Síntese e caracterização de NiO-CGO para anodo e eletrólitos sólidos e base de Céria para SOFC

The direct use of natural gas makes the Solid Oxide Fuel Cell (SOFC) potentially more competitive with the current energy conversions technologies. The Intermediate Temperature SOFC (IT-SOFC) offer several advantages over the High Temperature SOFC (HT-SOFC), which includes better thermal compatibility among components, fast start with lower energy consumption, manufacture and operation cost reduction. The CeO2 based materials are alternatives to the Yttria Stabilized Zirconia (YSZ) to application in SOFC, as they have higher ionic conductivity and less ohmic losses comparing to YSZ, and they can operate at lower temperatures (500-800°C). Ceria has been doped with a variety of cations, although, the Gd3+ has the ionic radius closest to the ideal one to form solid solution. These electrolytes based in ceria require special electrodes with a higher performance and chemical and termomechanical compatibility. In this work compounds of gadolinia-doped ceria, Ce1-xGdxO2-δ (x = 0,1; 0,2 and 0,3), used as electrolytes, were synthesized by polymeric precursors method, Pechini, as well as the composite material NiO - Ce0,9Gd0,1O1,95, used as anode, also attained by oxide mixture method, mixturing the powders of the both phases calcinated already. The materials were characterized by X ray diffraction, dilatometry and scanning electronic microscopy. The refinement of the diffraction data indicated that all the Ce1-xGdxO2-δ powders were crystallized in a unique cubic phase with fluorite structure, and the composite synthesized by Pechini method produced smaller crystallite size in comparison with the same material attained by oxide mixture method. All the produced powders had nanometric characteristics. The composite produced by Pechini method has microstructural characteristics that can increase the triple phase boundaries (TPB) in the anode, improving the cell efficiency, as well as reducing the mass transport mechanism effect that provokes anode degradation

Adsorção de Pb(II) utilizando adsorvente composto por montmorilonita e dolomita

The destructive impact of improper disposal of heavy metals in the environment increases as a direct result of population explosion, urbanization and industrial expansion and technological developments. Argil are potential materials for adsorption of inorganic and the pelletization of it is required for use in adsorptive columns of fixed bed. The low cost and the possibility of regeneration makes these materials attractive for use in the purification process, capable of removing inorganic compounds in contaminated aquatic environments. In this work was made pellets of a mixture of dolomite and montmorillonite by wet agglomeration, in different percentages. The removal of Pb (II) was investigated through experimental studies, and was modeled by kinetic models and isotherms of adsorption. The materials were characterized using the techniques of XRD, TG / DTA, FT-IR, and surface area by BET method. The results showed the adsorption efficiency of the contaminant by the composite material studied in synthetic solution. The study found that the adsorption follows the Langmuir model, and the kinetics of adsorption follows the model of pseudosecond order

Design of composites for thermal management: Aluminum reinforced with diamond-containing bimodal particle mixtures

A new design route is proposed in order to fabricate aluminum matrix diamond-containing composite materials with optimized values of thermal conductivity (TC) for thermal management applications. The proper size ratio and proportions of particulate diamond–diamond and diamond–SiC bimodal mixtures are selected based on calculations with predictive schemes, which combine two main issues: (i) the volume fraction of the packed particulate mixtures, and (ii) the influence of different types of particulates (with intrinsically different metal/reinforcement interfacial thermal conductances) on the overall thermal conductivity of the composite material. The calculated results are validated by comparison with measurements on composites fabricated by gas pressure infiltration of aluminum into preforms of selected compositions of particle mixtures. Despite the relatively low quality (low price) of the diamond particles used in this work, outstanding values of TC are encountered: a maximum of 770 W/m K for Al/diamond–diamond and values up to 690 W/m K for Al/diamond–SiC.

Surface irregularity factor as a parameter to evaluate the fatigue damage state of CFRP

This work presents an optical non-contact technique to evaluate the fatigue damage state of CFRP structures measuring the irregularity factor of the surface. This factor includes information about surface topology and can be measured easily on field, by techniques such as optical perfilometers. The surface irregularity factor has been correlated with stiffness degradation, which is a well-accepted parameter for the evaluation of the fatigue damage state of composite materials. Constant amplitude fatigue loads (CAL) and realistic variable amplitude loads (VAL), representative of real in- flight conditions, have been applied to “dog bone” shaped tensile specimens. It has been shown that the measurement of the surface irregularity parameters can be applied to evaluate the damage state of a structure, and that it is independent of the type of fatigue load that has caused the damage. As a result, this measurement technique is applicable for a wide range of inspections of composite material structures, from pressurized tanks with constant amplitude loads, to variable amplitude loaded aeronautical structures such as wings and empennages, up to automotive and other industrial applications.

Nanocarbon-Supported Electrocatalysts for the Alkaline Water Splitting and Fuel Cells

Electrocatalysts play a significant role in the processes of electrochemical energy conversion. This thesis focuses on the preparation of carbon-supported nanomaterials and their application as electrocatalysts for alkaline water electrocatalysis and fuel cell. A general synthetic route was developed, i.e., species intercalate into carbon layers of graphite forming graphite intercalation compound, followed by dispersion producing graphenide solution, which then as reduction agent reacts with different metal sources generating the final materials. The first metal precursor used was non-noble metal iron salt, which generated iron (oxide) nanoparticles finely dispersed on carbon layers in the final composite materials. Meanwhile, graphite starting materials differing in carbon layer size were utilized, which would diversify corresponding graphenide solutions, and further produce various nanomaterials. The characterization results showed that iron (oxide) nanoparticles varying in size were obtained, and the size was determined by the starting graphite material. It was found that they were electrocatalytically active for oxygen reactions. In particular, the one with small iron (oxide) nanoparticles showed excellent electrocatalytic activity for both oxygen reduction reaction (ORR) and oxygen evolution reaction (OER). Afterwards, the metal precursor was tuned from non-noble metal salt to noble metal salt. It was confirmed that carbon-supported Rh, Pt, and RhPt (oxide) nanoparticle composite materials were also successfully obtained from the reaction between graphenide solution and corresponding noble metal precursor. The electrochemical measurements showed that the prepared noble metal-based nanomaterials were quite effective for hydrogen evolution reaction (HER) electrocatalysis, and the Rh sample could also display excellent electrocatalytic property towards OER. Moreover, by this synthetic approach carbon-supported noble metal Pt and non-noble metal nickel (Ni) composite material was also prepared. Therefore, the utilization efficiency of noble metal could be improved. The prepared NiPt sample displayed a property close to benchmark HER electrocatalyst.

Newly developed electrosynthesis of Layered Double Hydroxides: application to sensing, energy storage and conversion

Layered Double hydroxides (LDHs) have been widely studied for their plethora of fascinating features and applications. The potentiostatic electrodeposition of LDHs has been extensively applied in the literature as a fast and direct method to substitute classical chemical routes. However, it does not usually allow for a fine control of the M(II)/M(III) ratio in the synthesized material and it is not suitable for large anions intercalation. Therefore, in this work a novel protocol has been proposed with the aim to overcome all these constraints using a method based on potentiodynamic synthesis. LDHs of controlled composition were prepared using different molar ratios of the trivalent to bivalent cations in the electrolytic solution ranging from 1:1 to 1:4. Moreover, we were able to produce electrochemically LDHs intercalated with carbon nanomaterials for the first time. A one-step procedure which contemporaneously allows for the Ni/Al-LDH synthesis, the reduction of graphene oxide (GO) and its intercalation inside the structure has been developed. The synthesised materials have been applied in several fields of interest. First of all, LDHs with a ratio 3:1 were exploited, and displayed good performances as catalysts for 5-(hydroxymethyl)furfural electro-oxidation, thus suggesting to carry out further investigation for applications in the field of industrial catalysis. The same materials, but with different metals ratios, were tested as catalysts for Oxygen Evolution Reaction, obtaining results comparable to LDHs synthesised by the classical co-precipitation method and also a better activity with respect to LDHs obtained by the potentiostatic approach. The composite material based on LDH and reduced graphene oxide was employed to fabricate a cathode of a hybrid supercapacitor coupled with an activated carbon anode. We can thus conclude that, to date, the potentiodynamic method has the greatest potential for the rapid synthesis of reproducible films of Co and Ni-based LDHs with controlled composition.

Nanostructured smart materials as functional components of medical devices

The field of medical devices has experienced, more than others, technological advances, developments and innovations, thanks to the rapidly expanding scientific knowledge and collaboration between different disciplines such as biology, engineering and materials science. The design of functional components can be achieved by exploiting composite materials based on nanostructured smart materials, that due to the inherent characteristics of single constituents develop unique properties that make them suitable for different applications preserving excellent mechanical proprieties. For instance, recent developments have focused on the fabrication of piezoelectric devices with multiple biomedical functions, as actuation and sensing functions in one component for monitoring pressure signals. The present Ph.D. Thesis aims at investigating nanostructured smart materials embedded into a polymeric matrix to obtain a composite material that can be used as a functional component for medical devices. (i) Nanostructured piezoelectric material with self-sensing capability was successfully manufactured by using ceramic (i.e. lead zirconate titanate (PZT)) and (ii) polymeric (i.e. poly(vinylidene fluoride-trifluoro ethylene (PVDF-TRFE)) piezoelectric materials. PZT nanofibers were obtained by sol-gel electrospinning starting from synthetized PZT precursor solution. Synthesis, sol-gel electrospinning process, and thermal treatment were accurately controlled to obtain PZT nanofibers dimensionally stable with densely packed grains in the perovskite phase. To guarantee the impact resistance of the laminate, the morphology and size of the hosting filler were accurately designed by increasing the surface area to volume ratio. Moreover, to solve the issue relative to the mechanical discrepancy between rigid electronic materials/soft human tissues/different material of the device (iii) a nanostructured flexible composite material based on a network of Poly-L-lactic acid (PLLA) made of curled nanofibers that present a tuneable mechanical response as a function of the applied stress was successful fabricated.

Non-line-of-sight localization with frequency-selective metasurfaces

An emerging technology, that Smart Radio Environments rely on to improve wireless link quality, are Reconfigurable Intelligent Surfaces (RISs). A RIS, in general, can be understood as a thin layer of EM composite material, typically mounted on the walls or ceilings of buildings, which can be reconfigured even after its deployment in the network. RISs made by composing artificial materials in an engineered way, in order to obtain unconventional characteristics, are called metasurfaces. Through the programming of the RIS, it is possible to control and/or modify the radio waves that affect it, thus shaping the radio environment. To overcome the limitations of RISs, the metaprism represents an alternative: it is a passive and non-reconfigurable frequency-selective metasurface that acts as a metamirror to improve the efficiency of the wireless link. In particular, using an OFDM (Orthogonal Frequency-Division Multiplexing) signaling it is possible to control the reflection of the signal, suitably selecting the sub-carrier assigned to each user, without having to interact with the metaprism or having to estimate the CSI. This thesis investigates how OFDM signaling and metaprism can be used for localization purposes, especially to extend the coverage area at low cost, in a scenario where the user is in NLoS (Non-line-of-sight) conditions with respect to the base station, both single antenna. In particular, the paper concerns the design of the analytical model and the corresponding Matlab implementation of a Maximum Likelihood (ML) estimator able to estimate the unknown position, behind an obstacle, from which a generic user transmits to a base station, exploiting the metaprism.

Numerical modeling on the short-term response of fiber-reinforced concrete round panels

Fiber-reinforced concrete is a composite material consisting of discrete, discontinuous, and uniformly distributed fibers in plain concrete primarily used to enhance the tensile properties of the concrete. FRC performance depends upon the fiber, interface, and matrix properties. The use of fiber-reinforced concrete has been increasing substantially in the past few years in different fields of the construction industry such as ground-level application in sidewalks and building floors, tunnel lining, aircraft parking, runways, slope stabilization, etc. Many experiments have been performed to observe the short-term and long-term mechanical behavior of fiber-reinforced concrete in the last decade and numerous numerical models have been formulated to accurately capture the response of fiber-reinforced concrete. The main purpose of this dissertation is to numerically calibrate the short-term response of the concrete and fiber parameters in mesoscale for the three-point bending test and cube compression test in the MARS framework which is based on the lattice discrete particle model (LDPM) and later validate the same parameters for the round panels. LDPM is the most validated theory in mesoscale theories for concrete. Different seeds representing the different orientations of concrete and fiber particles are simulated to produce the mean numerical response. The result of numerical simulation shows that the lattice discrete particle model for fiber-reinforced concrete can capture results of experimental tests on the behavior of fiber-reinforced concrete to a great extent.

Fiber-reinforced Composite as Oral Implant Material. Experimental studies of glass fiber and bioactive glass in vitro and in vivo

Fiber-reinforced composite as oral implant material: Experimental studies of glass fiber and bioactive glass in vitro and in vivo Department of Prosthetic Dentistry and Biomaterials Science, Institute of Dentistry, University of Turku, Turku, Finland 2008. Biocompatibility and mechanical properties are important variables that need to be determined when new materials are considered for medical implants. Special emphasis was placed on these characteristics in the present work, which aimed to investigate the potential of fiber-reinforced composite (FRC) material as an oral implant. Furthermore, the purpose of this study was to explore the effect of bioactive glass (BAG) on osseointegration of FRC implants. The biocompatibility and mechanical properties of FRC implants were studied both in vitro and in vivo. The mechanical properties of the bulk FRC implant were tested with a cantilever bending test, torsional test and push-out test. The biocompatibility was first evaluated with osteoblast cells cultured on FRC substrates. Bone bonding was determined with the mechanical push-out test and histological as well as histomorplanimetric evaluation. Implant surface was characterized with SEM and EDS analysis. The results of these studies showed that FRC implants can withstand the static load values comparably to titanium. Threaded FRC implants had significantly higher push-out strength than the threaded titanium implants. Cell culture study revealed no cytotoxic effect of FRC materials on the osteoblast-like-cells. Addition of BAG particles enhanced cell proliferation and mineralization of the FRC substrates The in vivo study showed that FRC implants can withstand static loading until failure without fracture. The results also suggest that the FRC implant is biocompatible in bone. The biological behavior of FRC was comparable to that of titanium after 4 and 12 weeks of implantation. Furthermore, addition of BAG to FRC implant increases peri-implant osteogenesis and bone maturation.

Non-resorbable glass fibre-reinforced composite with porous surface as bone substitute material: Experimental studies in vitro and in vivo focused on bone-implant interface

The development of load-bearing osseous implant with desired mechanical and surface properties in order to promote incorporation with bone and to eliminate risk of bone resorption and implant failure is a very challenging task. Bone formation and resoption processes depend on the mechanical environment. Certain stress/strain conditions are required to promote new bone growth and to prevent bone mass loss. Conventional metallic implants with high stiffness carry most of the load and the surrounding bone becomes virtually unloaded and inactive. Fibre-reinforced composites offer an interesting alternative to metallic implants, because their mechanical properties can be tailored to be equal to those of bone, by the careful selection of matrix polymer, type of fibres, fibre volume fraction, orientation and length. Successful load transfer at bone-implant interface requires proper fixation between the bone and implant. One promising method to promote fixation is to prepare implants with porous surface. Bone ingrowth into porous surface structure stabilises the system and improves clinical success of the implant. The experimental part of this work was focused on polymethyl methacrylate (PMMA) -based composites with dense load-bearing core and porous surface. Three-dimensionally randomly orientated chopped glass fibres were used to reinforce the composite. A method to fabricate those composites was developed by a solvent treatment technique and some characterisations concerning the functionality of the surface structure were made in vitro and in vivo. Scanning electron microscope observations revealed that the pore size and interconnective porous architecture of the surface layer of the fibre-reinforced composite (FRC) could be optimal for bone ingrowth. Microhardness measurements showed that the solvent treatment did not have an effect on the mechanical properties of the load-bearing core. A push-out test, using dental stone as a bone model material, revealed that short glass fibre-reinforced porous surface layer is strong enough to carry load. Unreacted monomers can cause the chemical necrosis of the tissue, but the levels of leachable resisidual monomers were considerably lower than those found in chemically cured fibre-reinforced dentures and in modified acrylic bone cements. Animal experiments proved that surface porous FRC implant can enhance fixation between bone and FRC. New bone ingrowth into the pores was detected and strong interlocking between bone and the implant was achieved.

Repair of segmental bone defects with fiber-reinforced composite: a study of material development and an animal model on rabbits

The Repair of segmental defects in load-bearing long bones is a challenging task because of the diversity of the load affecting the area; axial, bending, shearing and torsional forces all come together to test the stability/integrity of the bone. The natural biomechanical requirements for bone restorative materials include strength to withstand heavy loads, and adaptivity to conform into a biological environment without disturbing or damaging it. Fiber-reinforced composite (FRC) materials have shown promise, as metals and ceramics have been too rigid, and polymers alone are lacking in strength which is needed for restoration. The versatility of the fiber-reinforced composites also allows tailoring of the composite to meet the multitude of bone properties in the skeleton. The attachment and incorporation of a bone substitute to bone has been advanced by different surface modification methods. Most often this is achieved by the creation of surface texture, which allows bone growth, onto the substitute, creating a mechanical interlocking. Another method is to alter the chemical properties of the surface to create bonding with the bone – for example with a hydroxyapatite (HA) or a bioactive glass (BG) coating. A novel fiber-reinforced composite implant material with a porous surface was developed for bone substitution purposes in load-bearing applications. The material’s biomechanical properties were tailored with unidirectional fiber reinforcement to match the strength of cortical bone. To advance bone growth onto the material, an optimal surface porosity was created by a dissolution process, and an addition of bioactive glass to the material was explored. The effects of dissolution and orientation of the fiber reinforcement were also evaluated for bone-bonding purposes. The Biological response to the implant material was evaluated in a cell culture study to assure the safety of the materials combined. To test the material’s properties in a clinical setting, an animal model was used. A critical-size bone defect in a rabbit’s tibia was used to test the material in a load-bearing application, with short- and long-term follow-up, and a histological evaluation of the incorporation to the host bone. The biomechanical results of the study showed that the material is durable and the tailoring of the properties can be reproduced reliably. The Biological response - ex vivo - to the created surface structure favours the attachment and growth of bone cells, with the additional benefit of bioactive glass appearing on the surface. No toxic reactions to possible agents leaching from the material could be detected in the cell culture study when compared to a nontoxic control material. The mechanical interlocking was enhanced - as expected - with the porosity, whereas the reinforcing fibers protruding from the surface of the implant gave additional strength when tested in a bone-bonding model. Animal experiments verified that the material is capable of withstanding load-bearing conditions in prolonged use without breaking of the material or creating stress shielding effects to the host bone. A Histological examination verified the enhanced incorporation to host bone with an abundance of bone growth onto and over the material. This was achieved with minimal tissue reactions to a foreign body. An FRC implant with surface porosity displays potential in the field of reconstructive surgery, especially regarding large bone defects with high demands on strength and shape retention in load-bearing areas or flat bones such as facial / cranial bones. The benefits of modifying the strength of the material and adjusting the surface properties with fiber reinforcement and bone-bonding additives to meet the requirements of different bone qualities are still to be fully discovered.

Unidirectional fiber-reinforced composite as an oral implant abutment material: Experimental studies of E-glass fiber/BisGMA-TEGDMA polymer in vitro

Fiber-reinforced composites (FRCs) are a new group of non-metallic biomaterials showing a growing popularity in many dental and medical applications. As an oral implant material, FRC is biocompatible in bone tissue environment. Soft tissue integration to FRC polymer material is unclear. This series of in vitro studies aimed at evaluating unidirectional E-glass FRC polymer in terms of mechanical, chemical, and biological properties in an attempt to develop a new non-metallic oral implant abutment alternative. Two different types of substrates were investigated: (a) Plain polymer (BisGMA 50%–TEGDMA 50%) and (b) Unidirectional FRC. The mechanical behavior of high fiber-density FRCs was assessed using a three-point bending test. Surface characterization was performed using scanning electron and spinning disk confocal microscopes. The surface wettability/energy was determined using sessile drop method. The blood response, including blood-clotting ability and platelet morphology was evaluated. Human gingival fibroblast cell responses - adhesion kinetics, adhesion strength, and proliferation activity - were studied in cell culture environment using routine test conditions. A novel tissue culture method was developed and used to evaluate porcine gingival tissue graft attachment and growth on the experimental composite implants. The analysis of the mechanical properties showed that there is a direct proportionality in the relationship between E-glass fiber volume fraction and toughness, modulus of elasticity, and load bearing capacity; however, flexural strength did not show significant improvement when high fiber-density FRC is used. FRCs showed moderate hydrophilic properties owing to the presence of exposed glass fibers on the polymer surface. Blood-clotting time was shorter on FRC substrates than on plain polymer. The FRC substrates also showed higher platelet activation state than plain polymer substrates. Fibroblast cell adhesion strength and proliferation rate were highly pronounced on FRCs. A tissue culture study revealed that gingival epithelium and connective tissue established an immediate close contact with both plain polymer and FRC implants. However, FRC seemed to guide epithelial migration outwards from the tissue/implant interface. Due to the anisotropic and hydrophilic nature of FRC, it can be concluded that this material enhances biological events related with soft tissue integration on oral implant surface.

Simultaneous Drying and Separation of Composite Agricultural Material for Hay Processing

In composite agricultural materials such as grass, tee, medicinal plants; leaves and stems have a different drying time. By this behavior, after leaving the dryer, the stems may have greater moisture content than desired, while the leaves one minor, which can cause either the appearance of fungi or the collapse of the over-dried material. Taking into account that a lot of grass is dehydrated in forced air dryers, especially rotary drum dryers, this research was developed in order to establish conditions enabling to make a separation of the components during the drying process in order to provide a homogeneous product at the end. For this, a rotary dryer consisting of three concentric cylinders and a circular sieve aligned with the more internal cylinder was proposed; so that, once material enters into the dryer in the area of the inner cylinder, stems pass through sieve to the middle and then continue towards the external cylinder, while the leaves continue by the inner cylinder. For this project, a mixture of Ryegrass and White Clover was used. The characteristics of the components of a mixture were: Drying Rate in thin layer and in rotation, Bulk density, Projected Area, Terminal velocity, weight/Area Ratio, Flux through Rotary sieve. Three drying temperatures; 40°C, 60° C and 80° C, and three rotation speeds; 10 rpm, 20 rpm and 40 rpm were evaluated. It was found that the differences in drying time are the less at 80 °C when the dryer rotates at 40 rpm. Above this speed, the material adheres to the walls of the dryer or sieve and does not flow. According to the measurements of terminal velocity of stems and leaves of the components of the mixture, the speed of the air should be less than 1.5 m s-1 in the inner drum for the leaves and less than 4.5 m s-1 in middle and outer drums for stems, in such way that only the rotational movement of the dryer moves the material and achieves a greater residence time. In other hand, the best rotary sieve separation efficiencies were achieved when the material is dry, but the results are good in all the moisture contents. The best rotary speed of sieve is within the critical rotational speed, i.e. 20 rpm. However, the rotational speed of the dryer, including the sieve in line with the inner cylinder should be 10 rpm or less in order to achieve the greatest residence times of the material inside the dryer and the best agitation through the use of lifting flights. With a finite element analysis of a dryer prototype, using an air flow allowing speeds of air already stated, I was found that the best performance occurs when, through a cover, air enters the dryer front of the Middle cylinder and when the inner cylinder is formed in its entirety through a sieve. This way, air flows in almost equal amounts by both the middle and external cylinders, while part of the air in the Middle cylinder passes through the sieve towards the inner cylinder. With this, leaves do not adhere to the sieve and flow along drier, thanks to the rotating movement of the drums and the showering caused by the lifting flights. In these conditions, the differences in drying time are reduced to 60 minutes, but the residence time is higher for the stems than for leaves, therefore the components of the mixture of grass run out of the dryer with the same desired moisture content.