The early metallurgy in Southwestern Iberia: metals from the Chalcolithic Settlement of São Pedro (Redondo)

Archaeological excavations carried out in the archaeological site of São Pedro (Southern Portugal) revealed a Chalcolithic settlement occupied in different moments of the 3rd millennium BC. The material culture recovered includes different types of materials, such as ceramics, lithics and metals. The later comprises about 30 artefacts with different typologies such as tools (e.g. awls, chisels and a saw) and weapons (e.g. daggers and arrowheads) mostly belonging to the 2nd and 3rd quarter of the 3rd millennium BC. In the present work the collection of chalcolithic metallic artefacts recovered in São Pedro was characterized. Analytical studies involved micro energy dispersive X-ray fluorescence spectrometry (micro-EDXRF) to determine elemental composition, together with optical microscopy and Vickers microhardness testing for microstructural characterisation and hardness determination. Main results show copper with variable amounts of arsenic and very low content of other impurities, such as iron. Moreover, nearly half of the collection is composed by arsenical copper alloys (As > 2 wt.%) and an association was found between arsenic content and typology since the weapons group (mostly daggers) present higher values than tools (mostly awls). These results suggest some criteria in the selection of arsenic-rich copper ores or smelting products. Furthermore, after casting an artefact would have been hammered, annealed and sometimes, finished with a hammering operation. Additionally, microstructural variations in this collection reveal somewhat different operational conditions during casting, annealing and forging, as expected in such a primitive metallurgy. Moreover the operational sequence seems to be used to achieve the required shape to the object, rather than to intentionally make the alloy harder. Overall, this study suggests that Chalcolithic metallurgists might have a poor control of the addition of arsenic and/or were unable to use this element to increase the hardness of tools and weapons. Finally, the compositions, manufacturing processes and hardness were compared to those from neighbouring regions and different chronological periods.

In Search of the Origins of Modernism: Venice and the Crisis of Classical Architecture in the mid-eighteenth century

This paper attempts to prove that in the years 1735 to 1755 Venice was the birthplace and cradle of Modern architectural theory, generating a major crisis in classical architecture traditionally based on the Vitruvian assumption that it imitates early wooden structures in stone or in marble. According to its rationalist critics such as the Venetian Observant Franciscan friar and architectural theorist Carlo Lodoli (1690-1761) and his nineteenth-century followers, classical architecture is singularly deceptive and not true to the nature of materials, in other words, dishonest and fallacious. This questioning did not emanate from practising architects, but from Lodoli himself– a philosopher and educator of the Venetian patriciate – who had not been trained as an architect. The roots of this crisis lay in a new approach to architecture stemming from the new rationalist philosophy of the Enlightenment age with its emphasis on reason and universal criticism.

Compact saloplastic membranes of natural polysaccharides for soft tissue engineering

The regeneration of soft biological tissues requires new substitutes that exhibit mechanical properties similar to the native tissue. Herein, thin saloplastic membranes with tunable physical properties are prepared by complexation of chitosan and alginate solutions containing different concentrations of sodium chloride. Polyelectrolyte complexes (PECs) are transferred to flat Petri dishes for compaction into membrane shapes by sedimentation and solvent evaporation. All membranes are resistant to degradation by lysozyme and are stable in solutions with pH values between 1 and 13. Immersing the different membranes in new doping solutions of increasing salt concentrations triggers the typical saloplastic behavior, with a high water absorption and decrease of the rigidity and ultimate tensile strength. The range of such variations is tuned by the sodium chloride amount used in the synthesis: high salt concentrations increase water uptake and tensile moduli, while decreasing the ultimate strength. Cellular assays demonstrate high proliferation rates and viability of L929 fibroblasts seeded onto the most rigid membranes. The results validate the use of saloplastic membranes as soft tissue substitutes for future biomedical applications.

Performance of a fly ash geopolymeric mortar for coating of ordinary portland cement concrete exposed to harsh chemical environments

Premature degradation of ordinary Portland cement (OPC) concrete infrastructures is a current and serious problem with overwhelming costs amounting to several trillion dollars. The use of concrete surface treatments with waterproofing materials to prevent the access of aggressive substances is an important way of enhancing concrete durability. The most common surface treatments use polymeric resins based on epoxy, silicone (siloxane), acrylics, polyurethanes or polymethacrylate. However, epoxy resins have low resistance to ultraviolet radiation while polyurethanes are sensitive to high alkalinity environments. Geopolymers constitute a group of materials with high resistance to chemical attack that could also be used for coating of concrete infrastructures exposed to harsh chemical environments. This article presents results of an experimental investigation on the resistance to chemical attack (by sulfuric and nitric acid) of several materials: OPC concrete, high performance concrete (HPC), epoxy resin, acrylic painting and a fly ash based geopolymeric mortar. Three types of acids, each with high concentrations of 10%, 20% and 30%, were used to simulate long term degradation by chemical attack. The results show that the epoxy resin had the best resistance to chemical attack, irrespective of the acid type and acid concentration.

Influence of type of binder and sand on the characteristics of masonry mortars

This study deals with the characterization of masonry mortars produced with different binders and sands. Several properties of the mortars were determined, like consistence, compressive and flexural strengths, shrinkage and fracture energy. By varying the type of binder (Portland cement, hydrated lime and hydraulic lime) and the type of sand (natural or artificial), it was possible to draw some conclusions about the influence of the composition on mortars properties. The results showed that the use of Portland cement makes the achievement of high strength classes easier. This was due to the slower hardening of lime compared with cement. The results of fracture energy tests showed much higher values for artificial sand mortars when compared with natural sand ones. This is due to the higher roughness of artificial sand particles which provided better adhesion between sand and binder.

Seismic evaluation of environmentally degraded FRP-strengthened masonry walls

Fiber Reinforced Polymers (FRPs) have been extensively used for externally bonded reinforcement of masonry structures during the last years. Available information shows that FRPs can significantly improve the seismic performance of masonry elements without altering their structural mass. However, the durability and long-term performance of the strengthened elements are not clearly known yet. Recent experimental results show that environmental conditions can lead to degradation of the bond between FRP and masonry and FRP delaminations. But the effect of these local degradation mechanisms on the global structural response is not studied yet. This paper is therefore aimed at numerically investigating the effect of environmental degradation on the global performance of strengthened masonry walls. The nonlinear behavior of masonry walls strengthened with FRP composites is initially simulated with the aim of a FE package. The adopted numerical modeling strategy is verified by comparison of numerical and experimental results. The model, once validated, is used for investigating the effect of materials and bond degradation on the global behavior and failure modes of strengthened walls. The effect of strengthening scheme on the long-term performance of strengthened walls is also investigated. The degradation data are taken from experimental tests previously performed by the authors. The numerical results show that the effect of local material degradation on the global response of strengthened walls depends on the strengthening schemes, and severity of the environmental conditions. Moreover, environmental induced degradations and FRP delaminations can lead to change of expected failure modes in the strengthened elements. These observations, that are usually neglected at the design stage, can be critical in the long-term performance of strengthened structures.

Comparative environmental life-cycle analysis of concretes using biomass and coal fly ashes as partial cement replacement material

Nowadays, the concrete production sector is challenged by attempts to minimize the usage of raw materials and energy consumption, as well as by environmental concerns. Therefore, it is necessary to choose better options, e.g. new technologies or materials with improved life-cycle performance. One solution for using resources in an efficient manner is to close the materials' loop through the recycling of materials that result either from the end-of-life of products or from being the by-product of an industrial process. It is well known that the production of Portland cement, one of the materials most used in the construction sector, has a significant contribution to the environmental impacts, mainly related with carbon dioxide emission. Therefore, the study and utilization of by-products or wastes usable as cement replacement in concrete can supply more sustainable options, provided that these type of concrete produced has same durability and equivalent quality properties as standard concrete. This work studied the environmental benefits of incorporating different percentages of two types of fly ashes that can be used in concrete as cement replacement. These ashes are waste products of power and heat production sectors using coal or biomass as fuels. The results showed that both ashes provide a benefit for the concrete production both in terms of environmental impact minimization and a better environmental performance through an increase in cement replacement. It is possible to verify that the incorporation of fly ashes is a sustainable option for cement substitution and a possible path to improve the environmental performance of the concrete industry.

Effects of residues on the degradation of PHA produced from mixed microbial cultures and processed in extrusion

Thermal degradation upon melting is one of the major drawbacks reported for polyhydroxyalkanoates (PHA). However, the role of residues originating from the fermentation and the extraction steps on the thermal stability of this class of biopolymers still needs to be clarified. In the particular case of PHA produced from mixed microbial cultures (MMC), this topic is even less documented in the literature. Here, two polyhydroxy(butyrate-co-valerate) (PHBV) produced from MMC enriched in PHA accumulating organisms and fed with cheese whey were studied. A micro extrusion line is used to produce filaments and assess the processability and the degradation of processed PHBV. The prototype micro extrusion line allows for studying grams of materials. The two PHBV contain 18 mol% HV. PHBV was recovered with 11 wt% residues, and further submitted to a purification procedure resulting in a second biopolyester containing less than 2 wt% impurities. The thermorheological characterization of the two PHBV is first presented, together with their semicrystalline properties. Then the processing windows of the two biopolyesters are presented. Finally, the properties of extruded filaments are reported and the thermomechanical degradation of PHBV is extensively studied. The structure was assessed by wide angle X-ray diffraction, mechanical and rheological properties are reported, thermal properties are studied with differential scanning calorimetry and thermogravimetric analysis, whereas Fourier Transform Infrared spectroscopy was used to assess the impact of the extrusion on PHBV chemical structure. All results obtained with the two PHBV are compared to assess the effects of residues on both PHBV processability and degradation.

Tailoring microstructure and physical properties of poly(vinylidene fluoride–hexafluoropropylene) porous films

This paper presents a systematic study for the production of poly(vinylidene fluoride-hexafluoropropylene), P(VDF-HFP), porous films using solvent evaporation (SE) and non-solvent induced phase separation (NIPS) techniques. Parameters such as volume fraction of the copolymer solution, film thickness, time exposure to air, non-solvent and temperature of the coagulation bath were investigated on the morphology, crystallization and mechanical properties of the samples. Films with different porous morphologies including homogeneous pore sizes, macrovoids and spherulites were obtained depending on the processing conditions, which in turn affect the wettability and mechanical properties of the material. Knowing that the phase content of the films also depends on the processing conditions, this paper shows that P(VDF-HFP) films with tailored porous morphology, electroactive phase content, hydrophobicity, cristallinity and mechanical properties can be achieved for a specific application using the adequate SE and NIPS techniques conditions.

Mechanical performance of natural fiber-reinforced composites for the strengthening of masonry

The growing concerns regarding the environmental impact generated by the use of inorganic materials in different fields of application increased the interest towards products based on materials with low environmental impact. In recent years, researchers have turned their attention towards the development of materials obtained from renewable sources, easily recoverable or biodegradable at the end of use. In the field of civil structures, a few attempts have been done to replace the most common composites (e.g. carbon and glass fibers) by materials less harmful to the environment, as natural fibers. This work presents a comprehensive experimental research on the mechanical performance of natural fibers for the strengthening of masonry constructions. Flax, hemp, jute, sisal and coir fibers have been investigated both from physical and mechanical points of view. The fibers with better performance were tested together with three different matrices (two of organic nature) in order to produce composites. These experimental results represent a useful database for understanding the potentialities of natural fibers as strengthening systems.

The mineralogy and chemistry of the German and Portuguese tiles used to face a historic building in the Amazon region and their natural susceptibility to tropical weathering

During the 19th century, the most prominent buildings of the city of Belém were faced entirely with tiles manufactured in Portugal and Germany, which now exhibit distinct degrees of degradation. The Pinho mansion is one of the most important of these buildings and was selected for the investigation of the action of the tropical Amazonian climate on the degradation of the tiles. To achieve this objective, the tiles were mapped for organic and inorganic degradation, and samples were collected for analysis. The minerals were determined by XRD, the chemical composition by classical wet methods and SEM/EDS, and the microorganisms under the microscope. The results show that the German and Portuguese tiles are quite different in their composition. While both ceramic bodies are composed of SiO2 and Al2O3, CaO was found only in the Portuguese tile. The low Na2O and K2O contents indicate the addition of materials to reduce the fusion temperature. SiO2 and PbO are the main constituents of the glaze, with CoO and FeO being added as pigment. The ceramic body of the German tiles is constituted of quartz, mullite, and cristobalite, in contrast with the Portuguese tiles, which are made of quartz, gehlenite, diopside, calcite, and feldspars. The glazes are XRD-amorphous. The chemical and mineralogical differences between the German and Portuguese tiles indicate that they were produced from different raw materials under distinct thermal processes. The most prominent weathering-related modifications are the thin layers (German tiles), oxidation stains, dark stains, the detachment of the tile (Portuguese tiles), loss of the glaze and powdering of the ceramic body (Portuguese tiles) through the establishment of Cyanophyta and Bacillariophyta.. The distinct degradation patterns of the tiles exposed to the tropical Amazon climate are a consequence of their distinct mineralogy and chemistry.

Tailored deposition of coloured coatings: on the widening of the available colour range

Dissertação de mestrado integrado em Engenharia de Materiais

Self-compacting concrete and conventional concrete in the arena Pernambuco: comparative study of durability indicators and economic feasibility

This study addressed the application, strength and durability of self-compacting concrete (SCC) in a large-scale construction site, comparing its performance with vibrated conventional concrete (CC) with similar characteristics, assessing its economic feasibility. The studies were undertaken in the Arena Pernambuco project and involved the concreting during May, June and July 2012, for data collection, accompanying the routine concrete control tests and performing specific strength and durability tests. The SCC compressive strength was on average 4.5% higher than the CC one, and its formwork reinforced to withstand greater lateral pressure of the fresh concrete. The durability indicators results were in favour of SCC, which cost was 13.5% higher than CC.

Development of advanced cell/tissue culture systems, based on enhanced polymeric scaffolds and sophisticated bioreactors, for tissue engineering applications

Programa Doutoral em Engenharia Biomédica

Nanocomposites: the contribution of multiscale modelling to improve the dispersion levels

Tese de Doutoramento em Ciência e Engenharia de Polímeros e Compósitos