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Aliphatic isocyanurates are nowadays used routinely in the development of advanced materials like polyurethane nanocomposites and 3D-printed components, due to their versatile reactivity and the good mechanical and optical properties they confer to the final material. In these applications, a control of the properties at the micro- and nanoscale is desired, therefore a deep understanding of intermolecular interactions is required. Using ab-initio calculations and molecular dynamics simulations, the intermolecular interactions of aliphatic isocyanurates are investigated in detail. The presence of an isocyanate-isocyanurate interaction is demonstrated, and the strong dispersion character of isocyanurate-based interactions is revealed. Calculations of the free energy of binding of the different interactions in gas and liquid phase are provided. The microscopic structure of aliphatic functional and non-functional isocyanurates is analysed and related to the different interaction types, and finally their possible relationship with macroscopic dynamic variables is discussed, This project has received funding from the European Union’s Horizon 2020 - Research and Innovation Framework Programme under the Marie Skłodowska-Curie Grant Agreement no. 642890 (http://thelink-project.eu/) and it was partially supported by the Portuguese Science and Technology Foundation (FCT) in the framework of the Strategic Funding UID/FIS/04650/2013, by the FCT grant SFRH/BD/128666/2017 and by the project “ SearchON2: Revitalization of HPC infrastructure of Uminho” (NORTE07-0162-FEDER-0000869), under the National Strategic Reference Framework, through the European Regional Development Fund. The authors also acknowledge the Texas Advanced Computing Center (TACC) at The University of Texas at Austin for providing HPC resources that have contributed to the research results reported within this paper

Tsunamis from earthquakes of various magnitudes have affected Cascadia in the past. Simulations of Mw>7.5–9.2 earthquakes constrained by earthquake rupture physics and geodetic locking models sh...

From California to British Columbia, the Pacific Northwest coast bears an omnipresent earthquake and tsunami hazard from the Cascadia subduction zone. Multiple lines of evidence suggests that magnitude eight and greater megathrust earthquakes have occurred - the most recent being 321 years ago (i.e., 1700 A.D.). Outstanding questions for the next great megathrust event include where it will initiate, what conditions are favorable for rupture to span the convergent margin, and how much slip may be expected. We develop the first 3-D fully dynamic rupture simulations for the Cascadia subduction zone that are driven by fault stress, strength and friction to address these questions. The initial dynamic stress drop distribution in our simulations is constrained by geodetic coupling models, with segment locations taken from geologic analyses. We document the sensitivity of nucleation location and stress drop to the final seismic moment and coseismic subsidence amplitudes. We find that the final earthquake size strongly depends on the amount of slip deficit in the central Cascadia region, which is inferred to be creeping interseismically, for a given initiation location in southern or northern Cascadia. Several simulations are also presented here that can closely approximate recorded coastal subsidence from the 1700 A.D. event without invoking localized high-stress asperities along the down-dip locked region of the megathrust. These results can be used to inform earthquake and tsunami hazards for not only Cascadia, but other subduction zones that have limited seismic observations but a wealth of geodetic inference.

During the last few decades, the interest over chalcopyrite and related photovoltaics has been growing due the outstanding structural and electrical properties of the thin-film Cu(In,Ga)Se2 photoabsorber. More recently, thin film deposition through solution processing has gained increasing attention from the industry, due to the potential low-cost and high-throughput production. To this end, the elimination of the selenization procedure in the synthesis of Cu(In,Ga)Se2 nanoparticles with following dispersion into ink formulations for printing/coating deposition processes are of high relevance. However, most of the reported syntheses procedures give access to tetragonal chalcopyrite Cu(In,Ga)Se2 nanoparticles, whereas methods to obtain other structures are scarce. Herein, we report a large-scale synthesis of high-quality Cu(In,Ga)Se2 nanoparticles with wurtzite hexagonal structure, with sizes of 10–70 nm, wide absorption in visible to near-infrared regions, and [Cu]/[In + Ga] ≈ 0.8 and [Ga]/[Ga + In] ≈ 0.3 metal ratios. The inclusion of the synthesized NPs into a water-based ink formulation for screen printing deposition results in thin films with homogenous thickness of ≈4.5 µm, paving the way towards environmentally friendly roll-to-roll production of photovoltaic systems., This research was funded by the Portuguese Foundation for Science and Technology (PTDC/CTM-ENE/5387/2014, PTDC/NAN-MAT/28745/2017, UID/FIS/04650/2020, UID/QUI/ 0686/2020, PTDC/FIS-MAC/28157/2017, POCI-01-0145-FEDER-028108, SFRH/BD/121780/2016); the Basque Government Industry Department (ELKARTEK, HAZITEK); the National Science Foundation (DMR-2003783 grant); the Search-ON2: revitalization of HPC infrastructure of UMinho, (NORTE07-0162-FEDER-000086), co-funded by the North Portugal Regional Operational Programme (ON.2-O Novo Norte), under the National Strategic Reference Framework (NSRF), through the European Regional Development Fund (ERDF). The use of the Advanced Photon Source, an Office of Science User Facility operated for the U.S. Department of Energy (DOE) Office of Science by Argonne National Laboratory, was supported by the U.S. DOE under Contract No. DE-AC02-06CH11357.

Colloidal synthesis is harnessed for the gram-scale preparation of hexagonal-shaped plate-like Bi

The Cascadia Subduction Zone (CSZ) is a 1,200 km plate boundary that poses the greatest seismic hazard in the Pacific Northwest United States. Cascadia tsunamis have been the primary subject of studies on tsunami scenarios along the United States west coast. However, the geographic extent as well as the final size of potential future ruptures in Cascadia are poorly known. This has caused the result of previous studies to remain mostly hypothetical and simply serve as “worst-case scenarios”.In this study, we calculate the hazard of M7-9 earthquakes using more realistic models that systematically vary both the geographic extent and slip of the rupture. To achieve this goal, we use rupture simulations derived from locking models to provide estimates of coseismic deformation at the ocean floor, and design several rupture scenarios with variable hypocenters and rupture propagation. We then apply shallow water approximation to simulate the full tsunami waveforms and generate tsunami amplitude profiles along the Cascadia coastline. By varying the seismic moment thresholds of the rupture models, we find that regional maximum coastal amplitudes are not unique for a given rupture size. This phenomenon is mostly due to the special coastal geometry as well as the particular slip partitioning of the elongated north-south rupture. In fact, our simulations reveal that beyond a magnitude of Mw≈8.5, increasing the rupture size will not significantly vary the tsunami hazard, especially in southern Cascadia, with the central segments playing the most crucial role. This result has significant implications in identifying the main sources of tsunami hazard along the US west coast, especially as the worst-case rupture scenario does not uniquely correspond to the worst-case tsunami scenario at a given location.

The recent 2019 Ridgecrest earthquake sequence in southern California jostled the seismological community by revealing a complex and cascading foreshock series that culminated in a Mw 7.1 mainshock. But the central Garlock fault, despite being located immediately south of this sequence, did not coseismically fail. Instead, the Garlock fault underwent postseismic creep and exhibited a sizeable earthquake swarm. The dynamic details of the rupture process during the mainshock are largely unknown, as is the amount of stress needed to bring the Garlock fault to failure. We present an integrated view of how stresses changed on the Garlock fault during and after the mainshock using a combination of tools including kinematic slip inversion, Coulomb stress change (ΔCFS), and dynamic rupture modeling. We show that positive ΔCFSs cannot easily explain observed aftershock patterns on the Garlock fault but are consistent with where creep was documented on the central Garlock fault section. Our dynamic model is able to reproduce the main slip asperities and kinematically estimated rupture speeds (≤2 km/s) during the mainshock, and suggests the temporal changes in normal and shear stress on the Garlock fault were the greatest near the end of rupture. The largest static and dynamic stress changes on the Garlock fault we observe from our models coincide with the creeping region, suggesting that positive stress perturbations could have caused this during or after the mainshock rupture. This analysis of near-field stress-change evolution gives insight into how the Ridgecrest sequence influenced the local stress field of the northernmost eastern California shear zone.

Colloidal synthesis is harnessed for the gram-scale preparation of hexagonal-shaped plate-like Bi2Te2.7Se0.3 particles, yielding nearly 5 g of the product in one experiment. The resultant textured particles are highly crystalline, phase-pure, chemically uniform, and can serve as a starting material for the preparation of bulk thermoelectrics for room temperature applications. The consolidation occurs via spark plasma sintering, which affords nanostructured n-type Bi2Te2.7Se0.3 material exhibiting a high figure of merit ZT ≈ 1 at 373 K with an average ZT ≈ 0.93 (300-473 K). Our experimental and theoretical studies indicate that the high thermoelectric performance is attributed to a favorable combination of the resultant transport properties. Specifically, bottom-up formation of the plate-like particles results in the substantial reduction of thermal conductivity by nanostructuring as observed experimentally and can be ascribed to phonon scattering at grain boundaries and suppressed bipolar conduction. When coupled with high electrical conductivity, which is preserved at the bulk scale as confirmed by ab initio calculations, these factors boost the thermoelectric performance of the as-synthesized n-type Bi2Te2.7Se0.3 bulk nanostructured alloy to the state-of-the-art level. The combination of a newly developed scalable colloidal synthesis with optimized spark plasma sintering constitutes a convenient route to nanostructured bulk thermoelectrics, which is an interesting pathway for the preparation of simple and complex thermoelectric chalcogenides., This work was supported by Portuguese National Funding Agency for Science, Research and Technology (FCT) under the UT-BORN-PT project (UTAP-EXPL/CTE/0050/2017). B. A. K. acknowledges funding of this work by the Robert A. Welch Foundation (grant no. F-1464).

Nanogels, due to their unique properties, have potential for promising applications in several fields. There is a growing interest in understanding which are the mechanisms controlling their properties, as those depend not only on composition but also on internal structure. In this work, dissipative particle dynamics simulations were applied to simulate the formation of nanogels from monodisperse end-functionalised polymer chains, with the cross-linking reaction modelled using a distance-based algorithm, including a reversible intermediate step. Nanogel properties are studied by calculating their swelling transition curves and structure properties, such as network defects and entanglement state. Various chain lengths, reaction schemes, nanogel in silico synthesis methods and solvent ratios are compared and discussed, showing how these factors influence the nanogel swelling behaviour and structure. Our results show that, in order to be compared with experiments, nanogel simulations should carefully consider processing parameters., This project has received funding from the European Union’s Horizon 2020-Research and Innovation Framework Programme under the Marie Skłodowska-Curie Grant Agreement no. 642890 (http://thelink-project.eu/) and it was partially supported by the Portuguese Foundation for Science and Technology (FCT) in the framework of the Strategic Funding UIDB/04650/2020-2023, by the FCT grant SFRH/BD/128666/2017. The authors acknowledge FCT and the National Advanced Computing Network (RNCA) for providing HPC resources from cluster Bob at Minho Advanced Computing Center (MACC).

The production, processing, and application of aliphatic isocyanate (NCO)-based thermosets such as polyurethane coatings and adhesives are generally limited by the surprisingly high viscosity of tri-functionality and higher-functionality isocyanurates. These compounds are essential crosslinking additives for network formation. However, the mechanism by which these high viscosities are caused is not yet understood. In this work, model aliphatic isocyanurates were synthesized and isolated in high purity (>99%), and their viscosities were accurately determined. It was shown that the presence of the NCO group has a strong influence on the viscosity of the system. From density functional theory calculations, a novel and significant bimolecular binding potential of −8.7 kJ/mol was identified between NCO groups and isocyanurate rings, confirming the important role of the NCO group. This NCO-to-ring interaction was proposed to be the root cause for the high viscosities observed for NCO-functional isocyanurate systems. Molecular dynamics simulations carried out to further confirm this influence also suggest that the NCO-to-ring interaction causes a significant additional contribution to viscosity. Finally, model functional isocyanurates were further reacted into densely crosslinked polyisocyanurate networks which showed interesting material properties

Precipitation is the most important weather parameter in the Philippines. Made up of more than 7100 islands, the Philippine archipelago is an agricultural country that depends on rain-fed crops. Located in the western rim of the North West Pacific Ocean, this tropical island country is very vulnerable to tropical cyclones that lead to severe flooding events. Recently, satellite-based precipitation estimates have improved significantly and can serve as alternatives to ground-based observations. These data can be used to fill data gaps not only for climatic studies, but can also be utilized for disaster risk reduction and management activities. This study characterized the statistical errors of daily precipitation from four satellite-based rainfall products from (1) the Tropical Rainfall Measuring Mission (TRMM), (2) the CPC Morphing technique (CMORPH) of NOAA and (3) the Global Satellite Mapping of Precipitation (GSMAP) and (4) Precipitation Estimation from Remotely Sensed information using Artificial Neural Networks (PERSIANN). Precipitation data were compared to 52 synoptic weather stations located all over the Philippines. Results show GSMAP to have over all lower bias and CMORPH with lowest Mean Absolute Error (MAE) and Root Mean Square Error (RMSE). In addition, a dichotomous rainfall test reveals GSMAP and CMORPH have low Proportion Correct (PC) for convective and stratiform rainclouds, respectively. TRMM consistently showed high PC for almost all raincloud types. Moreover, all four satellite precipitation showed high Correct Negatives (CN) values for the north-western part of the country during the North-East monsoon and spring monsoonal transition periods.

Aliphatic diisocyanates and their derivatives are key liquid components in the industrial processing of polyurethane materials. In particular, for the synthesis of crosslinked polyurethane materials, the higher functionality molecules obtained by reacting three -or more- diisocyanates are of interest. However, despite their widespread application, the relation between molecular structure and macroscopic physical properties, in particular viscosity, is poorly understood in these systems. In this work, we introduce a new force field parameter set, GAFF-IC, based on the widely-used and versatile GAFF force field, meant for accurate predictions of physical properties of isocyanate-based molecular liquids. The new parameters allow to predict the vaporization enthalpies and densities of several isocyanate-based molecules, which are found in excellent agreement with the available experimental data. The effectiveness and transferability of the improved parameters is verified by calculating the viscosities of several isocyanates, isocyanate dimers (uretdiones) and isocyanate trimers (isocyanurates), resulting in accurate viscosity predictions in excellent agreement with experimental values., This project has received funding from the European Union’s Horizon 2020 research and innovation program under the Marie Sk lodowska-Curie Grant Agreement no. 642890 (http://thelink-project.eu/) and it was partially supported by the Portuguese Foundation for Science and Technology (FCT) in the framework of the Strategic Funding UID/FIS/04650/2013, and by the project ”Search-ON2: Revitalization of HPC infrastructure of Uminho” (NORTE-07-0162-FEDER-0000869), under the National Strategic Reference Framework, through the European Regional Development Fund

The recently-observed self-assembly of certain salphen-based compounds into neuron-like networks of microrings interconnected with nano-thin strings may suggest a new highly-potent tool for nanoscale patterning. However, the mechanism behind such phenomena needs to be clarified before they can be applied in materials design. Here we show that, in contrast with what was initially presumed, the emergence of a “rings-and-rods” pattern is unlikely to be explained by merging, collapse and piercing of vesicles as in previously reported cases of nanorings self-assembly via non-bonding interactions. We propose an alternative explanation: the compounds under study form a 1D coordination polymer, the fibres of which are elastic enough to fold into toroidal globules upon solvent evaporation, while being able to link separate chains into extended networks. This becomes possible because the structure of the compound's scaffold is found to adopt a very different conformation from that inferred in the original work. Based on ab initio and molecular dynamics calculations we propose a step-by-step description of self-assembly process of a supramolecular structure which explains all the observed phenomena in a simple and clear way. The individual roles of the compound' s scaffold structure, coordination centres, functional groups and solvent effects are also explained, opening a route to control the morphology of self-assembled networks and to synthesize new compounds exhibiting similar behaviour., Spanish MINECO, project CTQ-201460419-R. NORTE-07-0162-FEDER-000086. FP7-PEOPLE-ITN2008-238363, info:eu-repo/semantics/publishedVersion

Comunicação em painel apresentada no E-MRS 2013 - Symposium B, To improve the efficiency of organic solar cells is necessary, for instance, to increase the open-circuit voltage or increase sun-light absorption by covering complementary regions of the solar spectrum. This can be achieved by using a donor-acceptor system composed of two polymers. The versatility of these materials has the advantage of enabling the control of morphology at nanoscale, and thus the design of an adequate interface to improve the device efficiency, using for instance nanoimprint lithography. However, proper control of the molecular organization of both polymers at polymer-polymer interface is difficult and strongly depends on the experimental conditions used. Polymer chains can present different conformations relative to the interface, creating different conjugated strand arrangements whose disorder degree can affect energy and charge transfer. Thus, understanding this effect is of utmost importance to improve the efficiency of excitonic solar cells. In this work we present a Monte Carlo model that uses a proper description of polymer-polymer interface nanomorpholy and considers the main physical processes that mediate excitons and charges dynamics. Our results show that the amount of charge extracted from the interface is sensible to polymer strand orientation and to the presence of the diffusive layer formed by the mixture of both polymers., Fundação para a Ciência e a Tecnologia (FCT)

Polymeric composite materials reinforced by curved cylindrical inclusions of very high aspect ratio are studied for their elastic stiffness. The waviness and curliness of the fibres are described by sinusoidal and helical models with different amplitudes and spiral radii, respectively. Effects are investigated in detail by finite element-based homogenisation methods, analytical models and molecular dynamics simulations. Within the finite element models two types of discretisation are considered for the fibres, using continuum solid and beam elements, respectively. Periodic boundary conditions or a special set of mixed boundary conditions are applied for approximating the effective elastic properties. The analytical investigations use a mean-field approximation in which inhomogeneities are split into unconnected segments of appropriate orientation, the elasticity tensor being calculated with a Mori–Tanaka method. It is shown that both curved fibre geometries, sinusoidal and helical, significantly reduce the longitudinal elastic stiffness of the composite. Beam element-based fibre models and analytical solutions give low and high estimates, respectively, for the elastic constants. The continuum mechanical results are found to be in good agreement with the molecular dynamics predictions.

Organic and hybrid perovskite based solar cells have a huge potential to significantly contribute to a clean electricity supply of the future. However, so far they exhibit complex and hierarchical degradation paths and their understanding can only be acquired through the application of complementary chemical and physical characterization techniques. This limited device stability is the main hurdle for a successful and large scale market introduction of these emerging solar cell technologies. Our StableNextSol Action has created a highly interdisciplinary network of laboratories, as well as corresponding industry, overall more than 120 partners, with complementary analytical techniques for the study and understanding of the degradation mechanisms occurring in state-of-the-art devices. Our Action integrates and generates fundamental knowledge and expertise to foster disruptive innovations targeted to mitigate device failure and to propose and develop new concepts for more stable solar cells. Value is added to the entire value chain of photovoltaic research at European and international level, as well as variety decision makers in the public sector by supporting specialisation policy and standards still lacking in this research field. The outcome of the Action will contribute to resolve the global challenges facing the industry and this COST Action initiative has brought together all these expertises and resources to promote the cooperation between different sectors, academia, public authorities and industry.

In this work, we report on the production of Ge nanoparticles (NPs) in an inert Ar gas atmosphere by pulsed laser deposition (PLD) at room temperature (RT). The direct deposition of energetic particles/droplets resulting from the ablation process of the target material has been avoided by using an original and customized off-axis shadow mask (shadowed off-axis) deposition set-up where the NPs deposition on the substrate takes place by means of scattering between the NPs formed in the vapor phase and the background Ar atoms. It is found that the Ar gas pressure parameter has a relevant role in the crystallization process, with better crystallinity obtained as the background Ar pressure is raised for the given experimental conditions. © Springer-Verlag 2012

During the last years it has been clear that it is importance to understand and control the nanostructure of the active polymer layer used in optoelectronic devices, like polymer diodes, solar cells or field effect transistors. Several experimental studies have shown that the nanostructure of polymer thin films used in these optoelectronic devices depends on the conditions used to deposit the polymer layer between the electrodes. As a result, in solid state conjugated polymer chains tend to be stacked and aligned relative to the electrodes creating domains with different sizes that influence the performance of these devices. To understand how the spatial arrangement of polymer chains affects the functioning of optoelectronic devices, we performed computer simulations using our mesoscopic model based on a generalized dynamic Monte Carlo method. We focus our study on the influence of the nanomorphology on the electric properties of polymer light emitting diodes. Our results show that for a pristine polymer layer and in the presence of ohmic contacts between the electrodes and the polymer layer, the electric properties of the device, namely current density, charge density, internal electric field and the number of charges that undergo recombination strongly depends on the polymer morphology at nanoscale., Fundação para a Ciência e a Tecnologia (FCT) - SFRH/BD/22143/2005, Fundo Europeu de Desenvolvimento Regional (FEDER) – Programa Operacional “Ciência , Tecnologia, Inovação” – POCTI/CTM/41574/2001, CONC-REEQ/443/EEI/2005

The actual interest on polymer light emitting diodes (PLEDs) is based on the fact that they are easy to process, which reduces the cost of fabrication and thus opening a new branch in the electronic market the low-cost electronics. However, these devices present a limited efficiency compared to their inorganic counterparts mainly due to the unbalanced charge injection, which reduces the fluorescence emission. One of the first strategies to improve PLEDs efficiency was using a bilayer structure composed by two polymers to improve charge injection and transport, and at the same time tune charge recombination zone to reduce the effect of the electrodes on exciton quenching. Although this is a very ingenious device architecture some of these bilayer devices showed a lower efficiency than it was expected. The reason for that is attributed to the dissolution of the first polymer layer by the solvent used for the deposition of the second polymer layer, which do not allow to create a define polymer/polymer interface. Although cross-linking the first polymer layer can solve this problem, there is not a clear understanding why the presence of a graded interface between both polymer layers can lead to a change on PLED efficiency. In order to clarify the effect of a graded polymer/polymer interface as compared to a sharp one on the functioning of a PLED, we performed computer experiments using a mesoscopic model of a bilayer PLED developed by us that considers the morphology of both polymers at nanoscale and their properties at molecular scale. The results present in this work show clearly a significant change on the charge recombination profile within the polymer device depending on the type of interface formed between the two polymers, which can be a plausible explanation for the loss of efficiency in the bilayer 7-CN-PPV/PPV LED., Fundação para a Ciência e a Tecnologia (FCT) - POCTI/CTM/41574/2001, CONC-REEQ/443/EEI/2005, SFRH/BD/22143/2005

Semiconductor polymers are successfully implemented in a broad range of applications such as light emitting diodes, field effect transistors and photovoltaic devices. Most of the achievements reached in the development of these devices were obtained at experimental level, being difficult to identify individually the influence of each factor that limits and controls these devices efficiency. One of the factors that strongly influence the performance of polymer-based devices is the presence of chemical defects in the polymer strands that change their molecular properties. As a result, these polymer strands can work like traps or deep energetic states for charge transport, leading, for instance, to a decrease on charge mobility. At experimental level it is a difficult task to isolate the influence of each type of chemical defects individually on the molecular properties of the polymer strands. It is in this context that theoretical modelling seems to be the most suitable approach to get a deep understanding of the influence of chemical defects on the molecular properties of semiconductor polymers. By performing quantum molecular dynamics calculations we study the influence of chemical defects on the molecular properties of poly(para-phenylenevinylene) (PPV). Our results show clearly a significant difference on the electronic properties of defective polymer strands (e.g. charge carrier localization, ionization potential, electron affinity and electric-field threshold for charge carrier mobility along the polymer backbone) as compared with defect-free strands., Fundação para a Ciência e a Tecnologia (FCT) - CONC-REEQ/443/EEI/2005, SFRH/BD/22143/2005

We have performed first principles density functional theory calculations to study the formation energy of point defects in TiC, TiO and TiCO compounds. The formation energy of isolated vacancies were obtained for different equilibrium conditions. For binary compounds, we have also calculated the formation energy of antisite defects. It was found that the defect formation energies strongly depend on the chemical environment. Our results show that C vacancies are easily formed in TiC and TiCO. For the TiO compound, Ti vacancies are highly probable to occur and O vacancies are also easily formed under titanium rich atmosphere., Fundação para a Ciência e a Tecnologia (FCT) – Programa Operacional “Ciência , Tecnologia, Inovação” – CONC-REEQ/443/EEI/2005, POCTI/CTM/69362/2006

The recast of the Energy Performance of Buildings Directive settle that by 2020 all new buildings should reach nearly zero energy levels (2018 for buildings owned or occupied by public authorities). Therefore, technicians involved in the design, management and approval of buildings should be able to understand and apply nearly zero energy buildings (nZEB) concepts in both new buildings and refurbishment of existing ones. At European Union (EU) level there are differences in commitment to the EU targets and the construction of nZEB. Therefore, it is necessary to develop studies that demonstrate the advantages of the nZEB and ZEB design process that can increase the awareness of both building clients and other stakeholders regarding this issue. In this context, the aim of this paper is to assess the energy and environmental life-cycle performance of different renovation scenarios (Basic Renovation, nZEB and ZEB) for multifamily buildings in Portugal. This will be focused on the goals of the nZEB and ZEB design process and on the contribution of solar systems (both solar thermal collectors, STCs, and photovoltaic panels, PVs) to the achievement of those goals. The results presented in this paper show that, in the Portuguese climate and for a typical multi-family building, it is possible to overcome 100% of the energy needs for acclimatization and domestic hot water (DHW) preparation with the integration of solar systems. From the results, it is also possible to conclude that a significant amount of energy and carbon emissions are avoided for every renovation scenario during the considered lifetime (30 years) and that the nZEB and ZEB scenarios are cost-effective with attractive payback times., IEE Project SouthZEB (under the reference IEE/13/393), Portuguese Foundation for Science and Technology (FCT) in the framework of the Strategic Projects UID/ECI/04047/2013 and UID/FIS/04650/2013

Conjugated polymers show interesting properties that make them appropriated for nanoelectronics. Several studies of poly(p-phenylene vinylene) (PPV) have suggested that each polymer chain consists of several planar segments, with conjugation length of nanoscale dimension, linked by twists or kinks. A pronounced twist between two planar segments in a PPV chain not only causes loss of main-chain conjugation but it may also alter electron and hole mobility along the chain, which has further implications for the percolation of charge through the polymer film. We used self-consistent quantum molecular dynamics calculations to provide information on the electric field needed to move the injected charges (either electrons or holes) along the planar segments of PPV and to cross the twist between two planar segments perpendicular to each other. Field-dependent charge mobility was also estimated for conjugated segments of various lengths. Our results suggest that electrons can cross the twist between adjacent planar segments for lower applied electric fields than holes if there is no more than one electronic charge (electron or hole) on the PPV chain, otherwise similar fields are needed., Fundação para a Ciência e a Tecnologia FCT) Programa Operacional “Ciência , Tecnologia, Inovação” – POCTI/CTM/41574/2001, CONC-REEQ/443/EEI/2001 e SFRH/BD/11231/2002

Human dental enamel has a porous mesostructure at the nanometre to micrometer scales that affects its thermal and mechanical properties relevant to laser treatment. We exploit finite element models to investigate the response of this mesostructured enamel to mid infrared lasers (CO2 at 10.6 mm and Er:YAG at 2.94 mm). Our models might easily be adapted to investigate ablation of other brittle composite materials. The studies clarify the role of pore water in ablation, and lead to an understanding of the different responses of enamel to CO2 and Er:YAG lasers, even though enamel has very similar average properties at the two wavelengths. We are able to suggest effective operating parameters for dental laser ablation, which should aid the introduction of minimally-invasive laser dentistry. In particular, our results indicate that, if pulses of » 10 ms are used, the CO2 laser can ablate dental enamel without melting, and with minimal damage to the pulp of the tooth. Our results also suggest that pulses with 0.1-1 ms duration can induce high stress transients which may cause unwanted cracking., Fundação para a Ciência e a Tecnologia (FCT) Fundo Europeu de Desenvolvimento Regional (FEDER) – Programa Operacional “Ciência , Tecnologia, Inovação” POCTI/ESP/37944/2001 e SFRH/BD/4725/2001

We have used a self-consistent quantum molecular dynamics approach to calculate the mobility of both positive and negative polaron-type carriers on solated chains of poly(p-phenylene vinylene) (PPV) and some of its derivatives and the dependence of their mobility on the applied electric field. Our results suggest that polaron-type mobility along most of these polymer chains has a clear dependence on the electric field which is quite different from the result derived for bulk PPV-based materials., Fundação para a Ciência e a Tecnologia (FCT) Programa Operacional “Ciência , Tecnologia, Inovação” – POCTI/CTM/41574/2001, CONC-REEQ/443/EEI/2001 e SFRH/BD/11231/2002

We describe a new approach to model the dynamical structural modifications of ferroelectric polymer molecules induced by uniaxial stretching and by the application of electric fields of various strengths and orientations. Our approach combines a self-consistent quantum mechanical method with molecular dynamics, removing the need to use inter-atomic potentials in the dynamic calculations. Here we present results obtained for individual molecules of poly(vinylidene fluoride) in its alpha and beta form. The effects of structural disorder due to the presence of inverted monomer units in a “head-to-head” and “tail-to-tail” position are also discussed.

Using a mesoscopic modelling approach, the authors performed computer experiments to study the influence of polymer density on bipolar charge evolution through thin layers of polydiacetylene (PDA) exhibiting specific microstructures. We found that the competition between charge transport, trapping and recombination within the polymer layer leads to several general trends, some of them being non-intuitive, as one varies polymer density. Our results show that polymer density mainly affects current and recombination efficiencies in the absence of defects or impurity states. The overall trends depend both on chain orientation relative to the electrodes and on the strength of the external applied electric field. These results suggest that adequate modelling of charge transport in electronic and optoelectronic devices based on conducting and semiconducting polymers, such as PDA, must include their structure and related key factors at mesoscopic scale. Such models provide the necessary knowledge-base to optimize the polymer film structure for electronic applications., Fundação para a Ciência e a Tecnologia (FCT) – Programa Operacional “Ciência , Tecnologia, Inovação” – POCTI/CTM/41574/2001 e SFRH/BD/11231/2002, Comunidade Europeia (CE). Fundo Europeu de Desenvolvimento Regional (FEDER)

We present a finite element model to investigate the dynamic thermal and mechanical response of ceramic materials to pulsed infrared radiation. The model was applied to the specific problem of determining the influence of the pulse duration on the stress levels reached in human dental enamel irradiated by a CO2 laser at 10.6 mm with pulse durations between 0.1 and 100 ms and sub-ablative fluence. Our results indicate that short pulses with durations much larger than the characteristic acoustic relaxation time of the material can still cause high stress transients at the irradiated site, and indicate that pulse durations of the order of 10 ms may be more adequate both for enamel surface modification and for ablation than pulse durations up to 1 ms. The model presented here can easily be modified to investigate the dynamic response of ceramic materials to mid-infrared radiation and help determine optimal pulse durations for specific procedures., Fundação para a Ciência e a Tecnologia (FCT) – Programa Operacional “Ciência , Tecnologia, Inovação” – POCTI/ESP/37944/2001 e SFRH/BD/4725/2001.

The extent of genetic variation and levels of temporal and spatial heterogeneity was investigated, at six polymorphic protein-coding loci, in wild Atlantic salmon Salmo salar populations from six rivers of Asturias (Northern Spain). Also, stocks from northern Europe that were among those introduced to repopulate Asturian Rivers, and other wild Spanish and European populations were characterized. The lack of temporal variation observed suggests that effective population sizes of Asturian populations are sufficiently large to prevent extreme levels of genetic drift and that the introduced fish had a negligible contribution to the fisheries of Asturian rivers.

We present and discuss a set of boundary conditions (BCs) to use in three-dimensional, mesoscopic, finite element models of mid-infrared pulsed laser ablation of brittle materials. These models allow the study of the transient displacement and stress fields generated at micrometer scales during and after one laser pulse, where using conventional BCs may lead to some results without physical significance that can be considered an artefact of the calculations. The proposed BCs are tested and applied to a micrometer-scale continuous model of human dental enamel under CO2 radiation (10.6 mm, 0.35 ms pulse, sub-ablative fluence), giving rise to the following results: the highest stress is obtained at the irradiated surface of the model, at the end of the laser pulse, but afterwards it decreases rapidly until it becomes significantly lower than the stress in a region 2.5 mm deep in the model; a thermally induced vibration in the material is predicted. This non-intuitive dynamics in stress and displacement distribution cannot be neglected and has to be considered in dynamic laser ablation models, since it may have serious implications in the mechanisms of ablation., Fundação para a Ciência e a Tecnologia (FCT) – Programa Operacional “Ciência, Tecnologia, Inovação” - POCTI/ESP/37944/2001, SFRH/BD/4725/2001., Comunidade Europeia (CE). Fundo Europeu de Desenvolvimento Regional (FEDER).

We present an analytical model for a ceramic material (hydroxyapatite) containing nanometre-scale water pores, and use it to estimate the pressure at the pore as a function of temperature at the end of a single 0.35 µs laser pulse by Er:YAG (2.94 µm) and CO2 (10.6 µm) lasers. Our results suggest that the pressure at the pore is directly related to pore temperature, and that very high pressures can be generated simply by the thermal expansion of liquid water. Since the temperature reached at the pores at the end of the laser pulse is a strong function of pore size for Er:YAG lasers, but is independent of pore size for CO2 lasers, our present results provide a possible explanation for the fact that the enamel threshold ablation fluences are more variable for Er:YAG lasers than for CO2 lasers, and suggest that experimentalists should analyse their results accounting for factors (like age or type of tooth) that may change the pore size distribution in their samples., Comunidade Europeia (CE) - Fundo Comunitário Europeu (FEDER)., Fundação para a Ciência e a Tecnologia (FCT).

Poling processes play an important role in the design and preparation of many ferroelectric materials for practical uses in the field of sensors and actuators. Particularly, the processing of piezoelectric beta-poly(vinylidene fluoride) (PPVDF) involves mechanical stretching in order to transform the extruded a-phase into the P-phase and poling of this later material in order to optimize the piezoelectric response. This poling process affects the orientation of the dipolar moments of the beta-chains and improves the alpha to beta transformation. Poling processes in general and in PVDF in particular are still quite empirical because a firm understanding of the physical processes involved in poling has not been fully established. In the present work we use a self-consistent quantum molecular dynamics method to study the effect of the electric field on both alpha and beta chains of PVDF. The orientation of the dipolar moments in each chain as a function of an electric field and the accompanying structural modifications due to these reorientations will be the main parameters discussed. The theoretical results will be used to better understand the changes at a molecular level due to the poling process, as observed in FTIR experiments, performed in poled and non-poled beta-PVDF from the same batch., Comunidade Europeia (CE). Fundo Europeu de Desenvolvimento Regional (FEDER), Fundação para a Ciência e a Tecnologia (FCT) – Programa Operacional “Ciência, Tecnologia, Inovação POCTI/CTM/41574/2001, SFRH/BD/11231/2002, Grant POCTI/CTM/33501/99.

Introducing methoxy electron donor groups into a poly(para-phenylene vinylene) (PPV) chain will lead to the appearance of unique electronic properties at the molecular scale which should affect the overall properties of light-emitting diodes based on these polymers. Self-consistent quantum molecular dynamics calculations have been used to provide information on intra-molecular properties of poly(2,5-dimethoxy-para-phenylene vinylene) (DMeOPPV), which are relevant for the modelling and characterization of polymer light-emitting diodes at nanometric length scale. We focus our attention on those properties that have been somewhat neglected in previous literature: the charge distribution associated with positive and negative charge carriers and their intra-molecular mobility when an electric field is applied., Fundação para a Ciência e a Tecnologia (FCT) – Programa Operacional “Ciência, Tecnologia, Inovação” - POCTI/CTM/41574/2001, SFRH/BD/11231/2002., Comunidade Europeia (CE). Fundo Europeu de Desenvolvimento Regional (FEDER)

The performance of a single layer polymer light-emitting diode depends on several interdependent factors, although recombination between electrons and holes within the polymer layer is believed to play an important role. Our aim is to carry out computer experiments in which bipolar charge carriers are injected in polymer networks made of poly(p-phenylene vinylene) chains randomly oriented. In these simulations, we follow the charge evolution in time from some initial state to the steady state. The intra-molecular properties of the polymer molecules obtained from self-consistent quantum molecular dynamics calculations are used in the mesoscopic model. The purpose of the present work is to clarify the effects of intra-molecular charge mobility and energy disorder on recombination efficiency. In particular, we find that charge mobility along the polymer chains has a serious influence on recombination within the polymer layer. Our results also show that energy disorder due to differences in ionization potential and electron affinity of neighbouring molecules affects mainly recombinations that occur near the electrodes at polymer chains parallel to them., Fundação para a Ciência e a Tecnologia (FCT) – Programa Operacional “Ciência, Tecnologia, Inovação” - POCTI/CTM/41574/2001, Comunidade Europeia (CE). Fundo Europeu de Desenvolvimento Regional (FEDER)

Using a finite element approach the authors model the influence of enamel's microstructure and water distribution on the temperature and stress at the centre of the laser spot, for a CO2 laser working at 10.6 μm, with 0.35 μs pulse duration and subablative intensity. The authors found that the distribution of water in enamel significantly influences the stress generated at the end of one laser pulse: much lower (two orders of magnitude) stress values occur in models with homogeneously distributed water than in models with 0.27 vol.% water located in pores or 4 vol.% in layers. The amount of water in enamel has a strong influence on the stress distribution, but not on the maximum stress values reached. However, different water contents do not influence the temperature distribution in enamel. These results suggest that adequate modelling of the ablation mechanisms in enamel, as in other highly inhomogeneous materials, must include their structure at the mesoscopic scale., Comunidade Europeia (CE). Fundo Europeu de Desenvolvimento Regional (FEDER) - Programa Operacional "Ciência, Tecnologia, Inovação (POCTI) - POCTI/ESP/37944/2001., Fundação para a Ciência e a Tecnologia (FCT) - SFRH/BD/4725/2001.

The softness of conjugated polymers leads to strong coupling between polymer's electrons and lattice vibrations. Therefore, it is necessary to perform quantum molecular dynamics computer simulations in order to study their electronic and optical properties at molecular level. We have used self-consistent molecular dynamics calculations with inter-atomic forces evaluated from quantum mechanical calculations at the complete neglect of differential overlap level to discuss some of the issues relating to the electronic processes involved in polydiacetylene and poly(p-phenylene vinylene). Specifically addressed are the charge induced structural changes of the polymer chains and the intra-molecular charge mobility. The change in the chemical potential of individual polymer strands at zero temperature is also discussed. Our results suggest a geometrical distortion in the bond length distribution relative to the uncharged chains which is accompanied by changes in atomic charges at the distortion site. The charge carrier mobility is predicted to depend on the strength of the electric field, in accordance with experiments.

We present generalized Monte Carlo calculations to assess the effects of texture and related key factors on the properties of polymer-based light emitting diodes. We, describe one class of mesoscopic model giving specific realizations of the polymer network. The model, with simple physically based rules, shows the effects of polymer structural order on current flow, trapping and radiative and non-radiative charge recombination within the polymer layer. Interactions between charges are included explicitly, as are image interactions with the electrodes. It is important that these Coulomb interactions are not simplified to an averaged space charge, since the local interactions can lead to effective trapping of charge, even in the absence of defective chains or impurity trapping. There proves to be an important role for trapping, in which charges are localized for times long compared with transit times. The competition between current flow, trapping and radiative and non-radiative charge recombination means that some of the trends are not intuitively obvious. For example, if radiative recombination occurs only on short polymer chains, as is the case for certain polymer systems, the internal efficiency appears to saturate for a concentration of these shorter luminescent chains of about 20-30%. As the proportion of shorter chains increases, trapping increases, whereas current efficiency decreases. Our approach provides a natural link between atomistic models of individual polymer molecules and the macroscopic descriptions of device modelling. Such mesoscopic models provide a means to design better film structures, and hence to optimize the effectiveness of new organic materials in a range of applications., Engineering and Physical Sciences Research Council (EPSRC).

It is common to look at the atomic processes of removal of atoms or ions from surfaces. At this microscopic scale, one has to understand which surface ions are involved, which excited states are created, how electrons are transferred and scattered, and how the excitation leads to ion removal. It is even more common to look at continuum models of energy deposition in solids, and at the subsequent heat transfer In these macroscopic analyses, thermal conduction is combined with empirical assumptions about surface binding. Both these pictures are useful, and both pictures have weaknesses. The atomistic pictures concentrate on relatively few atoms, and do not recognize structural features or the energy and carrier fluxes on larger scales. The continuum macroscopic models leave out crystallographic information and the interplay of the processes with high nonequilibrium at smaller scales. Fortunately, there is a middle way: mesoscopic modeling, which both models the key microstructural features and provides a link between microscopic and macroscopic. In a mesoscopic model, the length scale is determined by the system; often this scale is similar to the grain size. Microstructural features like grain boundaries or dislocations are considered explicitly. The time scale in a mesoscopic model is determined by the ablation process (such as the pulse length:) rather than the short time limitations of molecular dynamics, yet the highly nonequilibrium behavior is adequately represented. Mesoscopic models are especially important when key process rates vary on a short length scale. Some microstructural feature (like those in dentine or dental enamel) may absorb light much more than others; other features (like grain boundaries) may capture carriers readily, or allow easier evaporation, or capture and retain charge (like grain boundaries); it is these processes which need a mesoscopic analysis. The results described will be taken largely from the work on MgO of Ribeiro, Ramos, and Stoneham for ablation by sub-band Sap light., Fundação para a Ciência e a Tecnologia (FCT) – PBICT/FIS/2151/95., Engineering and Physical Sciences Research Council (EPSRC) - GR/L02678, GR/L70615.

Conducting polymers have attracted much attention concerning the possibility of their use as active components of electronic and optoelectronic devices. We use a molecular dynamics method with semi-empirical quantum chemistry at CNDO (complete Neglect of differential overlap) level to study the chemical interactions between aluminium atoms and trans-polyacetylene during the interface formation. Our results suggest that aluminium dimer (Al2) bound to a polymer chain is energetically more favourable than the adsorption of isolated aluminium atoms. In both cases, the compound formation is accompanied by charge transfer between metal and polymer. As a result charge rearrangement among the polyacetylene atoms is induced. We shall describe the charge-induced structural relaxation of the trans-polyacetylene backbone which is accompanied by a local change in the electronic structure of the polymer, commonly called defects.

This paper presents some preliminary results on simulations of the absorption of high fluence laser radiation by a target surface. We show the role of absorbing defects and their concentration as well as the influence on target roughness of places that absorb radiation more strongly than others. We then develop a mesoscopic model, and find that the grain boundary width (including any atmosphere of defects or space charge region) is an important parameter., Junta Nacional de Investigação, Ciência e Tecnologia (JNICT) - PBIC/C/FIS/2151/95

[EN] Molecular electronics based on structures ordered as neural networks emerges as the next evolutionary milestone in the construction of nanodevices with unprecedented applications. However, the straightforward formation of geometrically defined and interconnected nanostructures is crucial for the production of electronic circuitry nanoequivalents. Here we report on the molecularly fine-tuned self-assembly of tetrakis-Schiff base compounds into nanosized rings interconnected by unusually large nanorods providing a set of connections that mimic a biological network of neurons. The networks are produced through self-assembly resulting from the molecular conformation and noncovalent intermolecular interactions. These features can be easily generated on flat surfaces and in a polymeric matrix by casting from solution under ambient conditions. The structures can be used to guide the position of electron-transporting agents such as carbon nanotubes on a surface or in a polymer matrix to create electrically conducting networks that can find direct use in constructing nanoelectronic circuits., The research leading to these results has received funding from ICIQ, ICREA, the Spanish Ministerio de Economia y Competitividad (MINECO) through project CTQ2011-27385 and the European Community Seventh Framework Program (FP7-PEOPLE-ITN-2008, CONTACT consortium) under grant agreement number 238363. We acknowledge E. C. Escudero-Adan, M. Martinez-Belmonte and E. Martin from the X-ray department of ICIQ for crystallographic analysis, and M. Moncusi, N. Argany, R. Marimon, M. Stefanova and L. Vojkuvka from the Servei de Recursos Cientifics i Tecnics from Universitat Rovira i Virgili (Tarragona, Spain).

The study of the average distance that singlet excitons travel during their lifetime in conjugated polymers has attracted considerable attention during the past decade, because of its importance in the functioning of many polymer-based optoelectronic devices, like solar cells and photodetectors. Intriguingly, different values of exciton diffusion length have been extracted from experiments on seemingly identical conjugated polymers. Here we use computer simulations to show that the observed discrepancies in the reported values of the exciton diffusion length may arise from differences in the orientation of conjugated polymer strands relative to the substrate surface, a factor which has been mostly overlooked. Our results show that, on pristine polymer nanodomains with conjugated strands perpendicular to the substrate surface, exciton migration length is approximately 30% and 40% lower than on those with parallel and random strand orientation relative to that surface, respectively, resulting from the different contents of physical traps present in nanodomains with different strand orientation. This work underlines the importance of molecular arrangement on exciton migration, and provides a novel theoretical framework for estimating the dependence of the exciton diffusion length with the orientation of conjugated polymers strands within the nanodomains, as well as helping the design of more efficient polymer-based optical and optoelectronic devices, such as optical sensors, photodiodes, photovoltaic cells and white light-emitting diodes., This work was supported by FEDER through the COMPETE Program and by the Portuguese Foundation for Science and Technology (FCT) in the framework of the Strategic Project PEST-C/FIS/UI607/2011, and under the projects CONC-REEQ/443/EEI/2005 and PEst-C-FIS/UI607/2011-2012. Two of us (H.M.G.C. and H. M. C. B.) are also indebted to FCT and POPH for financial support the post-doctoral grants SFRH/BPD/64554/2009 and SFRH/BPD/80561/2011.

The term cystic fibrosis (CF)-like disease is used to describe patients with a borderline sweat test and suggestive CF clinical features but without two CFTR(cystic fibrosis transmembrane conductance regulator) mutations. We have performed the extensive molecular analysis of four candidate genes (SCNN1A, SCNN1B, SCNN1G and SERPINA1) in a cohort of 10 uncharacterized patients with CF and CF-like disease. We have used whole-exome sequencing to characterize mutations in the CFTR gene and these four candidate genes. CFTR molecular analysis allowed a complete characterization of three of four CF patients. Candidate variants in SCNN1A, SCNN1B, SCNN1G and SERPINA1 in six patients with CF-like phenotypes were confirmed by Sanger sequencing and were further supported by in silico predictive analysis, pedigree studies, sweat test in other family members, and analysis in CF patients and healthy subjects. Our results suggest that CF-like disease probably results from complex genotypes in several genes in an oligogenic form, with rare variants interacting with environmental factors.

In the past few years, tribocorrosion has become a focus of research because of its relevance in terms of the future in-service degradation mechanisms of materials. In the particular case of decorative coatings, tribocorrosion is certainly one of the most important issues, and sweat corrosion and human contact wear are two other factors that may act as material selection tools. Thus, the current study aimed to investigate the tribocorrosion behavior of a new class of thin films, the Ti–C–O–N system, which is being developed to be used as a surface decorative material due to its relatively dark appearance. The films were prepared by reactive magnetron sputtering. The influence of the structural features on the tribocorrosion behavior is discussed., This research is supported by FEDER funds through COMPETE-Programa Operacional Factores de Competitividade and by national funds through the Fundacao para a Ciencia e a Tecnologia, project PTDC/CTM/69362/2006 and contract SFRH/BD/27569/2006.