derived to calculate the overlapped width of adjacent tracks and the number of overlapped scans in the center of the scanned track. The effect of oscillation frequency on the hardened depth was investigated by microscopic evaluation and hardness measurement. The homogeneity of hardness and hardened depth with different processing parameters were investigated. The hardness profiles were compared with the results obtained with conventional single-track hardening. LLOS was proved to be well suitable for surface hardening in a relatively large rectangular area with considerable depth of hardening. Compared with conventional single-track scanning, LLOS produced notably smaller hardened depths while at 40 and 100 Hz LLOS resulted in higher hardness within a depth of about 0.6 mm.