Unveiling the Inner Structure of Micrometric Hollow Polymeric Fibers Using Synchrotron X-Ray Nanotomography.

In this study, a novel application of synchrotron X-ray nanotomography based on high-resolution full-field transmission X-ray microscopy for characterizing the structure and morphology of micrometric hollow polymeric fibers is presented. By employing postimage analysis using an open-source software such as Tomviz and ImageJ, various key parameters in fiber morphology, including diameter, wall thickness, wall thickness distribution, pore size, porosity, and surface roughness, were assessed. Electrospun polycaprolactone fibers with micrometric diameters and submicrometric features with induced porosity via gas dissolution foaming were used to this aim. The acquired synchrotron X-ray nanotomography data were analyzed using two approaches: 3D tomographic reconstruction and 2D radiographic projection-based analysis. The results of the combination of both approaches demonstrate unique capabilities of this technique, not achievable by other available techniques, allowing for a full characterization of the internal and external morphology and structure of the fibers as well as to obtain valuable qualitative insights into the overall fiber structure.

Encapsulation of Copper Nanoparticles in Electrospun Nanofibers for Sustainable Removal of Pesticides.

The excellent catalytic properties of copper nanoparticles (CuNPs) for the degradation of the highly toxic and recalcitrant chlorpyrifos pesticide are widely known. However, CuNPs generally present low stability caused by their high sensitivity to oxidation, which leads to a change of the catalytic response over time. In the current work, the immobilization of CuNPs into a polycaprolactone (PCL) matrix via electrospinning was demonstrated to be a very effective method to retard air and solvent oxidation and to ensure constant catalytic activity in the long term. CuNPs were successfully anchored into PCL electrospun fibers in the form of Cu2O at different concentrations (from 1.25 wt % to 5 wt % with respect to the PCL), with no signs of loss by leaching out. The PCL mats loaded with 2.5 wt % Cu (PCL-2.5Cu) almost halved the initial concentration of pesticide (40 mg/L) after 96 h. This process was performed in two unprompted and continuous steps that consisted of adsorption, followed by degradation. Interestingly, the degradation process was independent of the light conditions (i.e., not photocatalytic), expanding the application environments (e.g., groundwaters). Moreover, the PCL-2.5Cu composite presents high reusability, retaining the high elimination capability for at least five cycles and eliminating a total of 100 mg/L of chlorpyrifos, without exhibiting any sign of morphological damages.

Density Gradients, Cellular Structure and Thermal Conductivity of High-Density Polyethylene Foams by Different Amounts of Chemical Blowing Agent.

LDPE (low-density polyethylene) foams were prepared using the improved compression moulding technique (ICM) with relative densities ranging from 0.3 to 0.7 and with different levels of chemical blowing agents (from 1% to 20%). The density gradients, cellular structure and thermal conductivity of the foams were characterized. The density and amount of CBA used were found to have a significant effect on the cellular structure both at the mesoscale (density gradients) and at the microscale (different cell sizes and cell densities). In addition, the thermal conductivity of the samples is very sensitive to the local structure where the heat flux is located. The technique used to measure this property, the Transient Plane Source method (TPS), makes it possible to detect the presence of density gradients. A simple method for determining these gradients based on thermal conductivity data was developed.

Super-Insulating Transparent Polyisocyanurate-Polyurethane Aerogels: Analysis of Thermal Conductivity and Mechanical Properties.

A family of transparent polyisocyanurate-polyurethane (PUR-PIR) aerogels with an interesting combination of physical properties were synthesized. First, their textural properties were analyzed aiming to study catalyst influence on the final porous structures and densities. Their thermal conductivities were measured at different temperatures allowing observation of a clear trend relating the initial formulation with the porous structure and reaching values as low as 12 mW/mK, the lowest found in the literature for aerogels based on this polymer matrix. Contributions to thermal conductivity were calculated, improving the understanding of the porous structure-insulating performance relationship. Moreover, their mechanical properties were studied (elastic modulus, stress at different strains and elastic behavior). The aerogels showed tunable stiffness (elastic modulus from 6.32 to 0.13 MPa) by changing the catalyst concentration and significant elasticity. Thus, super-insulating transparent PUR-PIR aerogels with tailored mechanical properties were obtained opening a wide range of potential applications in the energy, building, automotive and aeronautical sectors, among others. The exceptional insulation of silica aerogels was reached at the same time that their general brittleness was improved while keeping good transparency to visible light (85%, 650 nm). Therefore, these aerogels may constitute an alternative to silica aerogels.

Improving the Insulating Capacity of Polyurethane Foams through Polyurethane Aerogel Inclusion: From Insulation to Superinsulation.

A novel synthesis of polyurethane foam/polyurethane aerogel (PUF-PUA) composites is presented. Three different polyurethane reticulated foams which present the same density but different pore sizes (named S for small, M for medium, and L for large) have been used. After the characterization of the reference materials (either, foams, and pure aerogel), the obtained composites have been characterized in order to study the effect of the foam pore size on the final properties, so that density, shrinkage, porous structure, mechanical properties, and thermal conductivity are determined. A clear influence of the pore size on the density and shrinkage was found, and the lowest densities are those obtained from L composites (123 kg/m3). Moreover, the aerogel density and shrinkage have been significantly reduced through the employment of the polyurethane (PU) foam skeleton. Due to the enhanced mechanical properties of polyurethane aerogels, the inclusion of polyurethane aerogel into the foam skeleton helps to increase the elastic modulus of the foams from 0.03 and 0.08 MPa to 0.85 MPa, while keeping great flexibility and recovery ratios. Moreover, the synthesized PUF-PUA composites show an excellent insulating performance, reducing the initial thermal conductivity values from 34.1, 40.3, and 50.6 mW/(m K) at 10 °C for the foams S, M, and L, to 15.8, 16.6, and 16.1 mW/(m K), respectively. Additionally, the effect of the different heat transfer mechanisms to the total thermal conductivity is herein analyzed by using a theoretical model as well as the influence of the measurement temperature.

Thermal Conductivity of Nanoporous Materials: Where Is the Limit?

Nowadays, our society is facing problems related to energy availability. Owing to the energy savings that insulators provide, the search for effective insulating materials is a focus of interest. Since the current insulators do not meet the increasingly strict requirements, developing materials with a greater insulating capacity is needed. Until now, several nanoporous materials have been considered as superinsulators achieving thermal conductivities below that of the air 26 mW/(m K), like nanocellular PMMA/TPU, silica aerogels, and polyurethane aerogels reaching 24.8, 10, and 12 mW/(m K), respectively. In the search for the minimum thermal conductivity, still undiscovered, the first step is understanding heat transfer in nanoporous materials. The main features leading to superinsulation are low density, nanopores, and solid interruptions hindering the phonon transfer. The second crucial condition is obtaining reliable thermal conductivity measurement techniques. This review summarizes these techniques, and data in the literature regarding the structure and thermal conductivity of two nanoporous materials, nanocellular polymers and aerogels. The key conclusion of this analysis specifies that only steady-state methods provide a reliable value for thermal conductivity of superinsulators. Finally, a theoretical discussion is performed providing a detailed background to further explore the lower limit of superinsulation to develop more efficient materials.

Silica-Based Aerogel Composites Reinforced with Reticulated Polyurethane Foams: Thermal and Mechanical Properties.

In this work, silica aerogel composites reinforced with reticulated polyurethane (PU) foams have been manufactured having densities in the range from 117 to 266 kg/m3 and porosities between 85.7 and 92.3%. Two different drying processes were employed (ambient pressure drying and supercritical drying) and a surface modification step was applied to some of the silica formulations. These composites, together with the reference PU foam and the monolithic silica aerogels, were fully characterized in terms of their textural properties, mechanical properties and thermal conductivities. The surface modification with hexamethyldisilazane (HMDZ) proved to improve the cohesion between the reticulated foam and the silica aerogels, giving rise to a continuous network of aerogel reinforced by a polyurethane porous structure. The samples dried under supercritical conditions showed the best interaction between matrixes as well as mechanical and insulating properties. These samples present better mechanical properties than the monolithic aerogels having a higher elastic modulus (from 130 to 450 kPa), a really exceptional flexibility and resilience, and the capacity of being deformed without breaking. Moreover, these silica aerogel-polyurethane foam (Sil-PU) composites showed an excellent insulating capacity, reaching thermal conductivities as low as 14 mW/(m·K).

A New Methodology Based on Cell-Wall Hole Analysis for the Structure-Acoustic Absorption Correlation on Polyurethane Foams.

Polyurethane foams with a hybrid structure between closed cell and open cell were fabricated and fully characterized. Sound absorption measurements were carried out in order to assess their acoustic performance at different frequency ranges. The cellular structure of these systems was studied in detail by defining some novel structural parameters that characterize the cell wall openings such as the average surface of holes (Sh), the number of holes (h), and the area percentage thereof (%HCW). Therefore, these parameters allow to analyze quantitatively the effect of different structural factors on the acoustic absorption performance. It has been found that the parameters under study have a remarkable influence on the normalized acoustic absorption coefficient at different frequency ranges. In particular, it has been demonstrated that increasing the surface of the holes and the percentage of holes in the cell walls allows increasing the acoustic absorption of these types of foams, a promising statement for developing highly efficient acoustic insulators. Additionally, we could determine that a suitable minimum value of hole surface to reach the highest sound dissipation for these samples exists.

Optical Properties of Polyisocyanurate-Polyurethane Aerogels: Study of the Scattering Mechanisms.

Highly transparent polyisocyanurate-polyurethane (PUR-PIR) aerogels were synthesized, and their optical properties were studied in detail. After determining the density and structural parameters of the manufactured materials, we analyzed their optical transmittance. It was demonstrated that the catalyst content used to produce the aerogels can be employed to tune the internal structure and optical properties. The results show that the employment of lower catalyst amounts leads to smaller particles forming the aerogel and concomitantly to higher transmittances, which reach values of 85% (650 nm) due to aerogel particles acting as scattering centers. Thus, it was found that the lower this size, the higher the transmittance. The effect of the sample thickness on the transmittance was studied through the Beer-Lambert law. Finally, the scattering mechanisms involved in the light attenuation were systematically evaluated by measuring a wide range of light wavelengths and determining the transition between Rayleigh and Mie scattering when the particles were larger. Therefore, the optical properties of polyurethane aerogels were studied for the first time, opening a wide range of applications in building and energy sectors such as glazing windows.

Role of Air Bubble Inclusion on Polyurethane Reaction Kinetics.

In this study, we investigated the influence of mixing conditions on the foaming process of water blown polyurethane (PU) foams obtained at different mixing speeds (50, 500, 1000 and 2000 rpm). In particular, the morphological evolution during the foaming process, in terms of the bubble size and bubble density, was studied via optical observations, while the effects on the reaction kinetics were monitored using in situ FTIR spectroscopy. At the slow mixing speed (50 rpm), no air bubbles were included and the early foaming process was characterized by the formation of new bubbles (CO2 nucleation), provided by the blowing reaction. Later on, it was observed that the coalescence affected the overall foaming process, caused by the gelling reaction, which was inhibited by the indigent mixing conditions and could not withstand the bubbles expansion. As a result, a PU foam with a coarse cellular structure and an average bubble size of 173 µm was obtained. In this case, the bubbles degeneration rate, dN/dt, was -3095 bubble·cm-3·s-1. On the contrary, at 500 rpm, air bubbles were included into the PU reaction system (aeration) and no formation of new bubbles was observed during the foaming process. After this, the air bubbles underwent growth caused by diffusion of the CO2 provided by the blowing reaction. As the gelling reaction was not strongly depleted as in the case at 50 rpm, the coalescence less affected the bubble growth (dN/dt = -2654 bubble·cm-3·s-1), leading to a PU foam with an average bubble size of 94 µm. For the foams obtained at 1000 and 2000 rpm, the bubble degeneration was first affected by coalescence and then by Ostwald ripening, and a finer cellular structure was observed (with average bubble sizes of 62 µm and 63 µm for 1000 rpm and 2000 rpm, respectively). During the first foaming stage, the coalescence was less predominant in the bubble growth (with dN/dt values of -1838 bubble·cm-3·s-1 and -1601 bubble·cm-3·s-1, respectively) compared to 50 rpm and 500 rpm. This occurrence was ascribed to the more balanced process between the bubble expansion and the PU polymerization caused by the more suitable mixing conditions. During the late foaming stage, the Ostwald ripening was only responsible for the further bubble degeneration (with dN/dt values of -89 bubble·cm-3·s-1 and -69 bubble·cm-3·s-1, respectively).

Sub-pixel Tomographic Methods for Characterizing the Solid Architecture of Foams.

Three independent analysis methods were developed to investigate the distribution of solid mass in foams analyzed by X-ray tomography with effective pixel sizes larger than the thickness of the solid network (sub-pixel conditions). Validation of the methods was achieved by a comparison with the results obtained employing high-resolution tomography for the same set of foams. The foams showed different solid mass distribution, which varied from being preferentially located on the edges, with a fraction of mass in the struts nearing 0.6, to materials in which the fraction of mass in the struts was low, under 0.15. In all cases, the accuracy of the proposed approaches was greater for materials with a higher fraction of mass in the struts. The method based on deconvolution of the attenuation probability density function yielded the closest results to the high-resolution characterizations. In contrast, analysis of the solid matrix thickness distribution after watershed segmentation, and binarization of high thickness regions (struts segmentation) required normalization through macroscopic measurements and revealed higher deviations with respect to the high-resolution results. However, segmentation-based methods allowed investigation of the heterogeneity of the fraction of mass in the struts along the sample.

Characterization and Properties of Water-Blown Rigid Polyurethane Foams Reinforced with Silane-Modified Nanosepiolites Functionalized with Graphite.

In the present study, a promising flame retardant consisting of 80 wt% silane-modified nanosepiolites functionalized with 20 wt% graphite (SFG) is used to obtain a synergistic effect principally focussed on the thermal stability of water-blown rigid polyurethane (RPU) foams. Density, microcellular structure, thermal stability and thermal conductivity are examined for RPU foams reinforced with different contents of SFG (0, as reference material, 2, 4 and 6 wt%). The sample with 6 wt% SFG presents a slightly thermal stability improvement, although its cellular structure is deteriorated in comparison with the reference material. Furthermore, the influence of SFG particles on chemical reactions during the foaming process is studied by FTIR spectroscopy. The information obtained from the chemical reactions and from isocyanate consumption is used to optimize the formulation of the foam with 6 wt% SFG. Additionally, in order to determine the effects of functionalization on SFG, foams containing only silane-modified nanosepiolites, only graphite, or silane-modified nanosepiolites and graphite added separately are studied here as well. In conclusion, the inclusion of SFG in RPU foams allows the best performance to be achieved.

SEBS as an Effective Nucleating Agent for Polystyrene Foams.

Different percentages of an elastomeric phase of styrene-ethylene-butylene-styrene (SEBS) were added to a polystyrene (PS) matrix to evaluate its nucleating effect in PS foams. It has been demonstrated that a minimum quantity of SEBS produces a high nucleation effect on the cellular materials that are produced. In particular, the results show that by adding 2% of SEBS, it is possible to reduce the cell size by 10 times while maintaining the density and open cell content of the foamed materials. The influence of this polymeric phase on the glass transition temperature (Tg) and the shear and extensional rheological properties has been studied to understand the foaming behavior. The results indicate a slight increase in the Tg and a decrease of the shear viscosity, extensional viscosity, and strain hardening coefficient as the percentage of SEBS increases. Consequently, an increase in the density and a deterioration of the cellular structure is detected for SEBS amounts higher than 3%.

Effect of the Molecular Structure of TPU on the Cellular Structure of Nanocellular Polymers Based on PMMA/TPU Blends.

In this work, the effects of thermoplastic polyurethane (TPU) chemistry and concentration on the cellular structure of nanocellular polymers based on poly(methyl-methacrylate) (PMMA) are presented. Three grades of TPU with different fractions of hard segments (HS) (60%, 70%, and 80%) have been synthesized by the prepolymer method. Nanocellular polymers based on PMMA have been produced by gas dissolution foaming using TPU as a nucleating agent in different contents (0.5 wt%, 2 wt%, and 5 wt%). TPU characterization shows that as the content of HS increases, the density, hardness, and molecular weight of the TPU are higher. PMMA/TPU cellular materials show a gradient cell size distribution from the edge of the sample towards the nanocellular core. In the core region, the addition of TPU has a strong nucleating effect in PMMA. Core structure depends on the HS content and the TPU content. As the HS or TPU content increases, the cell nucleation density increases, and the cell size is reduced. Then, the use of TPUs with different characteristics allows controlling the cellular structure. Nanocellular polymers have been obtained with a core relative density between 0.15 and 0.20 and cell sizes between 220 and 640 nm.

Analysis of the Foaming Window for Thermoplastic Polyurethane with Different Hard Segment Contents.

A series of thermoplastic polyurethanes (TPUs) with different amounts of hard segments (HS) (40, 50 and 60 wt.%) are synthesized by a pre-polymer method. These synthesized TPUs are characterized by Shore hardness, gel permeation chromatography (GPC), differential scanning calorimetry (DSC), wide angle X-ray diffraction (WAXD), dynamic mechanical thermal analysis (DMTA), and rheology. Then, these materials are foamed by a one-step gas dissolution foaming process and the processing window that allows producing homogeneous foams is analyzed. The effect of foaming temperature from 140 to 180 °C on the cellular structure and on density is evaluated, fixing a saturation pressure of 20 MPa and a saturation time of 1 h. Among the TPUs studied, only that with 50 wt.% HS allows obtaining a stable foam, whose better features are reached after foaming at 170 °C. Finally, the foaming of TPU with 50 wt.% HS is optimized by varying the saturation pressure from 10 to 25 MPa at 170 °C. The optimum saturation and foaming conditions are 25 MPa and 170 °C for 1 h, which gives foams with the lowest relative density of 0.74, the smallest average cell size of 4 µm, and the higher cell nucleation density of 8.0 × 109 nuclei/cm3. As a final conclusion of this investigation, the TPU with 50 wt.% HS is the only one that can be foamed under the saturation and foaming conditions used in this study. TPU foams containing 50 wt.% HS with a cell size below 15 microns and porosity of 1.4-18.6% can be obtained using foaming temperatures from 140 to 180 °C, saturation pressure of 20 MPa, and saturation time of 1 h. Varying the saturation pressure from 10 to 25 MPa and fixing the foaming temperature of 170 °C and saturation pressure of 1 h results in TPU foams with a cell size of below 37 microns and porosity of 1.7-21.2%.

Nanoparticles Addition in PU Foams: The Dramatic Effect of Trapped-Air on Nucleation.

To determine the effect of nanoclays and trapped air on the formation of rigid polyurethane foams, three different production procedures were used. To study the influence of mixing at atmospheric pressure, two approaches were carried out employing either an electric or a magnetic stirrer. The third approach was executed by mixing under vacuum conditions with magnetic stirring. The samples thus obtained were characterized, and the effect of trapped air into the reactive mixtures was evaluated by analyzing the cellular structures. Different levels of trapped air were achieved when employing each manufacturing method. A correlation between the trapped air and the increase in the nucleation density when nanoclays were added was found: the cell nucleation density increased by 1.54 and 1.25 times under atmospheric conditions with electric and magnetic stirring, respectively. Nevertheless, samples fabricated without the presence of air did not show any nucleating effect despite the nanoclay addition (ratio of 1.09). This result suggests that the inclusion of air into the components is key for improving nucleation and that this effect is more pronounced when the polyol viscosity increases due to nanoclay addition. This is the most important feature determining the nucleating effect and, therefore, the corresponding cell size decreases.

Cyclic Gas Dissolution Foaming as an Approach for Simultaneously Reducing Cell Size and Relative Density in Nanocellular PMMA.

A new approach to produce nanocellular polymers combining small cell sizes with low relative densities is presented herein. This production method, based on gas dissolution foaming, consists of performing a double saturation and foaming cycle. Thus, nanocellular polymethylmethacrylate (PMMA) has been produced through a first saturation at different saturation conditions (6, 10, and 20 MPa and -32 °C), at constant foaming conditions (60 °C for 1 min). Then, the nanocellular PMMAs obtained from the previous step were again saturated at different saturation conditions, 10 MPa 24 °C, 31 MPa 24 °C, 35 MPa 22 °C, and 6 MPa -15 °C and foamed at different temperatures (40, 80 and 100 °C) for 1 min. This new approach allows the cells created in the first saturation and foaming cycle to further grow in the second cycle. This fact permits producing nanocellular polymethylmethacrylate sheets combining, for the first time in the literature, cell sizes of 24 nm with relative densities of 0.3.

Current Trends on Green Wireless Sensor Networks.

The issue of energy balancing in Wireless Sensor Networks is a pivotal one, crucial in their deployment. This problem can be subdivided in three areas: (i) energy conservation techniques, usually implying minimizing the cost of communication at the nodes since it is known that the radio is the biggest consumer of the available energy; (ii) energy-harvesting techniques, converting energy from not full-time available environmental sources and usually storing it; and (iii) energy transfer techniques, sharing energy resources from one node (either specialized or not) to another one. In this article, we survey the main contributions in these three areas and identify the main trending topics in recent research. A discussion and some future directions are also included.

Non-Orthogonal Multiple Access for Unicast and Multicast D2D: Channel Assignment, Power Allocation and Energy Efficiency.

Non-orthogonal multiple access (NOMA) techniques have emerged in the past years as a solution to approximate the throughput performance of wireless communications systems to their theoretical capacity region. We consider in this paper an optimization-based model for multicast device-to-device (MD2D) communications where the channels are not orthogonal and may be (partially or fully) shared among the transmitters in each cluster. This setting leads naturally to the introduction of NOMA transmitters and receivers who use successive interference cancellation (SIC) to separate the superposed signals. To analyze the role of NOMA in MD2D, its performance impact, potential performance gains and possible shortcomings, we formulate a model that includes SIC operations in the decoders, so that higher rates can be attained when several sources transmit on the same channel(s). We also investigate the energy efficiency of the network (global and max-min) through a dynamic power control algorithm and present a centralized and a semi-distributed solution to these optimization problems. Through numerical simulations, we show that NOMA is able to improve both the sum-rate and the max-min rate of a MD2D network even from a small degree of resource sharing. Furthermore, these gains also improve the global energy efficiency on the network, but not always the max-min energy efficiency of the devices.

Efficient Wind Speed Forecasting for Resource-Constrained Sensor Devices.

Wind energy harvesting technology is one of the most popular power sources for wireless sensor networks. However, given its irregular nature, wind energy availability experiences significant variations and, therefore, wind-powered devices need reliable forecasting models to effectively adjust their energy consumption to the dynamics of energy harvesting. On the other hand, resource-constrained devices with limited hardware capacities (such as sensor nodes) must resort to forecasting schemes of low complexity for their predictions in order to avoid squandering their scarce power and computing capabilities. In this paper, we present a new efficient ARIMA-based forecasting model for predicting wind speed at short-term horizons. The performance results obtained using real data sets show that the proposed ARIMA model can be an excellent choice for wind-powered sensor nodes due to its potential for achieving accurate enough predictions with very low computational burden and memory overhead. In addition, it is very simple to setup, since it can dynamically adapt to varying wind conditions and locations without requiring any particular reconfiguration or previous data training phase for each different scenario.