Molecular dynamics computer simulation of scratch resistance testing of polymers: visualization

Experimental scratch resistance testing provides two numbers: the penetration depth Rp and the healing depth Rh. In molecular dynamics computer simulations, we create a material consisting of N statistical chain segments by polymerization; a reinforcing phase can be included. Then we simulate the movement of an indenter and response of the segments during X time steps. Each segment at each time step has three Cartesian coordinates of position and three of momentum. We describe methods of visualization of results based on a record of 6NX coordinates. We obtain a continuous dependence on time t of positions of each of the segments on the path of the indenter. Scratch resistance at a given location can be connected to spatial structures of individual polymeric chains.

Mechanical, electrical and electro-mechanical properties of thermoplastic elastomer styrene–butadiene–styrene/multiwal carbon nanotubes composites

Composites of styrene–butadiene–styrene (SBS) block copolymer with multiwall carbon nanotubes were processed by solution casting to investigate the influence of filler content, the different ratios of styrene/butadiene in the copolymer and the architecture of the SBS matrix on the electrical, mechanical and electro-mechanical properties of the composites. It was found that filler content and elastomer matrix architecture influence the percolation threshold and consequently the overall composite electrical conductivity. Themechanical properties aremainly affected by the styrene and filler content. Hopping between nearest fillers is proposed as the main mechanism for the composite conduction. The variation of the electrical resistivity is linear with the deformation. This fact, together with the gauge factor values in the range of 2–18, results in appropriate composites to be used as (large) deformation sensors.

Electrospun silk-elastin-like fiber mats for tissue engineering applications

Protein-based polymers are present in a wide variety of organisms fulfilling structural and mechanical roles. Advances in protein engineering and recombinant DNA technology allow the design and production of recombinant protein-based polymers (rPBPs) with an absolute control of its composition. Although the application of recombinant proteins as biomaterials is still an emerging technology, the possibilities are limitless and far superior to natural or synthetic materials, as the complexity of the structural design can be fully customized. In this work, we report the electrospinning of two new genetically engineered silk-elastin-like proteins (SELPs) consisting of alternate silk- and elastin-like blocks. Electrospinning was performed with formic acid and aqueous solutions at different concentrations without addition of further agents. The size and morphology of the electrospun structures was characterized by scanning electron microscopy showing to be dependent of concentration and solvent used. Treatment with air saturated with methanol was employed to stabilize the structure and promote water insolubility through a time-dependent conversion of random coils into β-sheets (FTIR). The resultant methanol-treated electrospun mats were characterized for swelling degree (570-720%), water vapour transmission rate (1083 g/m2/day) and mechanical properties (modulus of elasticity of ~126 MPa). Furthermore, the methanol-treated SELP fiber mats showed no cytotoxicity and were able to support adhesion and proliferation of normal human skin fibroblasts. Adhesion was characterized by a filopodia-mediated mechanism. These results demonstrate that SELP fiber mats can provide promising solutions for the development of novel biomaterials suitable for tissue engineering applications.

Simulating scratch behavior of polymers with mesoscopic molecular dynamics

Part replacement and repair is needed in structures with moving parts because of scratchability and wear. In spite of some accumulation of experimental evidence, scratch resistance is still not well understood. We have applied molecular dynamics to study scratch resistance of amorphous polymeric materials through computer simulations. As a first approach, a coarse grain model was created for high density polyethylene at the mesoscale. We have also extended the traditional approach and used real units rather than reduced units (to our knowledge, for the first time), which enable an improved quantification of simulation results. The obtained results include analysis of penetration depth, residual depth and recovery percentage related to indenter force and size. Our results show there is a clear effect from these parameters on the tribological properties. We also discuss a "crooked smile" effect on the scratched surface and the reasons for its appearance.

Mechanical, electrical and electro-mechanical properties of thermoplastic elastomer styrene–butadiene–styrene/multiwall carbon nanotubes composites

Composites of styrene–butadiene–styrene (SBS) block copolymer with multiwall carbon nanotubes were processed by solution casting to investigate the influence of filler content, the different ratios of styrene/butadiene in the copolymer and the architecture of the SBS matrix on the electrical, mechanical and electro-mechanical properties of the composites. It was found that filler content and elastomer matrix architecture influence the percolation threshold and consequently the overall composite electrical conductivity. The mechanical properties are mainly affected by the styrene and filler content. Hopping between nearest fillers is proposed as the main mechanism for the composite conduction. The variation of the electrical resistivity is linear with the deformation. This fact, together with the gauge factor values in the range of 2–18, results in appropriate composites to be used as (large) deformation sensors.

Mechanical Behavior of the Lamellar Structure in Semi-Crystalline Polymers

We have employed molecular dynamics simulations to study the behavior of virtual polymeric materials under an applied uniaxial tensile load. Through computer simulations, one can obtain experimentally inaccessible information about phenomena taking place at the molecular and microscopic levels. Not only can the global material response be monitored and characterized along time, but the response of macromolecular chains can be followed independently if desired. The computer-generated materials were created by emulating the step-wise polymerization, resulting in self-avoiding chains in 3D with controlled degree of orientation along a certain axis. These materials represent a simplified model of the lamellar structure of semi-crystalline polymers,being comprised of an amorphous region surrounded by two crystalline lamellar regions. For the simulations, a series of materials were created, varying i) the lamella thickness, ii) the amorphous region thickness, iii) the preferential chain orientation, and iv) the degree of packing of the amorphous region. Simulation results indicate that the lamella thickness has the strongest influence on the mechanical properties of the lamella-amorphous structure, which is in agreement with experimental data. The other morphological parameters also affect the mechanical response, but to a smaller degree. This research follows previous simulation work on the crack formation and propagation phenomena, deformation mechanisms at the nanoscale, and the influence of the loading conditions on the material response. Computer simulations can improve the fundamental understanding about the phenomena responsible for the behavior of polymeric materials, and will eventually lead to the design of knowledge-based materials with improved properties.

Coupling Mechanical and Electrical Behavior in the Multi-scale Simulation of Polymer-based CNT Nanocomposites

A numeric model has been proposed to investigate the mechanical and electrical properties of a polymeric/carbon nanotube (CNT) composite material subjected to a deformation force. The reinforcing phase affects the behavior of the polymeric matrix and depends on the nanofiber aspect ratio and preferential orientation. The simulations show that the mechanical behavior of a computer generated material (CGM) depends on fiber length and initial orientation in the polymeric matrix. It is also shown how the conductivity of the polymer/CNT composite can be calculated for each time step of applied stress, effectively providing the ability to simulate and predict strain-dependent electrical behavior of CNT nanocomposites.

Energy harvesting performance of piezoelectric electrospun polymer fibers and polymer/ceramic composites

The energy harvesting efficiency of electrospun poly(vinylidene fluoride), its copolymer vinylidene fluoride-trifluoroethylene and composites of the later with piezoelectric BaTiOon interdigitated electrodes has been investigated. Further, a study of the influence of the electrospinning processing parameters on the size and distribution of the composites fibers has been performed. It is found that the best energy harvesting performance is obtained for the pure poly(vinylidene fluoride) fibers, with power outputs up to 0.03 W and 25 W under low and high mechanical deformation. The copolymer and the composites show reduced power output due to increased mechanical stiffness. The obtained values, among the largest found in the literature, the easy processing and the low cost and robustness of the polymer, demonstrate the applicability of the developed system.

Initial growth of maize in response to application of rock phosphate, vermicompost and endophytic bacteria

Due to the high energy requirement and demand for non-renewable resources for the production of chemical fertilizers, added also to the environmental impact caused by the use of such products, it is important to intensify research on bio-based agricultural inputs. The use of nitrogen-fixing endophytic and phosphate solubilizing bacteria can provide these nutrients to the plants from the air and poorly soluble phosphorus sources, such as phosphate rock. The objective of this study was to evaluate the nutrition and initial growth of maize (Zea mays L.) in response to the inoculation of nitrogen-fixing and rock phosphate solubilizing endophytic bacteria, in single or mixed formulation, applied with vermicompost. The treatments containing bacteria, both diazotrophic and phosphate solubilizing, when compared to controls, showed higher levels of leaf nitrogen and phosphorus in maize, as well as higher growth characteristics. The application of vermicompost showed synergistic effect when combined with endophytic bacteria. Thus, the innovation of the combination of the studied factors may contribute to the early development of maize.

Effect of filler content on morphology and physical-chemical characteristics of poly(vinylidene fluoride)/NaY-zeolite filled membranes

Poly(vinylidene fluoride) electrospun membranes have been prepared with different NaY zeolite contents up to 32%wt. Inclusion of zeolites induces an increase of average fiber size from ~200 nm in the pure polymer up to ~500 nm in the composite with 16%wt zeolite content. For higher filler contents, a wider distribution of fibers occurs leading to a broader size distributions between the previous fiber size values. Hydrophobicity of the membranes increases from ~115º water contact angle to ~128º with the addition of the filler and is independent on filler content, indicating a wrapping of the zeolite by the polymer. The water contact angle further increases with fiber alignment up to ~137º. Electrospun membranes are formed with ~80 % of the polymer crystalline phase in the electroactive  phase, independently on the electrospinning processing conditions or filler content. Viability of MC3T3-E1 cells on the composite membranes after 72 h of cell culture indicates the suitability of the membranes for tissue engineering applications.

Synthesis, structure, and optical properties of an alternating calix[4]arene-based meta-linked phenylene ethynylene copolymer

Novel alternating copolymers comprising biscalix[4]arene-p-phenylene ethynylene and m-phenylene ethynylene units (CALIX-m-PPE) were synthesized using the Sonogashira-Hagihara cross-coupling polymerization. Good isolated yields (60-80%) were achieved for the polymers that show M-n ranging from 1.4 x 10(4) to 5.1 x 10(4) gmol(-1) (gel permeation chromatography analysis), depending on specific polymerization conditions. The structural analysis of CALIX-m-PPE was performed by H-1, C-13, C-13-H-1 heteronuclear single quantum correlation (HSQC), C-13-H-1 heteronuclear multiple bond correlation (HMBC), correlation spectroscopy (COSY), and nuclear overhauser effect spectroscopy (NOESY) in addition to Fourier transform-Infrared spectroscopy and microanalysis allowing its full characterization. Depending on the reaction setup, variable amounts (16-45%) of diyne units were found in polymers although their photophysical properties are essentially the same. It is demonstrated that CALIX-m-PPE does not form ground-or excited-state interchain interactions owing to the highly crowded environment of the main-chain imparted by both calix[4]arene side units which behave as insulators inhibiting main-chain pi-pi staking. It was also found that the luminescent properties of CALIX-m-PPE are markedly different from those of an all-p-linked phenylene ethynylene copolymer (CALIX-p-PPE) previously reported. The unexpected appearance of a low-energy emission band at 426 nm, in addition to the locally excited-state emission (365 nm), together with a quite low fluorescence quantum yield (Phi = 0.02) and a double-exponential decay dynamics led to the formulation of an intramolecular exciplex as the new emissive species.

Equilibrium self-assembly of colloids with distinct interaction sites: Thermodynamics, percolation, and cluster distribution functions

We calculate the equilibrium thermodynamic properties, percolation threshold, and cluster distribution functions for a model of associating colloids, which consists of hard spherical particles having on their surfaces three short-ranged attractive sites (sticky spots) of two different types, A and B. The thermodynamic properties are calculated using Wertheim's perturbation theory of associating fluids. This also allows us to find the onset of self-assembly, which can be quantified by the maxima of the specific heat at constant volume. The percolation threshold is derived, under the no-loop assumption, for the correlated bond model: In all cases it is two percolated phases that become identical at a critical point, when one exists. Finally, the cluster size distributions are calculated by mapping the model onto an effective model, characterized by a-state-dependent-functionality (f) over bar and unique bonding probability (p) over bar. The mapping is based on the asymptotic limit of the cluster distributions functions of the generic model and the effective parameters are defined through the requirement that the equilibrium cluster distributions of the true and effective models have the same number-averaged and weight-averaged sizes at all densities and temperatures. We also study the model numerically in the case where BB interactions are missing. In this limit, AB bonds either provide branching between A-chains (Y-junctions) if epsilon(AB)/epsilon(AA) is small, or drive the formation of a hyperbranched polymer if epsilon(AB)/epsilon(AA) is large. We find that the theoretical predictions describe quite accurately the numerical data, especially in the region where Y-junctions are present. There is fairly good agreement between theoretical and numerical results both for the thermodynamic (number of bonds and phase coexistence) and the connectivity properties of the model (cluster size distributions and percolation locus).

Power converter topologies for wind energy conversion systems: Integrated modeling, control strategy and performance simulation

This paper presents new integrated model for variable-speed wind energy conversion systems, considering a more accurate dynamic of the wind turbine, rotor, generator, power converter and filter. Pulse width modulation by space vector modulation associated with sliding mode is used for controlling the power converters. Also, power factor control is introduced at the output of the power converters. Comprehensive performance simulation studies are carried out with matrix, two-level and multilevel power converter topologies in order to adequately assert the system performance. Conclusions are duly drawn.

Light pollution and energy efficiency: a case study of the village of Vialonga

Since industrialization and the formation of larger urban centers in the nineteenth century, pollution of the environment was always present in daily life in various ways, namely in the form of light. Light pollution can cause various consequences, both for humans and for their ecosystem, producing effects on environmental, social, economic and scientific level. In Portugal, the lighting is responsible for 3% of total electricity consumption, energy costs are in some cases more than 50% towards the costs incurred by municipalities with energy, checking-in recent years a trend similar to that improvement of illumination levels in the region (about 4 to 5% per year). Proper use of lighting brings many benefits both to the citizen and environment, since greater energy efficiency can contribute to reducing CO2 emissions, energy costs, as well as to decrease the use of resources not-renewable and/or contamination of renewable resources, which can occurs in the process of obtaining electricity. The present study has a main goal to analyze the illuminance levels associated to the public lighting of the village of Vialonga, Vila Franca de Xira (Portugal), to verify if it is efficient. The aim is also to relate the efficiency of street lighting with the existence of light pollution.

The condensation and ordering of models of empty liquids

We consider a simple model consisting of particles with four bonding sites ("patches"), two of type A and two of type B, on the square lattice, and investigate its global phase behavior by simulations and theory. We set the interaction between B patches to zero and calculate the phase diagram as the ratio between the AB and the AA interactions, epsilon(AB)*, varies. In line with previous work, on three-dimensional off-lattice models, we show that the liquid-vapor phase diagram exhibits a re-entrant or "pinched" shape for the same range of epsilon(AB)*, suggesting that the ratio of the energy scales - and the corresponding empty fluid regime - is independent of the dimensionality of the system and of the lattice structure. In addition, the model exhibits an order-disorder transition that is ferromagnetic in the re-entrant regime. The use of low-dimensional lattice models allows the simulation of sufficiently large systems to establish the nature of the liquid-vapor critical points and to describe the structure of the liquid phase in the empty fluid regime, where the size of the "voids" increases as the temperature decreases. We have found that the liquid-vapor critical point is in the 2D Ising universality class, with a scaling region that decreases rapidly as the temperature decreases. The results of simulations and theoretical analysis suggest that the line of order-disorder transitions intersects the condensation line at a multi-critical point at zero temperature and density, for patchy particle models with a re-entrant, empty fluid, regime. (C) 2011 American Institute of Physics. [doi: 10.1063/1.3657406]