Digital microfluidic devices: the role of the dielectric layer

Digital microfluidics (DMF) is a field which has emerged in the last decade as a re-liable and versatile tool for sensing applications based on liquid reactions. DMF allows the discrete displacement of droplets, over an array of electrodes, by the application of voltage, and also the dispensing from a reservoir, mixing, merging and splitting fluidic operations. The main drawback of these devices is due to the need of high driving volt-ages for droplet operations. In this work, alternative dielectric layers combinations were studied aiming the reduction of these driving voltages. DMF chips were designed, pro-duced and optimized according to the theory of electrowetting-on-dielectric, adopting different combinations of parylene-C and tantalum pentoxide (Ta2O5) as dielectric ma-terials, and Teflon as hydrophobic layer. With both devices’ configurations, i.e., Parylene as single dielectric, and multilayer chips combining Parylene and Ta2O5, it was possible to perform all the fluidic opera-tions in the microliter down to hundreds of nanoliters range. Multilayer chips presented significant reduction on driving voltages for droplet op-erations in silicone oil filler medium: from 70 V (parylene only) down to 30 V (parylene/Ta2O5) for dispensing; and from 50 V (parylene only) down to 15 V (parylene/Ta2O5) for movement. Peroxidase colorimetric reactions were successfully performed as proof-of-concept, using multilayer configuration devices.

Experimental and modeling studies on reverse electrodialysis for sustainable power generation

A potentially renewable and sustainable source of energy is the chemical energy associated with solvation of salts. Mixing of two aqueous streams with different saline concentrations is spontaneous and releases energy. The global theoretically obtainable power from salinity gradient energy due to World’s rivers discharge into the oceans has been estimated to be within the range of 1.4-2.6 TW. Reverse electrodialysis (RED) is one of the emerging, membrane-based, technologies for harvesting the salinity gradient energy. A common RED stack is composed by alternately-arranged cation- and anion-exchange membranes, stacked between two electrodes. The compartments between the membranes are alternately fed with concentrated (e.g., sea water) and dilute (e.g., river water) saline solutions. Migration of the respective counter-ions through the membranes leads to ionic current between the electrodes, where an appropriate redox pair converts the chemical salinity gradient energy into electrical energy. Given the importance of the need for new sources of energy for power generation, the present study aims at better understanding and solving current challenges, associated with the RED stack design, fluid dynamics, ionic mass transfer and long-term RED stack performance with natural saline solutions as feedwaters. Chronopotentiometry was used to determinate diffusion boundary layer (DBL) thickness from diffusion relaxation data and the flow entrance effects on mass transfer were found to avail a power generation increase in RED stacks. Increasing the linear flow velocity also leads to a decrease of DBL thickness but on the cost of a higher pressure drop. Pressure drop inside RED stacks was successfully simulated by the developed mathematical model, in which contribution of several pressure drops, that until now have not been considered, was included. The effect of each pressure drop on the RED stack performance was identified and rationalized and guidelines for planning and/or optimization of RED stacks were derived. The design of new profiled membranes, with a chevron corrugation structure, was proposed using computational fluid dynamics (CFD) modeling. The performance of the suggested corrugation geometry was compared with the already existing ones, as well as with the use of conductive and non-conductive spacers. According to the estimations, use of chevron structures grants the highest net power density values, at the best compromise between the mass transfer coefficient and the pressure drop values. Finally, long-term experiments with natural waters were performed, during which fouling was experienced. For the first time, 2D fluorescence spectroscopy was used to monitor RED stack performance, with a dedicated focus on following fouling on ion-exchange membrane surfaces. To extract relevant information from fluorescence spectra, parallel factor analysis (PARAFAC) was performed. Moreover, the information obtained was then used to predict net power density, stack electric resistance and pressure drop by multivariate statistical models based on projection to latent structures (PLS) modeling. The use in such models of 2D fluorescence data, containing hidden, but extractable by PARAFAC, information about fouling on membrane surfaces, considerably improved the models fitting to the experimental data.

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.(...)

Saloplastic membranes as green devices for soft tissue regeneration

Implantable devices must exhibit mechanical properties similar to native tissues to promote appropriate cellular behavior and regeneration. Herein, we report a new membrane manufacture method based on the synthesis of polyelectrolyte complexes (PECs) that exhibit saloplasticity, i.e. variable physical-chemistry using salt as a plasticizer. This is a Green Chemistry approach, as PECs generate structures that are stabilized solely by reversible electrostatic interactions, avoiding the use of harmful crosslinkers completely. Furthermore, natural polyelectrolytes - chitosan and alginate - were used. Upon mixing them, membranes were obtained by drying the PECs at 37ºC, yielding compact PECs without resorting to organicsolvents. The plasticizing effect of salt after synthesis was shown by measuring tensile mechanical properties, which were lower when samples were immersed in high ionic strength solutions.Salt was also used during membrane synthesis in different quan- tities (0 M, 0.15 M and 0.5 M in NaCl) yielding structures with no significant differences in morphology and degradation (around 15% after 3 months in lysozyme). However, swelling was higher (about 10x) when synthesized in the presence of salt. In vitro cell studies using L929 fibroblasts showed that cells adhered and proliferated preferentially in membranes fabricated in the presence of salt (i.e. the membranes with lower tensile strength). Structures with physical-chemical properties controlled with precision open a path to tissue engineering strategies depending on fine tuning mechanical properties and cellular adhesion simply by changing ionic strength during membrane manufacture

Bioactive nanocomposite spheres with proved shape memory capability in bone defects

Bioactive glass nanoparticles (BGNPs) promote an apatite surface layer in physiologic conditions that lead to a good interfacial bonding with bone.1 A strategy to induce bioactivity in non-bioactive polymeric biomaterials is to incorporate BGNPs in the polymer matrix. This combination creates a nanocomposite material with increased osteoconductive properties. Chitosan (CHT) is a polymer obtained by deacetylation of chitin and is biodegradable, non-toxic and biocompatible. The combination of CHT and the BGNPs aims at designing biocompatible spheres promoting the formation of a calcium phosphate layer at the nanocomposite surface, thus enhancing the osteoconductivity behaviour of the biomaterial. Shape memory polymers (SMP) are stimuli-responsive materials that offer mechanical and geometrical action triggered by an external stimulus.2 They can be deformed and fixed into a temporary shape which remains stable unless exposed to a proper stimulus that triggers recovery of their original shape. This advanced functionality makes such SMPs suitable to be implanted using minimally invasive surgery procedures. Regarding that, the inclusion of therapeutic molecules becomes attractive.  We propose the synthesis of shape memory bioactive nanocomposite spheres with drug release capability.3   1.  L. L. Hench, Am. Ceram. Soc. Bull., 1993, 72, 93-98. 2.  A. Lendlein and S. Kelch, Angew Chem Int Edit, 2002, 41, 2034-2057. 3.  Ã . J. Leite, S. G. Caridade and J. F. Mano, Journal of Non-Crystalline Solids (in Press)

Plastic-damage smeared crack model to simulate the behaviour of structures made by cement based materials

This work proposes a constitutive model to simulate nonlinear behaviour of cement based materials subjected to different loading paths. The model incorporates a multidirectional fixed smeared crack approach to simulate crack initiation and propagation, whereas the inelastic behaviour of material between cracks is treated by a numerical strategy that combines plasticity and damage theories. For capturing more realistically the shear stress transfer between the crack surfaces, a softening diagram is assumed for modelling the crack shear stress versus crack shear strain. The plastic damage model is based on the yield function, flow rule and evolution law for hardening variable, and includes an explicit isotropic damage law to simulate the stiffness degradation and the softening behaviour of cement based materials in compression. This model was implemented into the FEMIX computer program, and experimental tests at material scale were simulated to appraise the predictive performance of this constitutive model. The applicability of the model for simulating the behaviour of reinforced concrete shear wall panels submitted to biaxial loading conditions, and RC beams failing in shear is investigated.

Recycled asphalt mixtures with foamed bitumen: an alternative to build ecofriendly road pavements

Nowadays, recycling has become a very important objective for the society in the scope of a closed loop product life cycle. In recent years, new recycling techniques have been developed in the area of road pavements that allow the incorporation of high percentages of reclaimed asphalt (RA) materials in recycled asphalt mixtures. The use of foamed bitumen for production of recycled asphalt mixtures is one of those techniques, which also allows the reduction of the mixing temperatures (warm mix technology). However, it is important to evaluate if this solution can maintain or improve the performance of the resulting mixtures. Thus, the main aim of the present study is to assess the performance of warm recycled asphalt mixtures incorporating foamed bitumen as the new binder and 50% RA, in comparison with a control mixture using conventional bitumen. Four mixtures have been produced with 50% RA, one of them at typical high mixing temperatures with a conventional bitumen (control mixture) and the other three with foamed bitumen at different production temperatures. These four mixtures were tested to evaluate their compactability and water sensitivity. The laboratory test results showed that the production of recycled mixtures with foamed bitumen can be reduced by 40ºC without changing the performance of the resulting mixtures.

Dispersion and re-agglomeration of graphite nanoplates in polypropylene melts under controlled flow conditions

The kinetics of GnP dispersion in polypropylene melt was studied using a prototype small scale modular extensional mixer. Its modular nature enabled the sequential application of a mixing step, melt relaxation, and a second mixing step. The latter could reproduce the flow conditions on the first mixing step, or generate milder flow conditions. The effect of these sequences of flow constraints upon GnP dispersion along the mixer length was studied for composites with 2 and 10 wt.% GnP. The samples collected along the first mixing zone showed a gradual decrease of number and size of GnP agglomerates, at a rate that was independent of the flow conditions imposed to the melt, but dependent on composition. The relaxation zone induced GnP re-agglomeration, and the application of a second mixing step caused variable dispersion results that were largely dependent on the hydrodynamic stresses generated.

Controlo da qualidade de betões

Dissertação de mestrado em Construção e Reabilitação Sustentáveis

Estudo do trabalho numa empresa de produção de pneus e implementação de ferramentas Lean

Dissertação de mestrado integrado em Engenharia e Gestão Industrial

Structure-property relationships in polymer nanocomposites

Tese de Doutoramento em Ciência e Engenharia de Polímeros e Compósitos

Assessing the production of jet mix columns using alkali activated waste based on mechanical and financial performance and CO2 (eq) emissions

Recent research has proved the potential of alkaline activated fly-ash for soil stabilisation. However, such studies have not focused on the link between financial, mechanical and environmental aspects of this solution, but only on their absolute mechanical properties. The present paper characterises the mechanical behaviour of a large spectrum of activator-ash-soil combinations used to build jet mixing columns, analysing also the cost and CO2 (eq) emissions. The concern with these two vectors forced a decrease in the quantity of stabilising agent added to the soil, relatively to previous research, and the effects of such low quantities have not yet been published. However, the results clearly showed a significant improve in strength, still well above the average values expected when improving the stressstrain behaviour of a weak soil. Uniaxial compressive strength tests were used to assess the effects of the fly-ash percentage, the alkalieash ratio and the water content. The carbon calculator recently developed by the European Federation of Foundation Contractors and the Deep Foundations Institute was used to quantify the CO2 (eq) emissions associated with this technique. The financial cost was estimated based on the experience of a major Portuguese contractor. For comparison purposes, soil cement mixtures were also analysed, using similar conditions and tools used for the soil-ash analysis. Results showed that the cement and ash solutions are very similar in terms of overall performance, with some advantage of the former regarding financial cost, and a significant advantage of the latter regarding the CO2 (eq) emissions. This new grout, although it is in an embryonic stage, it has the potential for broader developments in the field.

Dispersion of fillers in viscoelastic polymer matrices using Eulerian-Lagrangian approaches

Understanding the behavior of c omplex composite materials using mixing procedures is fundamental in several industrial processes. For instance, polymer composites are usually manufactured using dispersion of fillers in polymer melt matrices. The success of the filler dispersion depends both on the complex flow patterns generated and on the polymer melt rheological behavior. Consequently, the availability of a numerical tool that allow to model both fluid and particle would be very useful to increase the process insight. Nowadays there ar e computational tools that allow modeling the behavior of filled systems, taking into account both the behavior of the fluid (Computational Rheology) and the particles (Discrete Element Method). One example is the DPMFoam solver of the OpenFOAM ® framework where the averaged volume fraction momentum and mass conservation equations are used to describe the fluid (continuous phase) rheology, and the Newton’s second law of motion is used to compute the particles (discrete phase) movement. In this work the refer red solver is extended to take into account the elasticity of the polymer melts for the continuous phase. The solver capabilities will be illustrated by studying the effect of the fluid rheology on the filler dispersion, taking into account different fluid types (generalized Newtonian or viscoelastic) and particles volume fraction and size. The results obtained are used to evaluate the relevance of considering the fluid complex rheology for the prediction of the composites morphology

Understanding the dispersion of fillers in polymer matrices

Understanding the mixing process of complex composite materials is fundamental in several industrial processes. For instance, the dispersion of fillers in polymer melt matrices is commonly employed to manufacture polymer composites, using a twin-screw extruder. The effectiveness of the filler dispersion depends not only on the complex flow patterns generated, but also on the polymer melt rheological behavior. Therefore, the availability of a numerical tool able to predict mixing, taking into account both fluid and particles phases would be very useful to increase the process insight, and thus provide useful guidelines for its optimization. In this work, a new Eulerian-Lagrangian numerical solver is developed OpenFOAM® computational library, and used to better understand the mechanisms determining the dispersion of fillers in polymer matrices. Particular attention will be given to the effect of the rheological model used to represent the fluid behavior, on the level of dispersion obtained. For the Eulerian phase the averaged volume fraction governing equations (conservation of mass and linear momentum) are used to describe the fluid behavior. In the case of the Lagrangian phase, Newton’s second law of motion is used to compute the particles trajectories and velocity. To study the effect of fluid behavior on the filler dispersion, several systems are modeled considering different fluid types (generalized Newtonian or viscoelastic) and particles volume fraction and size. The results obtained are used to correlate the fluid and particle characteristics on the effectiveness of mixing and morphology obtained.

Variation of the physicochemical and morphological characteristics of solvent casted poly(vinylidene fluoride) along its binary phase diagram with dimethylformamide

Poly(vinylidene fluoride), PVDF, films and membranes were prepared by solvent casting from dimethylformamide, DMF, by systematically varying polymer/solvent ratio and solvent evaporation temperature. The effect of the processing conditions on the morphology, degree of porosity, mechanical and thermal properties and crystalline phase of the polymer were evaluated. The obtained microstructure is explained by the Flory-Huggins theory. For the binary system, the porous membrane formation is attributed to a spinodal decomposition of the liquid-liquid phase separation. The morphological features were simulated through the correlation between the Gibbs total free energy and the Flory-Huggins theory. This correlation allowed the calculation of the PVDF/DMF phase diagram and the evolution of the microstructure in different regions of the phase diagram. Varying preparation conditions allow tailoring polymer 2 microstructure while maintaining a high degree of crystallinity and a large β crystalline phase content. Further, the membranes show adequate mechanical properties for applications in filtration or battery separator membranes.