Three-Dimensional-Printed Photocatalytic Sponges Decorated with Mn-Doped ZnO Nanoparticles.

The present work reports on the fabrication of high-density polyethylene sponges, decorated with Mn-doped ZnO nanostructures. The sponges were developed utilizing three-dimensional printing technology, while Mn-doped ZnO nanostructures, with varying doping levels, were grown at mild temperatures. The nanostructures were fully characterized by means of scanning electron microscopy, X-ray diffraction, and Raman spectroscopy, revealing the existence of Mn doping. Moreover, their photocatalytic properties were investigated using the degradation/decolorization of a commercially available liquid laundry detergent, based on synthetic, less foaming ingredients, under UV irradiation. The Mn-doped ZnO nanostructures show better photocatalytic activity at higher doping levels. This study demonstrates that it is possible to achieve the adequate degradation of a typical detergent solution in water by means of low-cost and environmentally friendly approaches, while Mn-doped ZnO/HDPE nanostructures are good candidates for real environmental applications.

Fabrication of mm-Scale Complementary Split Ring Resonators, for Potential Application as Water Pollution Sensors.

Rectangular, millimeter-scale complementary split ring resonators were fabricated, employing the so-called Computer Numerical Control method, combined with a home-built mechanical engraver. Their electromagnetic performance was thoroughly investigated with respect to their dimensions in the frequency regime between 2 and 9 GHz via combining experiments and corresponding theoretical simulations, wherein a considerably effective consistency was obtained. Moreover, their sensing response was extensively investigated against various aqueous solutions enriched with typical fertilizers used in agriculture, as well as detergents commonly used in every-day life. Corresponding experimental results evidently establish the capability of the studied metasurfaces as potential sensors against water pollution.

Meta-Atoms with Toroidal Topology for Strongly Resonant Responses.

A conductive meta-atom of toroidal topology is studied both theoretically and experimentally, demonstrating a sharp and highly controllable resonant response. Simulations are performed both for a free-space periodic metasurface and a pair of meta-atoms inserted within a rectangular metallic waveguide. A quasi-dark state with controllable radiative coupling is supported, allowing to tune the linewidth (quality factor) and lineshape of the supported resonance via the appropriate geometric parameters. By conducting a rigorous multipole analysis, we find that despite the strong toroidal dipole moment, it is the residual electric dipole moment that dictates the electromagnetic response. Subsequently, the structure is fabricated with 3D printing and coated with silver paste. Importantly, the structure is planar, consists of a single metallization layer and does not require a substrate when neighboring meta-atoms are touching, resulting in a practical, thin and potentially low-loss system. Measurements are performed in the 5 GHz regime with a vector network analyzer and a good agreement with simulations is demonstrated.

Highly ordered laser imprinted plasmonic metasurfaces for polarization sensitive perfect absorption.

We present polarization-sensitive gap surface plasmon metasurfaces fabricated with direct material processing using pulsed laser light, an alternative and versatile approach. In particular we imprint laser induced periodic surface structures on nanometer-thick Ni films, which are back-plated by a grounded dielectric layer with TiO2 and ZnO deposition followed by Au evaporation. The procedure results in a metal-insulator-metal type plasmonic metasurface with a corrugated top layer consisting of highly-ordered, sinusoidal shaped, periodic, thin, metallic nanowires. The metasurface sustains sharp, resonant gap surface plasmons and provides various opportunities for polarization control in reflection, which is here switched by the size and infiltrating material of the insulating cavity. The polarization control is associated with the polarization sensitive perfect absorption and leads to high extinction ratios in the near-IR and mid-IR spectral areas. Corresponding Fourier-transform infrared spectroscopy measurements experimentally demonstrate that the fabrication approach produces metasurfaces with very well-defined, controllable, sharp resonances and polarization sensitive resonant absorption response which, depending on the insulating cavity size, impacts either the normal or the parallel to the nanowires polarization.

Fabrication of Metasurfaces on Building Construction Materials for Potential Electromagnetic Applications in the Microwave Band.

Energy self-sufficiency, as well as optimal management of power in buildings is gaining importance, while obtaining power from traditional fossil energy sources is becoming more and more expensive. In this context, millimeter-scale metasurfaces can be employed to harvest energy from microwave sources. They can also be used as sensors in the microwave regime for efficient power management solutions. In the current study, a simple spray printing method is proposed to develop metasurfaces in construction materials, i.e., plasterboard and wood. Such materials are used in the interior design of buildings; therefore, the implementation of metasurfaces in large areas, such as walls, doors and floors, is realized. The fabricated metasurfaces were characterized regarding their electromagnetic performance. It is hereby shown that the investigated metasurfaces exhibit an efficient electromagnetic response in the frequency range (4-7 GHz), depending on the MS. Thus, spray-printed metasurfaces integrated on construction materials can potentially be used for electromagnetic applications, for buildings' power self-efficiency and management.

Methods of Preparation and Performance Evaluation of ABS/Mineral Microsphere Composites Produced through FDM and Compression Molding.

The use of amorphous microspheres as filler in composites is promising due to their light weight, low cost, incombustibility, and the ability to alter relevant properties of the final composite. Contrary to glass spheres, perlite microspheres are much cheaper and can be tailor-made to facilitate purpose-oriented alteration of the final composite. We report the use of perlite microspheres for the preparation of: (1) composites, through a compression molding (hot pressing) technique; and (2) composite filaments, in a single screw extruder, as well as their use for sample printing through Fused Deposition Modeling (FDM). Proper characterization of the produced composites allows for their evaluation in terms of physical, thermal, and mechanical properties and with regards to the manufacturing technique, the filler fraction, and size. Composite samples of acceptable quality in terms of filler survival and dispersion as well as mechanical properties were produced through compression molding using fine expanded perlite microspheres (<90 µm) up to an infill ratio of 40 vol.%. Fine fillers (<90 µm) performed well in FDM, allowing printing of composite dogbone samples with a higher Young's modulus and elongation and similar ultimate tensile strength compared to benchmark, up to an infill ratio of 20 vol.%. Composite samples present a slightly lower burning rate compared to those produced solely by ABS. Perlite microspheres present good workability in both applications, possessing satisfactory performance as filler in the composites, and can thus be assumed a promising multifunctional filler for various thermoplastics considering their low price, environmental impact, and fire rating.

3D Printed Metal Oxide-Polymer Composite Materials for Antifouling Applications.

Current technology to prevent biofouling usually relies on the use of toxic, biocide-containing materials, which can become a serious threat to marine ecosystems, affecting both targeted and nontargeted organisms. Therefore, the development of broad-spectrum, less toxic antifouling materials is a challenge for researchers; such materials would be quite important in applications like aquaculture. In this respect, surface chemistry, physical properties, durability and attachment scheme can play a vital role in the performance of the materials. In this work, acrylonitrile butadiene styrene (ABS)/micro ZnO or nano ZnO composite lattices with different metal oxide contents were developed using 3D printing. Their antifouling behavior was examined with respect to aquaculture applications by monitoring growth on them of the diatoms Navicula sp. and the monocellular algae Chlorella sp. with image analysis techniques. As shown, the presence of metal oxides in the composite materials can bring about antifouling ability at particular concentrations. The present study showed promising results, but further improvements are needed.

Obtaining Nanostructured ZnO onto Si Coatings for Optoelectronic Applications via Eco-Friendly Chemical Preparation Routes.

Although the research on zinc oxide (ZnO) has a very long history and its applications are almost countless as the publications on this subject are extensive, this semiconductor is still full of resources and continues to offer very interesting results worth publishing or warrants further investigation. The recent years are marked by the development of novel green chemical synthesis routes for semiconductor fabrication in order to reduce the environmental impacts associated with synthesis on one hand and to inhibit/suppress the toxicity and hazards at the end of their lifecycle on the other hand. In this context, this study focused on the development of various kinds of nanostructured ZnO onto Si substrates via chemical route synthesis using both classic solvents and some usual non-toxic beverages to substitute the expensive high purity reagents acquired from specialized providers. To our knowledge, this represents the first systematic study involving common beverages as reagents in order to obtain ZnO coatings onto Si for optoelectronic applications by the Aqueous Chemical Growth (ACG) technique. Moreover, the present study offers comparative information on obtaining nanostructured ZnO coatings with a large variety of bulk and surface morphologies consisting of crystalline nanostructures. It was revealed from X-ray diffraction analysis via Williamson-Hall plots that the resulting wurtzite ZnO has a large crystallite size and small lattice strain. These morphological features resulted in good optical properties, as proved by photoluminescence (PL) measurements even at room temperature (295 K). Good optical properties could be ascribed to complex surface structuring and large surface-to-volume ratios.

Polyethylene Migration from Food Packaging on Cheese Detected by Raman and Infrared (ATR/FT-IR) Spectroscopy.

For multiple years, food packaging migration has been a major concern in food and health sciences. Plastics, such as polyethylene, are continuously utilized in food packaging for preservation and easy handling purposes during transportation and storage. In this work, three types of cheese, Edam, Kefalotyri and Parmesan, of different hardness were studied under two complementary vibrational spectroscopy methods, ATR-FTIR and Raman spectroscopy, to determine the migration of low-density polyethylene from plastic packaging to the surface of cheese samples. The experimental duration of this study was set to 28 days due to the degradation time of the selected cheese samples, which is clearly visible after 1 month in refrigerated conditions at 4 °C. Raman and ATR-FTIR measurements were performed at a 4-3-4-3 day pattern to obtain comparative results. Initially, consistency/repeatability measurement tests were performed on Day0 for each sample of all cheese specimens to understand if there is any overlap between the characteristic Raman and ATR-FTIR peaks of the cheese with the ones from the low-density polyethylene package. We provide evidence that on Day14, peaks of low-density polyethylene appeared due to polymeric migration in all three cheese types we tested. In all cheese samples, microbial outgrowth started to develop after Day21, as observed visually and under the bright-field microscope, causing peak reverse. Food packaging migration was validated using two different approaches of vibrational spectroscopy (Raman and FT-IR), revealing that cheese needs to be consumed within a short time frame in refrigerated conditions at 4 °C.

Thermoelectric Performance of Mechanically Mixed BixSb2-xTe3-ABS Composites.

In the current study, polymer-based composites, consisting of Acrylonitrile Butadiene Styrene (ABS) and Bismuth Antimony Telluride (BixSb2-xTe3), were produced using mechanical mixing and hot pressing. These composites were investigated regarding their electrical resistivity and Seebeck coefficient, with respect to Bi doping and BixSb2-xTe3 loading into the composite. Experimental results showed that their thermoelectric performance is comparable-or even superior, in some cases-to reported thermoelectric polymer composites that have been produced using other complex techniques. Consequently, mechanically mixed polymer-based thermoelectric materials could be an efficient method for low-cost and large-scale production of polymer composites for potential thermoelectric applications.

Control of Light Transmission in a Plasmonic Liquid Metacrystal.

In this study, we experimentally demonstrated the control of light transmission through a slab of plasmonic liquid metacrystal by an external electric field. By applying the external static field, we were able to induce macroscopic anisotropy, which caused the polarization-dependent suppression of transmission at resonant frequencies. Such behavior indicates the selective plasmon excitation governed by the orientation of the meta-atoms with respect to the polarization of the electromagnetic wave. The problem of light transmission through a plasmonic liquid metacrystal was analyzed theoretically from first principles, and the obtained results were compared with the experimental data.

Flexible 3D Printed Conductive Metamaterial Units for Electromagnetic Applications in Microwaves.

In this work we present a method for fabricating three dimensional, ultralight and flexible millimeter metamaterial units using a commercial household 3D printer. The method is low-cost, fast, eco-friendly and accessible. In particular, we use the Fused Deposition Modeling 3D printing technique and we fabricate flexible conductive Spilt Ring Resonators (SRRs) in a free-standing form. We characterized the samples experimentally through measurements of their spectral transmission, using standard rectangular microwave waveguides. Our findings show that the resonators produce well defined resonant electromagnetic features that depend on the structural details and the infiltrating dielectric materials, indicating that the thin, flexible and light 3D printed structures may be used as electromagnetic microwave components and electromagnetic fabrics for coating a variety of devices and infrastructure units, while adapting to different shapes and sizes.

Experimental Demonstration of Ultrafast THz Modulation in a Graphene-Based Thin Film Absorber through Negative Photoinduced Conductivity.

We present an experimental demonstration and interpretation of an ultrafast optically tunable, graphene-based thin film absorption modulator for operation in the THz regime. The graphene-based component consists of a uniform CVD-grown graphene sheet stacked on an SU-8 dielectric substrate that is grounded by a metallic ground plate. The structure shows enhanced absorption originating from constructive interference of the impinging and reflected waves at the absorbing graphene sheet. The modulation of this absorption, which is demonstrated via a THz time-domain spectroscopy setup, is achieved by applying an optical pump signal, which modifies the conductivity of the graphene sheet. We report an ultrafast (on the order of few ps) absorption modulation on the order of 40% upon photoexcitation. Our results provide evidence that the optical pump excitation results in the degradation of the graphene THz conductivity, which is connected with the generation of hot carriers, the increase of the electronic temperature, and the dominant increase of the scattering rate over the carrier concentration as found in highly doped samples.

3D micro-structured arrays of ZnΟ nanorods.

The fabrication of nanostructures with controlled assembly and architecture is very important for the development of novel nanomaterial-based devices. We demonstrate that laser techniques coupled with low-temperature hydrothermal growth enable complex three-dimensional ZnO nanorod patterning on various types of substrates and geometries. This methodology is based on a procedure involving the 3D scaffold fabrication using Multi-Photon Lithography of a photosensitive material, followed by Zn seeded Aqueous Chemical Growth of ZnO nanorods. 3D, uniformly aligned ZnO nanorods are produced. The increase in active surface area, up to 4.4 times in the cases presented here, provides a dramatic increase in photocatalytic performance, while other applications are also proposed.

Synthesis, structure, magnetic properties and aqueous solution characterization of p-hydroquinone and phenol iminodiacetate copper(II) complexes.

The reaction of Cu2+ acetate monohydrate with 2-[N,N'-bis(carboxymethyl)aminomethyl]-4-carboxyphenol (H4cacp), 2-[N,N-bis(carboxymethyl)aminomethyl]hydroquinone (H4cah) and the dinucleating 2,5-bis[N,N-bis(carboxymethyl)aminomethyl]hydroquinone (H6bicah) in water results in the formation of several Cu2+ species, which are in dynamic equilibrium in aqueous solution and their stability is pH dependent. A systematic crystallographic study of these species was pursued, resulting in the characterization of most of the species. Additional techniques were employed to characterize the molecules in the solid state (infrared spectroscopy) and in solution (UV-vis spectroscopy and electrochemistry). These measurements show that the Cu2+ ions are ligated mainly to the iminodiacetate at pH < 6, exhibiting only weak interactions with the phenol oxygen. At pH > 6, the phenol oxygen was deprotonated and dinuclear-bridged species, from the phenolate oxygen complexes exhibiting a Cu2+ 2O2 core, were isolated. The coordination environment around the copper ions varies between trigonal bipyramidal, tetragonal pyramidal and distorted octahedral geometries. The two unpaired electrons of the Cu2+ ions are found to be antiferromagnetically coupled. A survey of the magnetic and structural properties of the dinuclear phenoxide bridged Cu2+ complexes shows that the strength of the antiferromagnetic coupling is linearly dependent on the Cu-Ophenolate bond lengths, at bond distances below 1.98 angstroms. The effect of the Cu-O-Cu angles on the magnetic properties of the complexes is also discussed.