Biofunctional composite coating architectures based on polycaprolactone and nanohydroxyapatite for controlled corrosion activity and enhanced biocompatibility of magnesium AZ31 alloy

In this work a biofunctional composite coating architecture for controlled corrosion activity and enhanced cellular adhesion of AZ31 Mg alloys is proposed. The composite coating consists of a polycaprolactone (PCL) matrix modified with nanohydroxyapatite (HA) applied over a nanometric layer of polyetherimide (PEI). The protective properties of the coating were studied by electrochemical impedance spectroscopy (EIS), a non-disturbing technique, and the coating morphology was investigated by field emission scanning electron microscopy (FE-SEM). The results show that the composite coating protects the AZ31 substrate. The barrier properties of the coating can be optimized by changing the PCL concentration. The presence of nanohydroxyapatite particles influences the coating morphology and decreases the corrosion resistance. The biocompatibility was assessed by studying the response of osteoblastic cells on coated samples through resazurin assay, confocal laser scanning microscopy (CLSM) and scanning electron microscopy (SEM). The results show that the polycaprolactone to hydroxyapatite ratio affects the cell behavior and that the presence of hydroxyapatite induces high osteoblastic differentiation. (C) 2014 Elsevier B.V. All rights reserved.

Preliminary study on the production of functionally graded materials by friction stir processing

Dissertação apresentada na Faculdade de Ciências e Tecnologia da Universidade Nova de Lisboa para obtenção do grau de Mestre em Engenharia Mecânica

Multiobjective design of viscoelastic laminated composite sandwich panels

The optimal design of laminated sandwich panels with viscoelastic core is addressed in this paper, with the objective of simultaneously minimizing weight and material cost and maximizing modal damping. The design variables are the number of layers in the laminated sandwich panel, the layer constituent materials and orientation angles and the viscoelastic layer thickness. The problem is solved using the Direct MultiSearch (DMS) solver for multiobjective optimization problems which does not use any derivatives of the objective functions. A finite element model for sandwich plates with transversely compressible viscoelastic core and anisotropic laminated face layers is used. Trade-off Pareto optimal fronts are obtained and the results are analyzed and discussed.

Electrospun Polyaniline-Reduced Graphene Oxide Composite Nanofibers Based High Sensitive Ammonia Gas Sensor

Ammonia is an important gas in many power plants and industrial processes so its detection is of extreme importance in environmental monitoring and process control due to its high toxicity. Ammonia’s threshold limit is 25 ppm and the exposure time limit is 8 h, however exposure to 35 ppm is only secure for 10 min. In this work a brief introduction to ammonia aspects are presented, like its physical and chemical properties, the dangers in its manipulation, its ways of production and its sources. The application areas in which ammonia gas detection is important and needed are also referred: environmental gas analysis (e.g. intense farming), automotive-, chemical- and medical industries. In order to monitor ammonia gas in these different areas there are some requirements that must be attended. These requirements determine the choice of sensor and, therefore, several types of sensors with different characteristics were developed, like metal oxides, surface acoustic wave-, catalytic-, and optical sensors, indirect gas analyzers, and conducting polymers. All the sensors types are described, but more attention will be given to polyaniline (PANI), particularly to its characteristics, syntheses, chemical doping processes, deposition methods, transduction modes, and its adhesion to inorganic materials. Besides this, short descriptions of PANI nanostructures, the use of electrospinning in the formation of nanofibers/microfibers, and graphene and its characteristics are included. The created sensor is an instrument that tries to achieve a goal of the medical community in the control of the breath’s ammonia levels being an easy and non-invasive method for diagnostic of kidney malfunction and/or gastric ulcers. For that the device should be capable to detect different levels of ammonia gas concentrations. So, in the present work an ammonia gas sensor was developed using a conductive polymer composite which was immobilized on a carbon transducer surface. The experiments were targeted to ammonia measurements at ppb level. Ammonia gas measurements were carried out in the concentration range from 1 ppb to 500 ppb. A commercial substrate was used; screen-printed carbon electrodes. After adequate surface pre-treatment of the substrate, its electrodes were covered by a nanofibrous polymeric composite. The conducting polyaniline doped with sulfuric acid (H2SO4) was blended with reduced graphene oxide (RGO) obtained by wet chemical synthesis. This composite formed the basis for the formation of nanofibers by electrospinning. Nanofibers will increase the sensitivity of the sensing material. The electrospun PANI-RGO fibers were placed on the substrate and then dried at ambient temperature. Amperometric measurements were performed at different ammonia gas concentrations (1 to 500 ppb). The I-V characteristics were registered and some interfering gases were studied (NO2, ethanol, and acetone). The gas samples were prepared in a custom setup and were diluted with dry nitrogen gas. Electrospun nanofibers of PANI-RGO composite demonstrated an enhancement in NH3 gas detection when comparing with only electrospun PANI nanofibers. Was visible higher range of resistance at concentrations from 1 to 500 ppb. It was also observed that the sensor had stable, reproducible and recoverable properties. Moreover, it had better response and recovery times. The new sensing material of the developed sensor demonstrated to be a good candidate for ammonia gas determination.

Printable organic and inorganic materials for flexible electrochemical devices

Portuguese Science Foundation - project Electra PTDC/CTM/099124/2008 and the PhD grant SFRH/BD/45224. financial support: Professor E. Fortunato’s ERC 2008 Advanced Grant (INVISIBLE contract number 228144), “APPLE” FP7-NMP-2010-SME/262782-2 and “SMARTEC” FP7-ICT-2009.3.9/258203

Production and characterization of electrospun composite fibers: confinement of thermosensitive microgels

Materials engineering focuses on the assembly of materials´ properties to design new products with the best performance. By using sub-micrometer size materials in the production of composites, it is possible to obtain objects with properties that none of their compounds show individually. Once three-dimensional materials can be easily customized to obtain desired properties, much interest has been paid to nanostructured poly-mers in order to build biocompatible devices. Over the past years, the thermosensitive microgels have become more common in the framework of bio-materials with potential applicability in therapy and/or diagnostics. In addition, high aspect ratio biopolymers fibers have been produced using the cost-effective method called electrospinning. Taking advantage of both microgels and electrospun fibers, surfaces with enhanced functionalities can be obtained and, therefore employed in a wide range of applications. This dissertation reports on the confinement of stimuli-responsive microgels through the colloidal electro-spinning process. The process mainly depends on the composition, properties and patterning of the precur-sor materials within the polymer jet. Microgels as well as the electrospun non-woven mats were investigated to correlate the starting materials with the final morphology of the composite fibers. PNIPAAm and PNIPAAm/Chitosan thermosensitive microgels with different compositions were obtained via surfactant free emulsion polymerization (SFEP) and characterized in terms of chemical structure, morphology, thermal sta-bility, swelling properties and thermosensitivity. Finally, the colloidal electrospinning method was carried out from spinning solutions composed of the stable microgel dispersions (up to a concentration of about 35 wt. % microgels) and a polymer solution of PEO/water/ethanol mixture acting as fiber template solution. The confinement of microgels was confirmed by Scanning Electron Microscopy (SEM). The electrospinning process was statistically analysed providing the optimum set of parameters aimed to minimize the fiber diameter, which give rise to electrospun nanofibers of PNIPAAm microgels/PEO with a mean fiber diameter of 63 ± 25 nm.

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.

Shear strengthening of damaged reinforced concrete beams with hybrid composite plates

This paper aims to evaluate experimentally the potentialities of Hybrid Composite Plates (HCPs) technique for the shear strengthening of reinforced concrete (RC) beams that were previously subjected to intense damage in shear. HCP is a thin plate of Strain Hardening Cementitious Composite (SHCC) reinforced with Carbon Fiber Reinforced Polymer (CFRP) laminates. For this purpose, an experimental program composed of two series of beams (rectangular and T cross section) was executed to assess the strengthening efficiency of this technique. In the first step of this experimental program, the control beams, without steel stirrups, were loaded up to their shear failure, and fully unloaded. Then, these pre-damaged beams were shear strengthened by applying HCPs to their lateral faces by using a combination of epoxy adhesive and mechanical anchors. The bolts were applied with a certain torque in order to increase the concrete confinement. The obtained results showed that the increase of load carrying capacity of the damaged strengthened beams when HCPs were applied with epoxy adhesive and mechanical anchors was 2 and 2.5 times of the load carrying capacity of the corresponding reference beams (without HCPs) for the rectangular and T cross section beam series, respectively. To further explore the potentialities of the HCPs technique for the shear strengthening, the experimental tests were simulated using an advanced numerical model by a FEM-based computer program. After demonstration the good predictive performance of the numerical model, a parametric study was executed to highlight the influence of SHCC as an alternative for mortar, as well as the influence of torque level applied to the mechanical anchors, on the load carrying capacity of beams strengthened with the proposed technique.

Evaluation of the performance of recycled textile fibres in the mechanical behaviour of a gypsum and cork composite material

Given the need for using more sustainable constructive solutions, an innovative composite material based on a combination of distinct industrial by-products is proposed aiming to reduce waste and energy consumption in the production of construction materials. The raw materials are thermal activated flue-gas desulphurization (FGD) gypsum, which acts as a binder, granulated cork as the aggregate and recycled textile fibres from used tyres intended to reinforce the material. This paper presents the results of the design of the composite mortar mixes, the characterization of the key physical properties (density, porosity and ultrasonic pulse velocity) and the mechanical validation based on uniaxial compressive tests and fracture energy tests. In the experimental campaign, the influence of the percentage of the raw materials in terms of gypsum mass, on the mechanical properties of the composite material was assessed. It was observed that the percentage of granulated cork decreases the compressive strength of the composite material but contributes to the increase in the compressive fracture energy. Besides, the recycled textile fibres play an important role in the mode I fracture process and in the fracture energy of the composite material, resulting in a considerable increase in the mode I fracture energy.

Producing LFT composite parts for large consumption markets from thermoplastic powder-coated towpregs

Thermoplastic matrix composites are receiving increasing interest in last years. This is due to several advantageous properties and speed of processing of these materials as compared to their thermoset counterparts. Among thermoplastic composites, Long Fibre Thermoplastics (LFTs) have seen the fastest growth, mainly due to developments in the automotive sector. LFTs combine the (semi-)structural material properties of long (>1 cm) fibres, with the ease and speed of thermoplastic processing. This paper reports a study of a novel low-cost LFT technology and resulting composites. A patented powder-coating machine able to produce continuously pre-impregnated materials directly from fibre rovings and polymer powders was used to process glass-fibre reinforced polypropylene (GF/PP) towpregs. Such pre-impregnated materials were then chopped and used to make LFTs in a patented low-cost piston-blender developed by the Centre of Lightweight Structures, TUD-TNO, the Netherlands. The work allowed studying the most relevant towpreg production parameters and establishing the processing window needed to obtain a good quality GF/PP powder coated material. Finally, the processing window that allows producing LFTs of good quality in the piston-blender and the mechanical properties of final stamped GF/PP composite parts were also determined.

Novel hybrid multifunctional magnetoelectric porous composite films

Novel multifunctional porous films have been developed by the integration of magnetic CoFe2O4 (CFO) nanoparticles into poly(vinylidene fluoride)-Trifuoroethylene (P(VDF-TrFE)), taking advantage of the synergies of the magnetostrictive filler and the piezoelectric polymer. The porous films show a piezoelectric response with an effective d33 coefficient of -22 pC/N-1, a maximum magnetization of 12 emu.g-1 and a maximum magnetoelectric coefficient of 9 mV.cm-1.Oe-1. In this way, a multifunctional membrane has been developed suitable for advanced applications ranging from biomedical to water treatment.

Energy harvesting device based on a metallic glass/PVDF magnetoelectric laminated composite

A flexible and low cost energy harvester device based on the magnetoelectric (ME) effect has been designed using Fe64Co17Si7B12 as amorphous magnetostrictive ribbons and PVDF as the piezoelectric element. Sandwich-type laminated composite of 3 cm long has been fabricated by gluing these ribbons to the PVDF with the Devcon 5 minute epoxy. Good power output and power density of 6.4 μW and 1.5 mW/cm3, respectively, have been obtained through a multiplier circuit. All values have been measured at the magnetomechanical resonance of the laminate. The effect of the length of the ME laminate on the power output has been also studied, exhibiting a decay as the length of the ME laminate does. Nevertheless, good performance of such device has been obtained for a 0.5 cm long device, working already at 337 KHz, within the low radio frequency (LRF) range.

Mechanical, fatigue and wear properties of sintered Carbon Nanotube-based functionally graded materials

Tese de Doutoramento Engenharia Mecânica

Development of composite auxetic structures for civil engineering applications

Tese de Doutoramento em Engenharia Têxtil

Thermoset Composite Concrete Reinforcement, HR-325, Part 2, 1992

This is the second part of the final report submitted to the Iowa Department of Transportation. Part 1 contained a comparison of unaged fiber composite and steel dowels and derivation of the appropriate theoretical model for analyzing the results. Part 2 of this final report covers the theoretical and experimental models for accelerated aging of fiber composite reinforcing bars and dowels cast in a concrete environment. Part 2 contains results from testing of unaged and aged fiber composite dowels and steel dowels, in addition to unaged and aged fiber composite reinforcing bars. Additional tests have been performed on unaged dowels (both steel and fibercomposite) to verify results from Part 1 and to keep the testing program consistent. Slight modifications have been made to the dowel specimens presented in Part 1. These modifications are noted in the Section 3.4 of this report. The flexural modulus of elasticity for the FC dowel bar given in Part 1 of the final report (Table 3. 2) was for the incorrect structural shape (non-circular cross section). The value is corrected and given in Part 2 of the final report (Table 3.4 for the.modulus of elasticity supplied by the manufacturer, and Tables 3. 5 and 3. 6 for experimentally determined modulus of elasticities) • The value in Part 1 was not used for any analysis of the FC dowel bars.