Synthesis and characterization of novel 4H-pyran-4-ylidene indole-based heterocyclic systems for several optical applications

The development of organic materials displaying high two-photon absorption (TPA) has attracted much attention in recent years due to a variety of potential applications in photonics and optoelectronics, such as three-dimensional optical data storage, fluorescence imaging, two-photon microscopy, optical limiting, microfabrication, photodynamic therapy, upconverted lasing, etc. The most frequently employed structural motifs for TPA materials are donor–pi bridge–acceptor (D–pi–A) dipoles, donor–pi bridge–donor (D–pi–D) and acceptor–pi bridge-acceptor (A–pi–A) quadrupoles, octupoles, etc. In this work we present the synthesis and photophysical characterization of quadrupolar heterocyclic systems with potential applications in materials and biological sciences as TPA chromophores. Indole is a versatile building block for the synthesis of heterocyclic systems for several optoelectronic applications (chemosensors, nonlinear optical, OLEDs) due to its photophysical properties and donor electron ability and 4H-pyran-4-ylidene fragment is frequently used for the synthesis of red light-emitting materials. On the other hand, 2-(2,6-dimethyl-4H-pyran-4-ylidene)malononitrile (1) and 1,3-diethyl-dihydro-5-(2,6-dimethyl-4H-pyran-4-ylidene)-2-thiobarbituric (2) units are usually used as strong acceptor moieties for the preparation of π-conjugated systems of the push-pull type. These building blocks were prepared by Knoevenagel condensation of the corresponding ketone precursor with malononitrile or 1,3-diethyl-dihydro-2-thiobarbituric acid. The new quadrupolar 4H-pyran-4-ylidene fluorophores (3) derived from indole were prepared through condensation of 5-methyl-1H-indole-3-carbaldehyde with the acceptor precursors 1 and 2, in the presence of a catalytical amount of piperidine. The new compounds were characterized by the usual spectroscopic techniques (UV-vis., FT-IR and multinuclear NMR - 1H, 13C).

Sustainable mortars with incorporation of microencapsulated phase change materials

The construction industry is responsible for high energy and raw materials consumption. Thus, it is important to minimize the high energy consumption by taking advantage of renewable energy sources and reusing industrial waste, decreasing the extraction of natural materials. The mortars with incorporation of phase change materials (PCM) have the ability to regulate the temperature inside buildings, contributing to the thermal comfort and reduction of the use of heating and cooling equipment, using only the energy supplied by the sun. The simultaneous incorporation of PCM and fly ash (FA) can reduce the energy consumption and the amount of materials landfilled. However, the addition of these materials in mortars modifies its characteristics. The main purpose of this study was the production and characterization in the fresh and hardened state of mortars with incorporation of different contents of PCM and FA. The binders studied were aerial lime, hydraulic lime, gypsum and cement. The proportion of PCM studied was 0%, 20%, 40% and 60% of the mass of the sand. The content of fly ash added to the mortars was 0%, 20%, 40% and 60% of the mass of the binder. It was possible to observe that the incorporation of PCM and fly ash in mortars caused differences in properties such as workability, microstructure, water absorption, compressive strength, flexural strength and adhesion.

Recycled asphalt mixtures produced with high percentage of different waste materials

The use of sustainable solutions in construction is not just an option, but is increasingly becoming a need of the Society. Thus, nowadays the recycling of waste materials is a growing technology that needs to be continuously improved, namely by researching new solutions for waste valorisation and by increasing the amount of wastes reused. In the paving industry, the reuse of reclaimed asphalt (RA) is becoming common practice, but needs further research work. Thus, this study aims to increase the incorporation of RA and other waste materials in the production of recycled asphalt mixtures in order to improve their mechanical, environmental and economic performance. Recycled mixtures with 50% RA were analysed in this study, including: i) RA selection, preparation and characterization; ii) incorporation of other waste materials as binder additives or modifiers, like used motor oil (UMO) and waste high density polyethylene (HDPE); iii) production of different mixtures (without additives; with UMO; with UMO and HDPE) and comparison of their performance in order to assess the main advantages of each solution. With this study it was concluded that up to 7.5 % of UMO and 4.0 % of HDPE can be used in a new modified binder for asphalt mixtures with 50 % of RA, which have excellent properties concerning the rutting with WTS = 0.02 mm/103 cycles, the fatigue resistance with ε6 = 160.4, and water sensitivity with an ITSR of 81.9 %.

Application of acoustic emission technique for bond characterization in FRP-masonry systems

The acoustic emission (AE) technique is used for investigating the interfacial fracture and damage propagation in GFRP-and SRG-strengthened bricks during debonding tests. The bond behavior is investigated through single-lap shear bond tests and the fracture progress during the tests is recorded by means of AE sensors. The fracture progress and active debonding mechanisms are characterized in both specimen types with the aim of AE outputs. Moreover, a clear distinction between the AE outputs of specimens with different failure modes, in both SRG-and GFRP-strengthened specimens, is found which allows characterizing the debonding failure mode based on acoustic emission data.

Tensile creep of a structural epoxy adhesive: experimental and analytical characterization

Epoxy adhesives are nowadays being extensively used in Civil Engineering applications, mostly in the scope of the rehabilitation of reinforced concrete (RC) structures. In this context, epoxy adhesives are used to provide adequate stress transference from fibre reinforced polymers (FRP) to the surrounding concrete substrate. Most recently, the possibility of using prestressed FRPs bonded with these epoxy adhesives is also being explored in order to maximize the potentialities of this strengthening approach. In this context, the understanding of the long term behaviour of the involved materials becomes essential. Even when non-prestressed FRPs are used a certain amount of stress is permanently applied on the adhesive interface during the serviceability conditions of the strengthened structure, and the creep of the adhesive may cause a continuous variation in the deformational response of the element. In this context, this paper presents a study aiming to experimentally characterize the tensile creep behaviour of an epoxy-based adhesive currently used in the strengthening of concrete structures with carbon FRP (CFRP) systems. To analytically describe the tensile creep behaviour, the modified Burgers model was fitted to the experimental creep curves, and the obtained results revealed that this model is capable of predicting with very good accuracy the long term behaviour of this material up to a sustained stress level of 60% of the adhesive’s tensile strength.

Tensile and bond characterization of natural fibers embeeded in inorganic matrices

Innovative composite materials made of continuous fibers embedded in mortar matrices have been recently received attention for externally bonded reinforcement of masonry structures. In this regards, application of natural fibers for strengthening of the repair mortars is attractive due to their low specific weight, sustainability and recycability. This paper presents experimental characterization of tensile and pull-out behavior of natural fibers embedded in two different mortar-based matrices. A lime-based and a geopolymeric-based mortar are used as sustainable and innovative matrices. The obtained experimental results and observations are presented and discussed.

In-line rheo-optical characterization during small-scale polymer processing and compounding

As increasingly more sophisticated materials and products are being developed and times-to-market need to be minimized, it is important to make available fast response characterization tools using small amounts of sample, capable of conveying data on the relationships between rheological response, process-induced material structure and product characteristics. For this purpose, a single / twin-screw mini-extrusion system of modular construction, with well-controlled outputs in the range 30-300 g/h, was coupled to a in- house developed rheo-optical slit die able to measure shear viscosity and normal-stress differences, as well as performing rheo-optical experiments, namely small angle light scattering (SALS) and polarized optical microscopy (POM). In addition, the mini-extruder is equipped with ports that allow sample collection, and the extrudate can be further processed into products to be tested later. Here, we present the concept and experimental set-up [1, 2]. As a typical application, we report on the characterization of the processing of a polymer blend and of the properties of extruded sheets. The morphological evolution of a PS/PMMA industrial blend along the extruder, the flow-induced structures developed and the corresponding rheological characteristics are presented, together with the mechanical and structural characteristics of produced sheets. The application of this experimental tool to other material systems will also be discussed.

Study of the potential employment of Malvaceae Species in composites materials

The employ of vegetal fibers for textiles and composites represents a great potential in economic and social sustainable development. Some Malvaceae species are considered tropical cosmopolitans, such as from Sida genus. Several species of this genus provide excellent textile bast fibers, which are very similar in qualities to the jute textile fiber. The objective of the present study is present the physicochemical characterization of six Brazilian vegetal fibers: Sida rhombifolia L.; Sida carpinifolia L. f.; Sidastrum paniculatum (L.) Fryxell; Sida cordifolia L.; Malvastrum coromandelianum (L.) Gurck; Wissadula subpeltata (Kuntze) R.E.Fries. Respectively the two first species are from Brazilian Atlantic Forest biome and the four remaining from Brazilian Cerrado biome, despite of present in other regions of the planet. The stems of these species were retted in water at 37oC for 20 days. The fibers were tested in order to determine tensile rupture strength, tenacity, elongation, Young’s modulus, cross microscopic structure, Scanning Electronic Microscopy (SEM), regain, combustion, acid, alkali, organic solvent and cellulase effects, pH of the aqueous extract, Differential Scanning Calorimetry (DSC) and Thermogravimetric Analysis (TGA). The obtained values were compared with those from fibers of recognized applicability in the textile industry including hemp. The results are promising in terms of their employment in thermoset and thermoplastic medium resistance composites.

Characterization of physical, mechanical and chemical properties of quiscal fibres : the influence of atmospheric DBD plasma treatment

This paper reports the first attempt of characterizing various physical, mechanical and chemical properties of Quiscal fibres, used by the native communities in Chile and investigating the influence of atmospheric dielectric barrier discharge plasma treatment on various properties such as diameter and linear density, fat, wax and impurity%, moisture regain, chemical elements and groups, thermal degradation, surface morphology, etc. According to the experimental observations, Quiscal fibre has lower tenacity than most of the technical grade natural fibres such as sisal, hemp, flax, etc., and plasma treatment at optimum dose improved its tenacity to the level of sisal fibres. Plasma treatment also reduced the amount of fat, wax and other foreign impurities present in Quiscal fibres as well as removed lignin and hemicellulose partially from the fibre structure. Plasma treatment led to functionalization of Quiscal fibre surface with chemical groups, as revealed from attenuated total reflection spectroscopy and also confirmed from the elemental analysis using energy dispersive Xray technique and pH and conductivity measurements of fibre aqueous extract. The wetting behavior of Quiscal fibre also improved considerably through plasma treatment. However, untreated and plasma treated Quiscal fibres showed similar thermal degradation behavior, except the final degradation stage, in which plasma treated fibres showed higher stability and incomplete degradation unlike the untreated fibres. The experimental results suggested that the plasma treated Quiscal fibres, like other technical grade natural fibres, can find potential application as reinforcement of composite materials for various industrial applications.

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

Tese de Doutoramento Engenharia Mecânica

Electrochemical vs antibacterial characterization of ZrCN-Ag coatings

Nowadays, antibacterial properties are becoming a viable feature to be introduced in biomaterials due to the possibility of modifying the materials' surface used in medical devices in a micro/nano metric scale. As a result, it is mandatory to understand the mechanisms of the antimicrobial agents currently used and their possible failures. In this work, the antibacterial activity of ZrCNAg films is studied, taking into consideration the ability of silver nanoparticles to be dissolved when embedded into a ceramic matrix. The study focuses on the silver release evaluated by glow discharge optical emission spectroscopy and the effect of the fluid composition on this release. The results revealed a very low silver release of the films, leading to non-antibacterial activity of such materials. The silver release was found to be dependent on the electrolyte composition. NaCl (8.9 g L? 1) showed the lowest spontaneously silver ionization, while introducing the sulfates in Hanks' balanced salt solution (HBSS) such ionization is increased; finally, the proteins incorporated to the (HBSS) showed a reduction of the silver release, which also explains the low ionization in the culture medium (tryptic soy broth) that contains high quantities of proteins.

Characterization of dry-stack interlocking compressed earth blocks

Earth has been a traditional building material to construct houses in Africa. One of the most common techniques is the use of sun dried or kiln fired adobe bricks with mud mortar. Fired bricks are the main cause for deforestation in countries like Malawi. Although this technique is low-cost, the bricks vary largely in shape, strength and durability. This leads to weak houses which suffer considerable damage during floods and seismic events. One solution is the use of dry-stack masonry with stabilized interlocking compressed earth blocks (ICEB). This technology has the potential of substituting the current bricks by a more sustainable kind of block. This study was made in the context of the HiLoTec project, which focuses on houses in rural areas of developing countries. For this study, Malawi was chosen for a case study. This paper presents the experimental results of tests made with dry-stack ICEBs. Soil samples from Malawi were taken and studied. Since the experimental campaign could not be carried out in Malawi, a homogenization process of Portuguese soil was made to produce ICEBs at the University of Minho, Portugal. Then, the compression and tensile strength of the materials was determined via small cylinder samples. Subsequently, the compression and flexural strength of units were determined. Finally, tests to determine the compressive strength of both prisms and masonry wallets and to determine the initial shear strength of the dry interfaces were carried out. This work provides valuable data for low-cost eco-efficient housing

Assessment of the mechanical performance of recycled unbound materials for pavement subbase layers

The cyclic load triaxial test is a laboratory test that allows studying the mechanical behaviour of unbound granular materials used in base/subbase layers of road pavements. The resilient modulus and permanent strains are required as inputs in structural pavement design. This paper presents some results obtained for recycled materials (crushed concrete aggregate and blended crushed waste aggregate), with a view to promoting their use in pavement structures. Results relating to a reference material (limestone) are also presented, for comparison. All the test results discussed in this paper were obtained in variable cyclic radial pressure (VCP) tests. The tests performed (VCP) aim to study the influence of water content on the resilient modulus of recycled materials, as well as on the resistance to permanent deformation. Using the experimental data as a basis, further modelling work was carried out to establish the stresses developing in base/capping layers in typical Belgian road pavements. These numerical results allow to propose some simplifications of the stress paths applied in the testing procedures and to establish a new test protocol that also considers compaction during construction works. The results of this research work provide an excellent set of findings for the mechanical characterization of unbound base materials through the cyclic triaxial test, and contribute to a better understanding and correct application of recycled materials under geotechnical engineering background

Bombyx mori Silk Fibers: An outstanding family of materials

Designing novel multifunctional materials from natural resources is a challenging goal that has increasingly attracted researchers. Recently, the great potential of silk fibers has been recognized. The target readers for this review are researchers from different backgrounds (i.e., non-specialists in silk research) with special interests on the physical–chemical characterization of silk fibers, since their knowledge is crucial for the improvement of existent silk-based biomaterials and the basis for the development of new products. Examples of usual applications of Bombyx mori silk fibers are given and some of the most recent and exciting progress in new technological fields, is presented.

Production and characterization of ZrCN-Ag coatings deposited by mganetron sputtering

Tese de Doutoramento (Programa doutoral em Engenharia de Materiais)