Development of new membranes based on ionic liquid materials for gas separation

In the field of energy, natural gas is an essential bridge to a clean, low carbon, renewable energy era. However, natural gas processing and transportation regulation require the removal of contaminant compounds such as carbon dioxide (CO2). Regarding clean air, the increasing atmospheric concentrations of greenhouse gases, specifically CO2, is of particular concern. Therefore, new costeffective, high performance technologies for carbon capture have been researched and the design of materials with the ability to efficiently separate CO2 from other gases is of vital importance.(...)

Mechanical characterization of aortas using 2D ultrasound elastography

Rupture of aortic aneurysms (AA) is a major cause of death in the Western world. Currently, clinical decision upon surgical intervention is based on the diameter of the aneurysm. However, this method is not fully adequate. Noninvasive assessment of the elastic properties of the arterial wall can be a better predictor for AA growth and rupture risk. The purpose of this study is to estimate mechanical properties of the aortic wall using in vitro inflation testing and 2D ultrasound (US) elastography, and investigate the performance of the proposed methodology for physiological conditions. Two different inflation experiments were performed on twelve porcine aortas: 1) a static experiment for a large pressure range (0 – 140 mmHg); 2) a dynamic experiment closely mimicking the in vivo hemodynamics at physiological pressures (70 – 130 mmHg). 2D raw radiofrequency (RF) US datasets were acquired for one longitudinal and two cross-sectional imaging planes, for both experiments. The RF-data were manually segmented and a 2D vessel wall displacement tracking algorithm was applied to obtain the aortic diameter–time behavior. The shear modulus G was estimated assuming a Neo-Hookean material model. In addition, an incremental study based on the static data was performed to: 1) investigate the changes in G for increasing mean arterial pressure (MAP), for a certain pressure difference (30, 40, 50 and 60 mmHg); 2) compare the results with those from the dynamic experiment, for the same pressure range. The resulting shear modulus G was 94 ± 16 kPa for the static experiment, which is in agreement with literature. A linear dependency on MAP was found for G, yet the effect of the pressure difference was negligible. The dynamic data revealed a G of 250 ± 20 kPa. For the same pressure range, the incremental shear modulus (Ginc) was 240 ± 39 kPa, which is in agreement with the former. In general, for all experiments, no significant differences in the values of G were found between different image planes. This study shows that 2D US elastography of aortas during inflation testing is feasible under controlled and physiological circumstances. In future studies, the in vivo, dynamic experiment should be repeated for a range of MAPs and pathological vessels should be examined. Furthermore, the use of more complex material models needs to be considered to describe the non-linear behavior of the vascular tissue.

Influence of the molecular weight in mechanical properties and degradation kinetics of chitosan inverted colloidal crystals

Tissue engineering arises from the need to regenerate organs and tissues, requiring the development of scaffolds, which can provide an optimum environment for tissue growth. In this work, chitosan with different molecular weights was used to develop biodegradable 3D inverted colloidal crystals (ICC) structures for bone regeneration, exhibiting uniform pore size and interconnected network. Moreover, in vitro tests were conducted by studying the influence of the molecular weight in the degradation kinetics and mechanical properties. The production of ICC included four major stages: fabrication of microspheres; assembly into a cohesive structure, polymeric solution infiltration and microsphere removal. Chitosan’s degree of deacetylation was determined by infrared spectroscopy and molecular weight was obtained via capillary viscometry. In order to understand the effect of the molecular weight in ICC structures, the mass loss and mechanical properties were analyzed after degradation with lysozyme. Structure morphology observation before and after degradation was performed by scanning electron microscopy. Cellular adhesion and proliferation tests were carried out to evaluate ICC in vitro response. Overall, medium molecular weight ICC revealed the best balance in terms of mechanical properties, degradation rate, morphology and biological behaviour.

Evaluation of mechanical soft-abrasive blasting and chemical cleaning methods on alkyd-paint graffiti made on carbonate stones

In the context of this dissertation several studies were developed resulting in submission and publication “Evaluation of mechanical soft-abrasive blasting and chemical cleaning methods on alkyd-paint graffiti made on calcareous stones” to Journal of Cultural Heritage. (http://dx.doi.org/10.101 /j.culher.2014.10.004)

Ants in a hospital environment and their potential as mechanical bacterial vectors

Introduction We studied the richness and abundance of ant species, their bacteria and the bacteria isolated from patient clinical samples. Methods Ants were collected with baited traps at 64 sites in a public hospital in São Luis, State of Maranhão, Brazil. Results In total, 1,659 ants from 14 species were captured. The most frequent species were Crematogaster victima, Solenopsis saevissima, Tapinoma melanocephalum, Camponotus vittatus and Paratrechina fulva. Forty-one species of bacteria were isolated from the ants and 18 from patients. Conclusions Ants are potential vehicles for pathogenic and opportunistic bacteria, and they can represent a risk factor in nosocomial infections.

Damage propagation in composite Materials meso-mechanical models

Composite materials have a complex behavior, which is difficult to predict under different types of loads. In the course of this dissertation a methodology was developed to predict failure and damage propagation of composite material specimens. This methodology uses finite element numerical models created with Ansys and Matlab softwares. The methodology is able to perform an incremental-iterative analysis, which increases, gradually, the load applied to the specimen. Several structural failure phenomena are considered, such as fiber and/or matrix failure, delamination or shear plasticity. Failure criteria based on element stresses were implemented and a procedure to reduce the stiffness of the failed elements was prepared. The material used in this dissertation consist of a spread tow carbon fabric with a 0°/90° arrangement and the main numerical model analyzed is a 26-plies specimen under compression loads. Numerical results were compared with the results of specimens tested experimentally, whose mechanical properties are unknown, knowing only the geometry of the specimen. The material properties of the numerical model were adjusted in the course of this dissertation, in order to find the lowest difference between the numerical and experimental results with an error lower than 5% (it was performed the numerical model identification based on the experimental results).

Biotransformation/separation routes to obtain pure enantiomers

The objective of the work presented in this thesis was the development of an innovative approach for the separation of enantiomers of secondary alcohols, combining the use of an ionic liquid (IL) - both as solvent for conducting enzymatic kinetic resolution and as acylating agent - with the use of carbon dioxide (CO2) as solvent for extraction. Menthol was selected for testing this reaction/separation approach due to the increasing demand for this substance, which is widely used in the pharmaceutical, cosmetics and food industries. With a view to using an ionic ester as acylating agent, whose conversion led to the release of ethanol, and due to the need to remove this alcohol so as to drive reaction equilibrium forward, a phase equilibrium study was conducted for the ehtanol/(±)-menthol/CO2 system, at pressures between 8 and 10 MPa and temperatures between 40 and 50 oC. It was found that CO2 is more selective towards ethanol, especially at the lowest pressure and highest temperature tested, leading to separation factors in the range 1.6-7.6. The pressure-temperature-composition data obtained were correlated with the Peng-Robinson equation of state and the Mathias-Klotz-Prausnitz mixing rule. The model fit the experimental results well, with an average absolute deviation (AAD) of 3.7 %. The resolution of racemic menthol was studied using two lipases, namely lipase from Candida rugosa (CRL) and immobilized lipase B from Candida antarctica (CALB), and two ionic acylating esters. No reaction was detected in either case. (R,S)-1-phenylethanol was used next, and it was found that with CRL low, nonselective, conversion of the alcohol took place, whereas CALB led to an enantiomeric excess (ee) of the substrate of 95%, at 30% conversion. Other acylating agents were tested for the resolution of (±)-menthol, namely vinyl esters and acid anhydrides, using several lipases and varying other parameters that affect conversion and enantioselectivity, such as substrate concentration, solvent and temperature. One such acylating agent was propionic anhydride. It was thus performed a phase equilibrium study on the propionic anhydride/CO2 system, at temperatures between 35 and 50 oC. This study revealed that, at 35 oC and pressures from 7 MPa, the system is monophasic for all compositions. The enzymatic catalysis studies carried out with propionic anhydride revealed that the extent of noncatalyzed reaction was high, with a negative effect on enantioselectivity. These studies showed also that it was possible to reduce considerably the impact of the noncatalyzed reaction relative to the reaction catalyzed by CRL by lowering temperature to 4 oC. Vinyl decanoate was shown to lead to the best results at conditions amenable to a process combining the use of supercritical CO2 as agent for post-reaction separation. The use of vinyl decanoate in a number of IL solvents, namely [bmim][PF6], [bmim][BF4], [hmim][PF6], [omim][PF6], and [bmim][Tf2N], led to an enantiomeric excess of product (eep) values of over 96%, at about 50% conversion, using CRL. In n-hexane and supercritical CO2, reaction progressed more slowly.(...)

Bias in returns to tenure when firm wages and employment comove: A quantitative assessment and solution

It is well known that, unless worker-firm match quality is controlled for, returns to firm tenure (RTT) estimated directly via reduced form wage (Mincer) equations will be biased. In this paper we show that even if match quality is properly controlled for there is a further pervasive source of bias, namely the co-movement of firm employment and firm wages. In a simple mechanical model where human capital is absent and separation is exogenous we show that positively covarying shocks (either aggregate or firm level) to firms employment and wages cause downward bias in OLS regression estimates of RTT. We show that the long established procedures for dealing with "traditional" RTT bias do not circumvent the additional problem we have identified. We argue that if a reduced form estimation of RTT is undertaken, firm-year fixed effects must be added in order to eliminate this bias. Estimates from two large panel datasets from Portugal and Germany show that the bias is empirically important. Adding firm-year fixed effects to the regression increases estimates of RTT in the two respective countries by between 3.5% and 4.5% of wages at 20 years of tenure over 80% (50%) of the estimated RTT level itself. The results extend to tenure correlates used in macroeconomics such as the minimum unemployment rate since joining the firm. Adding firm-year fixed effects changes estimates of these effects also.

Continuous monitoring of concrete mechanical properties since an early age to support construction phasing

The assessment of concrete mechanical properties during construction of concrete structures is of paramount importance for many intrinsic operations. However many of the available non-destructive methods for mechanical properties have limitations for use in construction sites. One of such methodologies is EMM-ARM, which is a variant of classic resonant frequency methods. This paper aims to demonstrate the efforts towards in-situ applicability of EMMARM, as to provide real-time information about concrete mechanical properties such as E-modulus and compressive strength. To achieve the aforementioned objective, a set of adaptations to the method have been successfully implemented and tested: (i) the reduction of the beam span; (ii) the use of a different mould material and (iii) a new support system for the beams. Based on these adaptations, a reusable mould was designed to enable easier systematic use of EMMARM. A pilot test was successfully performed under in-situ conditions during a bridge construction.

Mortars with incorporation of PCM based in different binders: mechanical and thermal behavior

Currently we are witnessing a huge concern of society with the parameters of comfort of the buildings and the energetic consumptions. It is known that there is a huge consumption of non-renewable sources of energy. Thus, it is urgent to develop and explore ways to take advantage of renewable sources of energy by improving the energy efficiency of buildings. 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. However, the incorporation of phase change materials in mortars modifies its characteristics. The main purpose of this study was mechanical and thermal characterization of mortars with incorporation of PCM in mortars based in different binders. The binders studied were aerial lime, hydraulic lime, gypsum and cement. For each type of binder a reference composition (0% PCM) and a composition with incorporation of 40% of PCM were developed. It was possible to observe that the incorporation of PCM in mortars caused differences in properties such as workability, compressive strength, flexural strength and adhesion, however leads to an improvement of thermal behavior.

Mechanical characterization of old chestnut beams

The main objective of this work is to evaluate, by non-destructive techniques, seven old Chestnut beams. For that, after the geometric assessment and the detailed visual inspection that allowed to strength grade the beams, a series of non-destructive tests was setup. In a first step, non-destructive bending tests, under the elastic limit, were performed to quantify the modulus of elasticity in bending (MoE) of the seven beams. Then, Resistograph® and Pilodyn® tests were done to assess the superficial decay and to have aclearer idea of the voids dimensions. Then, two beams were tested in bending until failure to evaluate the bending strength. In a second step, end parts were cut from the beams, one per end of the beams, to perform Resistograph®, Pilodyn® and ultrasound tests, to quantify the density of the beams and to extract meso-specimens to be used in tension parallel to the grain tests

Influence of the wood mechanical properties in the dovetail joint behavior

The force distribution inside a dovetail joint is complex. Wood is simultaneously loaded in different directions in the several connected surfaces. The analytical solutions available for the analysis of the behavior of those carpentry joints rely on the mechanical properties of wood. In particular, the stiffness properties of wood under compression are crucial for the forces equilibrium. Simulations showed that the stiffness values considered in each of the springs normally assumed in the analytical models, have great influence in the bearing capacity and stiffness of the dovetail joints, with important consequence on the stress distribution over the overall structure. In a wide experimental campaign, the properties under compression of the most common wood species of existing timber structures have been determined. Then, a solved example of a dovetail joint is presented assuming different wood species and the corresponding strength and stiffness properties values obtained in the tests.

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.

Mechanical analysis of asphalt mixtures produced with waste plastic modified binders

This work compares the viscoelastic properties of an asphalt binder (70/100 pen) modified with different waste plastics and the mechanical properties of the resultant asphalt mixtures. Two different plastic wastes were used, namely recycled HDPE and EVA. Three different polymer modified binders were produced with these plastic wastes: i) 5% HDPE modified binder (P5); ii) 5% EVA modified binder (E5) and; iii) a modified binder with 4% of EVA and 2% HDPE (E4P2). Asphalt mixtures were produced with these modified binders, and their mechanical properties were analysed and compared with a conventional mixture produced with a 30/50 pen bitumen. It was possible to conclude that these recycled polymers are able to improve the mechanical performance of the asphalt mixtures used in road paving.