Síntese e caracterização de nanocompósitos magnéticos empregando polimerização radicalar em meios homogêneo (blk) e heterogêneo (miniemulsão)

Tese (doutorado)—Universidade de Brasília, Instituto de Química, Curso de Pós-Graduação em Química, 2016.

HIGH VOLTAGE ELECTROPHORETIC DEPOSITION FOR ELECTROCHEMICAL ENERGY STORAGE AND OTHER APPLICATIONS

High voltage electrophoretic deposition (HVEPD) has been developed as a novel technique to obtain vertically aligned forests of one-dimensional nanomaterials for efficient energy storage. The ability to control and manipulate nanomaterials is critical for their effective usage in a variety of applications. Oriented structures of one-dimensional nanomaterials provide a unique opportunity to take full advantage of their excellent mechanical and electrochemical properties. However, it is still a significant challenge to obtain such oriented structures with great process flexibility, ease of processing under mild conditions and the capability to scale up, especially in context of efficient device fabrication and system packaging. This work presents HVEPD as a simple, versatile and generic technique to obtain vertically aligned forests of different one-dimensional nanomaterials on flexible, transparent and scalable substrates. Improvements on material chemistry and reduction of contact resistance have enabled the fabrication of high power supercapacitor electrodes using the HVEPD method. The investigations have also paved the way for further enhancements of performance by employing hybrid material systems and AC/DC pulsed deposition. Multi-walled carbon nanotubes (MWCNTs) were used as the starting material to demonstrate the HVEPD technique. A comprehensive study of the key parameters was conducted to better understand the working mechanism of the HVEPD process. It has been confirmed that HVEPD was enabled by three key factors: high deposition voltage for alignment, low dispersion concentration to avoid aggregation and simultaneous formation of holding layer by electrodeposition for reinforcement of nanoforests. A set of suitable parameters were found to obtain vertically aligned forests of MWCNTs. Compared with their randomly oriented counterparts, the aligned MWCNT forests showed better electrochemical performance, lower electrical resistance and a capability to achieve superhydrophpbicity, indicating their potential in a broad range of applications. The versatile and generic nature of the HVEPD process has been demonstrated by achieving deposition on flexible and transparent substrates, as well as aligned forests of manganese dioxide (MnO2) nanorods. A continuous roll-printing HVEPD approach was then developed to obtain aligned MWCNT forest with low contact resistance on large, flexible substrates. Such large-scale electrodes showed no deterioration in electrochemical performance and paved the way for practical device fabrication. The effect of a holding layer on the contact resistance between aligned MWCNT forests and the substrate was studied to improve electrochemical performance of such electrodes. It was found that a suitable precursor salt like nickel chloride could be used to achieve a conductive holding layer which helped to significantly reduce the contact resistance. This in turn enhanced the electrochemical performance of the electrodes. High-power scalable redox capacitors were then prepared using HVEPD. Very high power/energy densities and excellent cyclability have been achieved by synergistically combining hydrothermally synthesized, highly crystalline α-MnO2 nanorods, vertically aligned forests and reduced contact resistance. To further improve the performance, hybrid electrodes have been prepared in the form of vertically aligned forest of MWCNTs with branches of α-MnO2 nanorods on them. Large- scale electrodes with such hybrid structures were manufactured using continuous HVEPD and characterized, showing further improved power and energy densities. The alignment quality and density of MWCNT forests were also improved by using an AC/DC pulsed deposition technique. In this case, AC voltage was first used to align the MWCNTs, followed by immediate DC voltage to deposit the aligned MWCNTs along with the conductive holding layer. Decoupling of alignment from deposition was proven to result in better alignment quality and higher electrochemical performance.

Dynamic mechanical-thermal, microstructural and mechanical analysis of ultra-light polymer-metal composites: influence of forming

A really particular and innovative metal-polymer sandwich material is Hybrix. Hybrix is a product developed and manufactured by Lamera AB, Gothenburg, Sweden. This innovative hybrid material is composed by two relatively thin metal layers if compared to the core thickness. The most used metals are aluminum and stainless steel and are separated by a core of nylon fibres oriented perpendicularly to the metal plates. The core is then completed by adhesive layers applied at the PA66-metal interface that once cured maintain the nylon fibres in position. This special material is very light and formable. Moreover Hybrix, depending on the specific metal which is used, can achieve a good corrosion resistance and it can be cut and punched easily. Hybrix architecture itself provides extremely good bending stiffness, damping properties, insulation capability, etc., which again, of course, change in magnitude depending in the metal alloy which is used, its thickness and core thickness. For these reasons nowadays it shows potential for all the applications which have the above mentioned characteristic as a requirement. Finally Hybrix can be processed with tools used in regular metal sheet industry and can be handled as solid metal sheets. In this master thesis project, pre-formed parts of Hybrix were studied and characterized. Previous work on Hybrix was focused on analyze its market potential and different adhesive to be used in the core. All the tests were carried out on flat unformed specimens. However, in order to have a complete description of this material also the effect of the forming process must be taken into account. Thus the main activities of the present master thesis are the following: Dynamic Mechanical-Thermal Analysis (DMTA) on unformed Hybrix samples of different thickness and on pre-strained Hybrix samples, pure epoxy adhesive samples analysis and finally moisture effects evaluation on Hybrix composite structure.

Development of hybrid UV VCSEL with organic active material and dielectric DBR mirrors for medical, sensoric and data storage applications

Lasers play an important role for medical, sensoric and data storage devices. This thesis is focused on design, technology development, fabrication and characterization of hybrid ultraviolet Vertical-Cavity Surface-Emitting Lasers (UV VCSEL) with organic laser-active material and inorganic distributed Bragg reflectors (DBR). Multilayer structures with different layer thicknesses, refractive indices and absorption coefficients of the inorganic materials were studied using theoretical model calculations. During the simulations the structure parameters such as materials and thicknesses have been varied. This procedure was repeated several times during the design optimization process including also the feedback from technology and characterization. Two types of VCSEL devices were investigated. The first is an index coupled structure consisting of bottom and top DBR dielectric mirrors. In the space in between them is the cavity, which includes active region and defines the spectral gain profile. In this configuration the maximum electrical field is concentrated in the cavity and can destroy the chemical structure of the active material. The second type of laser is a so called complex coupled VCSEL. In this structure the active material is placed not only in the cavity but also in parts of the DBR structure. The simulations show that such a distribution of the active material reduces the required pumping power for reaching lasing threshold. High efficiency is achieved by substituting the dielectric material with high refractive index for the periods closer to the cavity. The inorganic materials for the DBR mirrors have been deposited by Plasma- Enhanced Chemical Vapor Deposition (PECVD) and Dual Ion Beam Sputtering (DIBS) machines. Extended optimizations of the technological processes have been performed. All the processes are carried out in a clean room Class 1 and Class 10000. The optical properties and the thicknesses of the layers are measured in-situ by spectroscopic ellipsometry and spectroscopic reflectometry. The surface roughness is analyzed by atomic force microscopy (AFM) and images of the devices are taken with scanning electron microscope (SEM). The silicon dioxide (SiO2) and silicon nitride (Si3N4) layers deposited by the PECVD machine show defects of the material structure and have higher absorption in the ultra violet range compared to ion beam deposition (IBD). This results in low reflectivity of the DBR mirrors and also reduces the optical properties of the VCSEL devices. However PECVD has the advantage that the stress in the layers can be tuned and compensated, in contrast to IBD at the moment. A sputtering machine Ionsys 1000 produced by Roth&Rau company, is used for the deposition of silicon dioxide (SiO2), silicon nitride (Si3N4), aluminum oxide (Al2O3) and zirconium dioxide (ZrO2). The chamber is equipped with main (sputter) and assisted ion sources. The dielectric materials were optimized by introducing additional oxygen and nitrogen into the chamber. DBR mirrors with different material combinations were deposited. The measured optical properties of the fabricated multilayer structures show an excellent agreement with the results of theoretical model calculations. The layers deposited by puttering show high compressive stress. As an active region a novel organic material with spiro-linked molecules is used. Two different materials have been evaporated by utilizing a dye evaporation machine in the clean room of the department Makromolekulare Chemie und Molekulare Materialien (mmCmm). The Spiro-Octopus-1 organic material has a maximum emission at the wavelength λemission = 395 nm and the Spiro-Pphenal has a maximum emission at the wavelength λemission = 418 nm. Both of them have high refractive index and can be combined with low refractive index materials like silicon dioxide (SiO2). The sputtering method shows excellent optical quality of the deposited materials and high reflection of the multilayer structures. The bottom DBR mirrors for all VCSEL devices were deposited by the DIBS machine, whereas the top DBR mirror deposited either by PECVD or by combination of PECVD and DIBS. The fabricated VCSEL structures were optically pumped by nitrogen laser at wavelength λpumping = 337 nm. The emission was measured by spectrometer. A radiation of the VCSEL structure at wavelength 392 nm and 420 nm is observed.

Effect Of Platform Connection And Abutment Material On Stress Distribution In Single Anterior Implant-supported Restorations: A Nonlinear 3-dimensional Finite Element Analysis.

Although various abutment connections and materials have recently been introduced, insufficient data exist regarding the effect of stress distribution on their mechanical performance. The purpose of this study was to investigate the effect of different abutment materials and platform connections on stress distribution in single anterior implant-supported restorations with the finite element method. Nine experimental groups were modeled from the combination of 3 platform connections (external hexagon, internal hexagon, and Morse tapered) and 3 abutment materials (titanium, zirconia, and hybrid) as follows: external hexagon-titanium, external hexagon-zirconia, external hexagon-hybrid, internal hexagon-titanium, internal hexagon-zirconia, internal hexagon-hybrid, Morse tapered-titanium, Morse tapered-zirconia, and Morse tapered-hybrid. Finite element models consisted of a 4×13-mm implant, anatomic abutment, and lithium disilicate central incisor crown cemented over the abutment. The 49 N occlusal loading was applied in 6 steps to simulate the incisal guidance. Equivalent von Mises stress (σvM) was used for both the qualitative and quantitative evaluation of the implant and abutment in all the groups and the maximum (σmax) and minimum (σmin) principal stresses for the numerical comparison of the zirconia parts. The highest abutment σvM occurred in the Morse-tapered groups and the lowest in the external hexagon-hybrid, internal hexagon-titanium, and internal hexagon-hybrid groups. The σmax and σmin values were lower in the hybrid groups than in the zirconia groups. The stress distribution concentrated in the abutment-implant interface in all the groups, regardless of the platform connection or abutment material. The platform connection influenced the stress on abutments more than the abutment material. The stress values for implants were similar among different platform connections, but greater stress concentrations were observed in internal connections.

On the template synthesis of nanostructured inorganic/organic hybrid films

Prussian Blue has been introduced as a mediator to achieve stable, sensitive, reproducible, and interference-free biosensors. However, Na(+), Li(+), H(+), and all group II cations are capable to block the activity of Prussian Blue and, because Na(+) can be found in most human fluids, Prussian Blue analogs have already been developed to overcome this problem. These analogs, such as copper hexacyanoferrate, have also been introduced in a conducting polypyrrole matrix to create hybrid materials (copper hexacyanoferrate/polypyrrole, CuHCNFe/Ppy) with improved mechanical and electrochemical characteristics. Nowadays, the challenges in amperometric enzymatic biosensors consist of improving the enzyme immobilization and in making the chemical signal transduction more efficient. The incorporation of nanostructured materials in biosensors can optimize both steps and a nanostructured hybrid CuHCNFe/Ppy mediator has been developed using a template of colloidal polystyrene particles. The nanostructured material has achieved sensitivities 7.6 times higher than the bulk film during H(2)O(2) detection and it has also presented better results in other analytical parameters such as time response and detection limit. Besides, the nanostructured mediator was successfully applied at glucose biosensing in electrolytes containing Prussian Blue blocking cations. (C) 2008 The Electrochemical Society.

Synthesis and electrochemical properties of vanadyl phosphate di-hydrate/polyaniline derivatives hybrid films

Vanadyl phosphate and its hybrid compounds have proven to undergo electrochemical intercalation and de-intercalation of lithium ions, which enables its use as cathode material for Li ion rechargeable batteries. In this context, vanadyl phosphate di-hydrate/polyaniline derivatives hybrid films were synthesized via the exfoliation and reconstruction approach in order to evaluate their potential use as cathode in ion lithium batteries. X-ray diffraction patterns indicate that the lamellar structure of the inorganic matrix is maintained, consistent with the topotactic process. In the scanning electron micrographs, hybrid films exhibit rough surface consisting of warped and cracked crystallites, quite different from vanadyl phosphate di-hydrate square platelets crystallites. Electrochemical evaluation using cyclic voltammetry and charge-discharge galvanostatic techniques shows small differences between the charge and the discharge curves, indicating an irreversibility of the hybrid systems. (C) 2009 Elsevier B.V. All rights reserved.

Optimization study of hybrid spot-welded/bonded single-lap joints

Joining of components with structural adhesives is currently one of the most widespread techniques for advanced structures (e.g., aerospace or aeronautical). Adhesive bonding does not involve drilling operations and it distributes the load over a larger area than mechanical joints. However, peak stresses tend to develop near the overlap edges because of differential straining of the adherends and load asymmetry. As a result, premature failures can be expected, especially for brittle adhesives. Moreover, bonded joints are very sensitive to the surface treatment of the material, service temperature, humidity and ageing. To surpass these limitations, the combination of adhesive bonding with spot-welding is a choice to be considered, adding a few advantages like superior static strength and stiffness, higher peeling and fatigue strength and easier fabrication, as fixtures during the adhesive curing are not needed. The experimental and numerical study presented here evaluates hybrid spot-welded/bonded single-lap joints in comparison with the purely spot-welded and bonded equivalents. A parametric study on the overlap length (LO) allowed achieving different strength advantages, up to 58% compared to spot-welded joints and 24% over bonded joints. The Finite Element Method (FEM) and Cohesive Zone Models (CZM) for damage growth were also tested in Abaqus® to evaluate this technique for strength prediction, showing accurate estimations for all kinds of joints.

Tool effects on hybrid laminates drilling

Fiber reinforced plastics are increasing their importance as one of the most interesting groups of material on account of their low weight, high strength, and stiffness. To obtain good quality holes, it is important to identify the type of material, ply stacking sequence, and fiber orientation. In this article, the drilling of quasi-isotropic hybrid carbon +glass/epoxy plates is analyzed. Two commercial drills and a special step drill are compared considering the thrust force and delamination extension. Results suggest that the proposed step drill can be a suitable option in laminate drilling.

Damage assessment of drilled hybrid composite laminates

Hole drilling operations are common in fibre reinforced plastics - FRP’s - to facilitate fastener assembly to other parts in more complex structures. As these materials are non-homogeneous, drilling causes some damages, like delamination, for example. Delamination can be reduced by a careful selection of drilling parameters, drill material and drill bit geometry. In this work two types of laminates are drilled using different machining parameters and comparing drill geometries. Results show the importance of a cautious selection of these variables when composites’ drilling is involved.

Hybrid thermoset polymeric composites – an Innovation towards sustainability

In this study, a new waste management solution for thermoset glass fibre reinforced polymer (GFRP) based products was assessed. Mechanical recycling approach, with reduction of GFRP waste to powdered and fibrous materials was applied, and the prospective added-value of obtained recyclates was experimentally investigated as raw material for polyester based mortars. Different GFRP waste admixed mortar formulations were analyzed varying the content, between 4% up to 12% in weight, of GFRP powder and fibre mix waste. The effect of incorporation of a silane coupling agent was also assessed. Design of experiments and data treatment was accomplished through implementation of full factorial design and analysis of variance ANOVA. Added value of potential recycling solution was assessed by means of flexural and compressive loading capacity of GFRP waste admixed mortars with regard to unmodified polymer mortars. The key findings of this study showed a viable technological option for improving the quality of polyester based mortars and highlight a potential cost-effective waste management solution for thermoset composite materials in the production of sustainable concrete-polymer based products.

Assessment of the efficiency of prefabricated hybrid composite plates (HCPs) for retrofitting of damaged interior RC beam–column joints

The effectiveness of prefabricated hybrid composite plates (HCPs) as a seismic retrofitting solution for damaged interior RC beam-column joints is experimentally studied. HCP is composed of a thin plate made of strain hardening cementitious composite (SHCC) reinforced with CFRP sheets/laminates. Two full-scale severely damaged interior beam-column joints are retrofitted using two different configurations of HCPs. The effectiveness of these retrofitting solutions mainly in terms of hysteretic response, dissipated energy, degradation of secant stiffness, displacement ductility and failure modes are compared to their virgin states. According to these criteria, both solutions resulted in superior responses regarding the ones registered in their virgin states.

Flexural strengthening of RC beams using hybrid composite plate (HCP): experimental and analytical study

Hybrid Composite Plate (HCP) is a reliable recently proposed retrofitting solution for concrete structures, which is composed of a strain hardening cementitious composite (SHCC) plate reinforced with Carbon Fibre Reinforced Polymer (CFRP). This system benefits from the synergetic advantages of these two composites, namely the high ductility of SHCC and the high tensile strength of CFRPs. In the materialstructural of HCP, the ultra-ductile SHCC plate acts as a suitable medium for stress transfer between CFRP laminates (bonded into the pre-sawn grooves executed on the SHCC plate) and the concrete substrate by means of a connection system made by either chemical anchors, adhesive, or a combination thereof. In comparison with traditional applications of FRP systems, HCP is a retrofitting solution that (i) is less susceptible to the detrimental effect of the lack of strength and soundness of the concrete cover in the strengthening effectiveness; (ii) assures higher durability for the strengthened elements and higher protection to the FRP component in terms of high temperatures and vandalism; and (iii) delays, or even, prevents detachment of concrete substrate. This paper describes the experimental program carried out, and presents and discusses the relevant results obtained on the assessment of the performance of HCP strengthened reinforced concrete (RC) beams subjected to flexural loading. Moreover, an analytical approach to estimate the ultimate flexural capacity of these beams is presented, which was complemented with a numerical strategy for predicting their load-deflection behaviour. By attaching HCP to the beams’ soffit, a significant increase in the flexural capacity at service, at yield initiation of the tension steel bars and at failure of the beams can be achieved, while satisfactory deflection ductility is assured and a high tensile capacity of the CFRP laminates is mobilized. Both analytical and numerical approaches have predicted with satisfactory agreement, the load-deflection response of the reference beam and the strengthened ones tested experimentally.

An evaluation of parchments' degradation a hybrid approach

Parchment stands for a multifaceted material made from animal skin, which has been used for centuries as a writing support or as bookbinding. Due to the historic value of objects made of parchment, understanding their degradation and their condition is of utmost importance to archives, libraries and museums, i.e., the assessment of parchment degradation is mandatory, although it is hard to do with traditional methodologies and tools for problem solving. Hence, in this work we will focus on the development of a hybrid decision support system, in terms of its knowledge representation and reasoning procedures, under a formal framework based on Logic Programming, complemented with an approach to computing centered on Artificial Neural Networks, to evaluate Parchment Degradation and the respective Degree-of-Confidence that one has on such a happening.

Designing cnc knit for hybrid membrane and bending active structures

Recent advances in computation allow for the integration of design and simulation of highly interrelated systems, such as hybrids of structural membranes and bending active elements. The engaged complexities of forces and logistics can be mediated through the development of materials with project specific properties and detailing. CNC knitting with high tenacity yarn enables this practice and offers an alternative to current woven membranes. The design and fabrication of an 8m high fabric tower through an interdisciplinary team of architects, structural and textile engineers, allowed to investigate means to design, specify, make and test CNC knit as material for hybrid structures in architectural scale. This paper shares the developed process, identifies challenges, potentials and future work.