Novo conceito de juntas adesivas utilizando laminados de fibras e metal

Devido às necessidades da indústria atual é cada vez mais importante a utilização de métodos de união de materiais distintos. A utilização de adesivos no processo de produção de materiais compósitos tem uma grande aplicação, uma vez que permite ligar os diferentes materiais e ainda reduzir significativamente o peso do conjunto. Este trabalho teve como principal objetivo aumentar a resistência à delaminação de materiais compósitos no sentido da espessura, concretamente dos plásticos reforçados com fibras de carbono (CFRP), através da utilização de placas da liga de alumínio 2024-T3. Este conceito é muito semelhante ao utilizado nos laminados por fibras e metal (LFM) para aumentar a sua resistência à delaminação. Pretendeu-se também a identificação da configuração da junta que apresenta melhores resultados, comparativamente à junta de referência composta apenas por CFRP. Inicialmente, produziram-se apenas juntas de CFRP que foram utilizadas como comparação com os laminados de fibras e metal. Com o objetivo de melhorar a adesão entre os CFRP e a liga de alumínio, foram realizados três tratamentos superficiais diferentes, nomeadamente a lixagem, a anodização e o ataque com ácido. Posteriormente, foram produzidas as juntas com as seguintes configurações: CFRP-AL-CFRP, CFRP-AL-CFRP-AL-CFRP e AL-CFRP-AL. A realização deste trabalho permitiu concluir que com a adição de placas de alumínio, se conseguiu um melhoramento da resistência à delaminação das fibras de carbono e ainda um aumento da resistência específica no sentido da sua espessura. A JSS com a configuração AL-CFRP-AL e com comprimento de sobreposição de 50 mm foi a configuração que apresentou uma força de rotura mais elevada, ou seja, uma maior resistência à delaminação, comparativamente à junta de referência e às restantes configurações em estudo. A falha coesiva verificada perto da interface da junta AL-CFRP-AL, pode ser devida ao elevado comprimento de sobreposição e às diferentes elasticidades do alumínio e do CFRP, o que naturalmente levou a elevadas tensões localizadas nas extremidades da junta. Os resultados demostraram que é possível aumentar a resistência transversal do compósito utilizando uma placa de alumínio.

Lightweight metal halide and hydride fast Li ion conductors

This work was motivated by the extensive research on lithium solid state materials, which have attracted increasing interest for potential applications in hydrogen storage and/or lithium ion batteries due to their extraordinary properties. In this thesis, LiBH4-derived materials, LiInBr4 and complex phases based on lithium ammonia borane with potential use as solid state electrolytes were successfully synthesised and characterised.

Exploring redox-driven self-assembly of mixed metal polyoxometalates

How can we control the experimental conditions towards the isolation of specific structures? Why do particular architectures form? These are some challenging questions that synthetic chemists try to answer, specifically within polyoxometalate (POM) chemistry, where there is still much unknown regarding the synthesis of novel molecular structures in a controlled and predictive manner. This work covers a wide range of POM chemistry, exploring the redox self-assembly of polyoxometalate clusters, using both “one-pot”, flow and hydrothermal conditions. For this purpose, different vanadium, molybdenum and tungsten reagents, heteroatoms, inorganic salts and reducing agents have been used. The template effect of lone-pair containing pyramidal heteroatoms has been investigated. Efforts to synthesize new POM clusters displaying pyramidal heteroanions (XO32-, where X= S, Se, Te, P) are reported. The reaction of molybdenum with vanadium in the presence of XO32- heteroatoms is explored, showing how via the cation and experimental control it is possible to direct the self-assembly process and to isolate isostructural compounds. A series of four isostructural (two new, namely {Mo11V7P} and {Mo11V7Te} and two already known, namely {Mo11V7Se} and {Mo11V7S} disordered egg-shaped Polyoxometalates have been reported. The compounds were characterized by X-ray structural analysis, TGA, UV-Vis, FT-IR, Elemental and Flame Atomic Absorption Spectroscopy (FAAS) analysis and Inductively Coupled Plasma Optical Emission Spectroscopy (ICP-OES). Cyclic Voltammetry measurements have been carried out in all four compounds showing the effect of the ionic density of the heteroatom on the potential. High-Resolution ESI-MS studies have revealed that the structures retain their integrity in solution. Efforts to synthesize new mixed-metal compounds led to isolation, structural, and electronic characterization of the theoretically predicted, but experimentally elusive δ-isomer of the Keggin polyoxometalate cluster anion, {H2W4V9O33(C6H13NO3)}, by the reaction of tungstate(VI) and vanadium(V) with triethanolammonium ions (TEAH), acting as a tripodal ligand grafted to the surface of the cluster. Control experiments (in the absence of the organic compound) have proven that the tripodal ligand plays crucial role on the formation of the isomer. The six vanadium metal centres, which consist the upper part of the cluster, are bonded to the “capping” TEA tripodal ligand. This metal-ligand bonding directs and stabilises the formation of the final product. The δ-Keggin species was characterized by single-crystal X-ray diffraction, FT-IR, UV-vis, NMR and ESI-MS spectrometry. Electronic structure and structure-stability correlations were evaluated by means of DFT calculations. The compounds exhibited photochromic properties by undergoing single-crystal-to-single-crystal (SC-SC) transformations and changing colour under light. Non-conventional synthetic approaches are also used for the synthesis of the POM clusters comparing the classical “one-pot” reaction conditions and exploring the synthetic parameters of the synthesis of POM compounds. Reactions under hydrothermal and flow conditions, where single crystals that depend on the solubility of the minerals under hot water and high pressure can be synthesized, resulted in the isolation of two isostructural compounds, namely, {Mo12V3Te5}. The compound isolated from a continuous processing method, crystallizes in a hexagonal crystal system, forming a 2D porous plane net, while the compound isolated using hard experimental conditions (high temperature and pressure) crystallizes in monoclinic system, resulting in a different packing configuration. Utilizing these alternative synthetic approaches, the most kinetically and thermodynamically compounds would possibly be isolated. These compounds were characterised by single-crystal X-ray diffraction, FT-IR and UV-vis spectroscopy. Finally, the redox-controlled driven oscillatory template exchange between phosphate (P) and vanadate (V) anions enclosed in an {M18O54(XO4)2} cluster is further investigated using UV-vis spectroscopy as a function of reaction time, showed that more than six complete oscillations interconverting the capsule species present in solution from {P2M18} to {V2M18} were possible, provided that a sufficient concentration of the TEA reducing agent was present in solution. In an effort to investigate the periodicity of the exchange of the phosphate and vanadate anions, time dependent Uv-vis measurements were performed for a period at a range of 170-550 hours. Different experimental conditions were also applied in order to investigate the role of the reducing agent, as well as the effect of other experimental variables on the oscillatory system.

[Topographic map of portion of Aberdeen Proving Ground, Maryland, and topographical and architectural examples and exercises] /

Relief shown by contours.

Architectural-Physical Co-Design of 3D CPUs with Micro-Fluidic Cooling

The performance, energy efficiency and cost improvements due to traditional technology scaling have begun to slow down and present diminishing returns. Underlying reasons for this trend include fundamental physical limits of transistor scaling, the growing significance of quantum effects as transistors shrink, and a growing mismatch between transistors and interconnects regarding size, speed and power. Continued Moore's Law scaling will not come from technology scaling alone, and must involve improvements to design tools and development of new disruptive technologies such as 3D integration. 3D integration presents potential improvements to interconnect power and delay by translating the routing problem into a third dimension, and facilitates transistor density scaling independent of technology node. Furthermore, 3D IC technology opens up a new architectural design space of heterogeneously-integrated high-bandwidth CPUs. Vertical integration promises to provide the CPU architectures of the future by integrating high performance processors with on-chip high-bandwidth memory systems and highly connected network-on-chip structures. Such techniques can overcome the well-known CPU performance bottlenecks referred to as memory and communication wall. However the promising improvements to performance and energy efficiency offered by 3D CPUs does not come without cost, both in the financial investments to develop the technology, and the increased complexity of design. Two main limitations to 3D IC technology have been heat removal and TSV reliability. Transistor stacking creates increases in power density, current density and thermal resistance in air cooled packages. Furthermore the technology introduces vertical through silicon vias (TSVs) that create new points of failure in the chip and require development of new BEOL technologies. Although these issues can be controlled to some extent using thermal-reliability aware physical and architectural 3D design techniques, high performance embedded cooling schemes, such as micro-fluidic (MF) cooling, are fundamentally necessary to unlock the true potential of 3D ICs. A new paradigm is being put forth which integrates the computational, electrical, physical, thermal and reliability views of a system. The unification of these diverse aspects of integrated circuits is called Co-Design. Independent design and optimization of each aspect leads to sub-optimal designs due to a lack of understanding of cross-domain interactions and their impacts on the feasibility region of the architectural design space. Co-Design enables optimization across layers with a multi-domain view and thus unlocks new high-performance and energy efficient configurations. Although the co-design paradigm is becoming increasingly necessary in all fields of IC design, it is even more critical in 3D ICs where, as we show, the inter-layer coupling and higher degree of connectivity between components exacerbates the interdependence between architectural parameters, physical design parameters and the multitude of metrics of interest to the designer (i.e. power, performance, temperature and reliability). In this dissertation we present a framework for multi-domain co-simulation and co-optimization of 3D CPU architectures with both air and MF cooling solutions. Finally we propose an approach for design space exploration and modeling within the new Co-Design paradigm, and discuss the possible avenues for improvement of this work in the future.

Integrating Architecture for a Live-Work Lifestyle

Urban centers all around the world are striving to re-orient themselves to promoting ideals of human engagement, flexibility, openness and synergy, that thoughtful architecture can provide. From a time when solitude in one’s own backyard was desirable, today’s outlook seeks more, to cater to the needs of diverse individuals and that of collaborators. This thesis is an investigation of the role of architecture in realizing how these ideals might be achieved, using Mixed Use Developments as the platform of space to test these designs ideas on. The author also investigates, identifies, and re-imagines how the idea of live-work excites and attracts users and occupants towards investing themselves in Mixed Used Developments (MUD’s), in urban cities. On the premise that MUDs historically began with an intention of urban revitalization, lying in the core of this spatial model, is the opportunity to investigate what makes mixing of uses an asset, especially in the eyes to today’s generation. Within the framework of reference to the current generation, i.e. the millennial population and alike, who have a lifestyle core that is urban-centric, the excitement for this topic is in the vision of MUD’s that will spatially cater to a variety in lifestyles, demographics, and functions, enabling its users to experience a vibrant 24/7 destination. Where cities are always in flux, the thesis will look to investigate the idea of opportunistic space, in a new MUD, that can also be perceived as an adaptive reuse of itself. The sustainability factor lies in the foresight of the transformative and responsive character of the different uses in the MUD at large, which provides the possibility to cater to a changing demand of building use over time. Delving into the architectural response, the thesis in the process explores, conflicts, tensions, and excitements, and the nature of relationships between different spatial layers of permanence vs. transformative, public vs. private, commercial vs. residential, in such an MUD. At a larger scale, investigations elude into the formal meaning and implications of the proposed type of MUD’s and the larger landscapes in which they are situated, with attempts to blur the fine line between architecture and urbanism. A unique character of MUD’s is the power it has to draw in people at the ground level and lead them into exciting spatial experiences. While the thesis stemmed from a purely objective and theoretical standpoint, the author believes that it is only when context is played into the design thinking process, that true architecture may start to flourish. The unique The significance of this thesis lies on the premise that the author believes that this re-imagined MUD has immense opportunity to amplify human engagement with designed space, and in the belief that it will better enable fostering sustainable communities and in the process, enhance people’s lives.

Appraisal of open software for finite element simulation of 2D metal sheet laser cut.

FEA simulation of thermal metal cutting is central to interactive design and manufacturing. It is therefore relevant to assess the applicability of FEA open software to simulate 2D heat transfer in metal sheet laser cuts. Application of open source code (e.g. FreeFem++, FEniCS, MOOSE) makes possible additional scenarios (e.g. parallel, CUDA, etc.), with lower costs. However, a precise assessment is required on the scenarios in which open software can be a sound alternative to a commercial one. This article contributes in this regard, by presenting a comparison of the aforementioned freeware FEM software for the simulation of heat transfer in thin (i.e. 2D) sheets, subject to a gliding laser point source. We use the commercial ABAQUS software as the reference to compare such open software. A convective linear thin sheet heat transfer model, with and without material removal is used. This article does not intend a full design of computer experiments. Our partial assessment shows that the thin sheet approximation turns to be adequate in terms of the relative error for linear alumina sheets. Under mesh resolutions better than 10e−5 m , the open and reference software temperature differ in at most 1 % of the temperature prediction. Ongoing work includes adaptive re-meshing, nonlinearities, sheet stress analysis and Mach (also called ‘relativistic’) effects.

Effect of graphene substrate on the SERS Spectra of Aromatic bifunctional molecules on metal nanoparticles

The design of molecular sensors plays a very important role within nanotechnology and especially in the development of different devices for biomedical applications. Biosensors can be classified according to various criteria such as the type of interaction established between the recognition element and the analyte or the type of signal detection from the analyte (transduction). When Raman spectroscopy is used as an optical transduction technique the variations in the Raman signal due to the physical or chemical interaction between the analyte and the recognition element has to be detected. Therefore any significant improvement in the amplification of the optical sensor signal represents a breakthrough in the design of molecular sensors. In this sense, Surface-Enhanced Raman Spectroscopy (SERS) involves an enormous enhancement of the Raman signal from a molecule in the vicinity of a metal surface. The main objective of this work is to evaluate the effect of a monolayer of graphene oxide (GO) on the distribution of metal nanoparticles (NPs) and on the global SERS enhancement of paminothiophenol (pATP) and 4-mercaptobenzoic acid (4MBA) adsorbed on this substrate. These aromatic bifunctional molecules are able to interact to metal NPs and also they offer the possibility to link with biomolecules. Additionally by decorating Au or Ag NPs on graphene sheets, a coupled EM effect caused by the aggregation of the NPs and strong electronic interactions between Au or Ag NPs and the graphene sheets are considered to be responsible for the significantly enhanced Raman signal of the analytes [1-2]. Since there are increasing needs for methods to conduct reproducible and sensitive Raman measurements, Grapheneenhanced Raman Scattering (GERS) is emerging as an important method [3].

Structure-properties correlations in divalent metal phosphonates

Crystalline metal phosphonates may offer acidic sites, structural flexibility and guest molecules (H2O, heterocyclics, etc.) which can act as proton carriers. In addition, some frameworks are also amenable for post‐synthesis modifications in order to enhance desired properties [1,2]. In this work, we present the synthesis and structural characterization of two hydroxyphosphonoacetates hybrids based on magnesium, [Mg5(O3PCHOHCOO)2(HO3PCHOHCOO)2·8H2O] [Mg5(HPAA)2(H1HPAA)2·8H2O], and zinc, [Zn6K(O3PCHOHCOO)4(OH)·6.5H2O] [Zn6K(HPAA)4(OH)·6.5H2O]. Both solids present three-dimensional frameworks and their crystal structures were solved ab initio from X-ray powder diffraction. The proton conductivity of [Zn6K(HPAA)4(OH)·6.5H2O] as well as ammonia derivatives of M(II)(HO3PCHOHCOO)·2H2O [M(II)=Zn, Mg] will be reported and discussed.

Simulação computacional de medidas estereológicas em estruturas de metal duro (WC-Co)

This work focuses on the creation and applications of a dynamic simulation software in order to study the hard metal structure (WC-Co). The technological ground used to increase the GPU hardware capacity was Geforce 9600 GT along with the PhysX chip created to make games more realistic. The software simulates the three-dimensional carbide structure to the shape of a cubic box where tungsten carbide (WC) are modeled as triangular prisms and truncated triangular prisms. The program was proven effective regarding checking testes, ranging from calculations of parameter measures such as the capacity to increase the number of particles simulated dynamically. It was possible to make an investigation of both the mean parameters and distributions stereological parameters used to characterize the carbide structure through cutting plans. Grounded on the cutting plans concerning the analyzed structures, we have investigated the linear intercepts, the intercepts to the area, and the perimeter section of the intercepted grains as well as the binder phase to the structure by calculating the mean value and distribution of the free path. As literature shows almost consensually that the distribution of the linear intercepts is lognormal, this suggests that the grain distribution is also lognormal. Thus, a routine was developed regarding the program which made possible a more detailed research on this issue. We have observed that it is possible, under certain values for the parameters which define the shape and size of the Prismatic grain to find out the distribution to the linear intercepts that approach the lognormal shape. Regarding a number of developed simulations, we have observed that the distribution curves of the linear and area intercepts as well as the perimeter section are consistent with studies on static computer simulation to these parameters.

Towards near-infrared photoactivation of anticancer metal complexes.

171 p.

Heavy metal release due to aging effect during zero valent iron nanoparticles remediation

Zero valent iron nanoparticles (nZVI) represent a promising agent for environmental remediation. Nevertheless, their application presents some limitations regarding their rapid oxidation and aggregation in the media. The aim of this study was to determine the effect that nZVI aging has in heavy metal remediation in water. Contaminants studied were Zn, Cd, Ni, Cu and Cr, which are typical elements found in ground and wastewater. Results show a high contaminant removal capacity by the nZVI in the first 2 h of reaction. Nevertheless, for longer reaction times, some of the metal ions that had already been adsorbed in the nZVI were delivered to the water. Cd and Ni show the maximum delivery percentages (65 and 27% respectively after 21 days of contact time). The starting delivery time was shortened when applying lower nZVI amounts. No re-dissolution of Cr was observed in any circumstance because it was the only element incorporated into the nanoparticles core, as TEM images showed. Contaminant release from nZVI is probably due to nanoparticles oxidation caused by aging, which produced a pH decrease and nZVI surface crystallization.

O metal na arquitetura contemporânea paraibana 1990-2002

This essay studies about contemporary architecture in João Pessoa, capital city of Paraiba State, which analyzes the utilization of steel and aluminum materials from 1990 to 2002, period when significant increase of this utilization is seen. As references, the architectural analysis and Engel structures definitions were used to analyze 40 built buildings, universe researched, to bring together subsidies to comprehend the contemporary production, especially which use the metal as structural and esthetic-formal element

La responsabilidad social empresarial en el sector industrial de metales en la ciudad de Cuenca: propuesta del diseño de un plan de responsabilidad social empresarial para la Empresa Metal Print para el periodo 2016

El presente trabajo de titulación aborda la Responsabilidad Social Empresarial (RSE) un tema que toma mucha importancia en la actualidad ya que su objetivo fundamental es que las empresas encaminen sus esfuerzos en mantener un desarrollo sostenible con todas sus partes interesadas tanto en el ámbito económico, social y ambiental. Para empezar este trabajo se realiza una recopilación de bases teóricas sobre RSE con el objetivo de tener un amplio conocimiento sobre el tema de investigación. También se estudió la guía de Implementación de RSE elaborada por la Asociación de Empresarios Cristianos (ADEC) con la finalidad de entender la aplicación de los indicadores ADEC Ethos 2009 que ayudarán a determinar el nivel de RSE actual de las empresas del Sector Industrial de Fabricación de Metales Comunes (C24) en la ciudad de Cuenca. Se realizó un análisis más preciso a la empresa Metal Print con el propósito de conocer la situación actual del negocio y las prácticas que esta realiza con respecto a la RSE, la información obtenida será de gran importancia y se utilizarán los indicadores ADEC Ethos 2009 para poder interpretar los resultados obtenidos en la empresa. Para finalizar se elabora un plan que contiene varias estrategias enfocadas en contribuir al desarrollo de acciones de RSE que involucran precisamente a la empresa Metal Print, sus empleados, la comunidad y al medioambiente.

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.