Non-reciprocal electromagnetic metasurface based on the nonlinearity of a liquid metamaterial.

In this Letter, we propose the design of a non-reciprocal electromagnetic metasurface, which uses a highly nonlinear liquid metamaterial as a source of non-reciprocity. We show that the proposed metasurface, whose thickness is comparable to the wavelength, can exhibit a difference between the transmission coefficients in the forward and backward directions of up to 0.95. Moreover, the particularly high nonlinearity of the liquid metamaterial enables the radiation power required to induce the nonlinear effects to be considerably reduced compared with natural materials. The feasibility of the proposed metasurface has been verified by numerical simulations.

Glyphosate uses, adverse effects and alternatives: focus on the current scenario in Brazil.

Brazil, a global frontrunner in pesticide consumption and sales, particularly glyphosate, appears to be at odds with other countries that increasingly ban these products in their territories. This study gathers the values of Acceptable Daily Intake and Maximum Residue Limits (MRL) in the European Union for dozens of substances and subsequently contrasts them with the corresponding benchmarks upheld in Brazil concerning its predominant crops. Furthermore, this study delves into the toxicity levels and the potential health ramifications of glyphosate on humans through the ingestion of food containing its residues. The findings from this research underscore a notable surge in glyphosate and pesticide sales and usage within Brazil over the past decade. In stark contrast to its European counterparts, Brazil not only sanctioned the sale and application of 474 new pesticides in 2019, but extended the authorization for glyphosate sales while downgrading its toxicity classification. Finally, this review not only uncovers disparities among research outcomes but also addresses the complexities of replacing glyphosate and introduces environmentally friendlier alternatives that have been subject to evaluation in the existing literature.

Experimental Design Optimization of Acrylate-Tannin Photocurable Resins for 3D Printing of Bio-Based Porous Carbon Architectures.

In this work, porous carbons were prepared by 3D printing formulations based on acrylate-tannin resins. As the properties of these carbons are highly dependent on the composition of the precursor, it is essential to understand this effect to optimise them for a given application. Thus, experimental design was applied, for the first time, to carbon 3D printing. Using a rationalised number of experiments suggested by a Scheffé mixture design, the experimental responses (the carbon yield, compressive strength, and Young's modulus) were modelled and predicted as a function of the relative proportions of the three main resin ingredients (HDDA, PETA, and CN154CG). The results revealed that formulations containing a low proportion of HDDA and moderate amounts of PETA and CN154CG gave the best properties. Thereby, the optimised carbon structures had a compressive strength of over 5.2 MPa and a Young's modulus of about 215 MPa. The reliability of the model was successfully validated through optimisation tests, proving the value of experimental design in developing customisable tannin-based porous carbons manufactured by stereolithography.

A critical review on surface modifications mitigating dairy fouling.

Thermal treatments performed in food processing industries generate fouling. This fouling deposit impairs heat transfer mechanism by creating a thermal resistance, thus leading to regular shutdown of the processes. Therefore, periodic and harsh cleaning-in-place (CIP) procedures are implemented. This CIP involves the use of chemicals and high amounts of water, thus increasing environmental burden. It has been estimated that 80% of production costs are owed to dairy fouling deposit. Since the 1970s, different types of surface modifications have been performed either to prevent fouling deposition (anti-fouling) or to facilitate removal (fouling-release). This review points out the impacts of surface modification on type A dairy fouling and on cleaning behaviors under batch and continuous flow conditions. Both types of anti-fouling and fouling-release coatings are reported as well as the different techniques used to modify stainless steel surface. Finally, methods for testing and characterising the effectiveness of coatings in mitigating dairy fouling are discussed.

Conversion of Natural Tannin to Hydrothermal and Graphene-Like Carbons Studied by Wide-Angle X-ray Scattering.

The atomic structure of carbon materials prepared from natural tannin by two different techniques, high-temperature pyrolysis and low-temperature hydrothermal carbonization, was studied by wide-angle X-ray scattering. The obtained diffraction data were converted to the real space representation in the form of pair distribution functions. The X-ray photoelectron spectroscopy measurements provided information about the chemical state of carbon in tannin-based materials that was used to construct final structural models of the investigated samples. The results of the experimental data in both reciprocal and real spaces were compared with computer simulations based on the PM7 semiempirical quantum chemical method. Using the collected detailed information, structural models of the tannin-based carbons were proposed. The characteristics of the investigated materials at the atomic level were discussed in relation to their preparation method. The rearrangement of the tannin molecular structure and its transformation to graphene-like structure was described. The structure of tannin-based carbons pyrolyzed at 900 °C exhibited coherently scattering domains about 20 Å in size, consisting of two defected atomic layers and resembling a graphene-like arrangement.

Dielectric and Ultrasonic Properties of PDMS/TiO2 Nanocomposites.

This work presents the dielectric and ultrasonic properties of polydimethylsiloxane (PDMS) nanocomposites filled with titanium dioxide nanoparticles. The dielectric study was performed over a very broad range of frequencies (20 Hz-3 THz). The dielectric permittivity was almost frequency-independent in all the composites at room temperature over the whole range of measurement frequencies, and the dielectric losses were very low under these conditions (less than 2). The dielectric permittivity strongly increases with the nanoparticle concentration according to the Maxwell-Garnet model. Therefore, the investigated composites are suitable for various flexible electronic applications, particularly in the microwave and terahertz frequency ranges. Dielectric dispersion and increased attenuation of ultrasonic waves were observed at lower temperatures (below 280 K) due to the relaxation of polymer molecules at the PDMS/TiO2 interface and in the polymer matrix. The relaxation time followed the Vogel-Vulcher law, while the freezing temperature increased with the titanium dioxide concentration due to interactions between the polymer molecules and nanoparticles. The significant hysteresis in the ultrasonic properties indicated that titanium dioxide acts as a crystallization center. This is confirmed by the correlation between the hysteresis in the ultrasonic properties and the structure of the composites. The small difference in the activation energy values obtained from the ultrasonic and dielectric investigations is related to the fact that the dielectric dispersion is slightly broader than the Debye-type dielectric dispersion.

Evaluation of the CH4/CO2 separation by adsorption on coconut shell activated carbon: Impact of the gas moisture on equilibrium selectivity and adsorption capacity.

Upgrading biogas to biomethane is of great interest to change the energy matrix by feeding the renewable fuel produced from biomass waste into natural gas grids or directly using it to replace fossil fuels. The study aimed to assess the adsorption equilibrium of CH4, CO2, and H2O on a coconut-shell activated carbon (CAC 8X30) to provide data for further studies on its efficiency in upgrading biogas by Pressure Swing Adsorption (PSA). The adsorbent was characterized, and equilibrium parameters were estimated from monocomponent CH4, CO2, and H2O equilibrium isotherms. Binary and ternary equilibrium isotherms were simulated, and the selectivity and adsorption capacity of the CAC 8X30 were calculated in dry and wet conditions and then compared with zeolite 13X as a reference material. Regarding characterization, Nitrogen and Hydrogen Physisorption results indicated that 94 % of the pore volume is concentrated in the region of micropores. The adsorption affinity with CAC 8X30 estimated from monocomponent isotherms was in the order KH20>KCO2>KCH4. IAST-Langmuir model simulations presented good agreement with experimental binary equilibrium data. Further simulations indicated equilibrium selectivity for CO2 over CH4 (e.g., 4.7 at 1 bar and 298 K for a mixture of CH4/CO2, 60/40 vol%), which increased in the presence of moisture, indicating its suitability for upgrading humid biogas. Simulations for zeolite 13X suggested that the material is unsuitable in the presence of water vapor but presents higher selectivity than the CAC 8X30 in dry conditions. Hence, the integration of both materials might be helpful for biogas upgrading.

Systematic studies of tannin-formaldehyde aerogels: preparation and properties.

Gelation of tannin-formaldehyde (TF) solutions was systematically investigated by changing pH and concentration of TF resin in water. In this way we constructed the TF phase diagram, from which chemical hydrogels could be described, and also synthesized thermoreversible tannin-based hydrogels. Conditions of non-gelation were also determined. Hydrogels were dried in supercritical CO2, leading to a broad range of TF aerogels. The latter were investigated for volume shrinkage, total porosity, micro-, meso- and macropore volumes, Brunauer-Emmett-Teller (BET) surface area, microscopic texture, mechanical and thermal properties. All these properties are discussed in relation to each other, leading to an accurate and self-consistent description of these bioresource-based highly porous materials. The conditions for obtaining the highest BET surface area or mesopore volume were determined and explained in relation to the preparation conditions. The highest BET surface area, 880 m2 g-1, is remarkably high for organic aerogels derived from a natural resource.

Towards a surface metric to measure the dustiness of nanomaterial powders.

The relevance of dustiness methods is increasingly recognized in the preliminary exposure evaluation of workers handling nanomaterials in powder form, and should also be transposed to the assessment of environmental risk in the future. The methods currently recommended in the European standards are mainly based on determining a mass-based dustiness index [mg kg-1], whereas surface area is regularly put forward as a more appropriate determinant to assess the pulmonary toxicity of nanoparticles. In this study, we describe an operational methodology leading us to propose a surface metric to determine the dustiness index [m2 kg-1] of nanoparticulate matter. To this end, we demonstrate the equivalence between the external specific surface area of a nanopowder and that of its aerosol with five nanomaterials produced and used on an industrial scale, and covering a range of external specific surface areas from 35 to 230 m2 g-1. Compared to the conventional mass-based dustiness index, the surface-based dustiness index (1) is more discriminating, covering an additional order of magnitude, and (2) has an impact on the powder ranking with potential consequences on the preventive measures to be implemented. Finally, our proposal has the potential to be included in future revisions of European standards for workplace exposure and dustiness measurement, provided that further experimental results on surface-based dustiness indices support these preliminary data.

Influence of Anatomy, Microstructure, and Composition of Natural Fibers on the Performance of Thermal Insulation Panels.

The growing interest in environmentally friendly materials is leading to a re-evaluation of natural fibers for industrial applications in order to meet sustainability and low-cost objectives, especially for thermal insulation of buildings. This paper deals with the chemical and physical characterization of fibers extracted from seagrass (Posidonia oceanica) and alfa grass (Stipa tenacissima) for a possible substitution of synthetic materials for thermal insulation. Hemp (Cannabis sativa), a fiber broadly used, was also studied for comparison. The parameters characterized include porosity, thermal degradation, elemental composition, skeletal and particle density of the fibers as well as investigation of the thermal conductivity of fiber-based panels. Several technologies were involved in investigating these parameters, including mercury intrusion, thermogravimetric analysis, fluorescence spectroscopy, and fluid pycnometry. The fibers showed a degradation temperature between 316 and 340 °C for Posidonia, between 292 and 326 °C for alfa, and between 300 and 336 °C for hemp fibers. A high porosity allied with a reduced pore size was revealed for Posidonia (77%, 0.54 µm) compared to hemp (75%, 0.61 µm) and alfa (57%, 2.1 µm) raw fibers, leading to lower thermal conductivity values for the nonwoven panels based on Posidonia (0.0356-0.0392 W/m.K) compared to alfa (0.0365-0.0397 W/m.K) and hemp (0.0387-0.0427 W/m.K). Bulk density, operating temperature, and humidity conditions have been shown to be determining factors for the thermal performance of the panels.

Piezoelectric Nanogenerators Based On BaTiO3/PDMS Composites for High-Frequency Applications.

A series of highly flexible and environmentally friendly composites based on polydimethylsiloxane (PDMS) filled with 200 nm size ferroelectric BaTiO3 (BTO) particles at different concentrations (from 7 to 23 vol %) have been fabricated by a simple dispersion method. The dielectric, piezoelectric, and ultrasonic properties have been studied. The ferroelectric state of BTO was confirmed by differential scanning calorimetry and ultrasonic spectroscopy. The addition of BTO into PDMS strongly affects the dielectric properties of the composites. At low temperatures close to 160 K, the PDMS matrix exhibits a dielectric anomaly related to a dynamic glass transition, which shifts to higher temperatures as the BTO content increases due to the strong interaction between polymer chains and nanoparticles. Ultrasonic measurements demonstrate the appearance of a piezoelectric voltage signal on a thin plate of the composite with the highest available filler concentration (23 vol %) under longitudinal stress applied by a 10 MHz ultrasonic wave. As a result, at room temperature, the detected signal is characterized by output voltage and specific stored energy values of 10 mV and 367.3 MeV/m2, respectively, followed by a further increase with cooling to 35 mV at 150 K. The proposed BTO/PDMS composite system is thus a potential candidate for nanogenerators, namely, a simple, flexible, and lead-free device converting high-frequency (10 MHz) mechanical vibrations into electrical voltage.

Cytotoxicity and genotoxicity of nanosized and microsized titanium dioxide and iron oxide particles in Syrian hamster embryo cells.

Potential differences in the toxicological properties of nanosized and non-nanosized particles have been notably pointed out for titanium dioxide (TiO(2)) particles, which are currently widely produced and used in many industrial areas. Nanoparticles of the iron oxides magnetite (Fe(3)O(4)) and hematite (Fe(2)O(3)) also have many industrial applications but their toxicological properties are less documented than those of TiO(2). In the present study, the in vitro cytotoxicity and genotoxicity of commercially available nanosized and microsized anatase TiO(2), rutile TiO(2), Fe(3)O(4), and Fe(2)O(3) particles were compared in Syrian hamster embryo (SHE) cells. Samples were characterized for chemical composition, primary particle size, crystal phase, shape, and specific surface area. In acellular assays, TiO(2) and iron oxide particles were able to generate reactive oxygen species (ROS). At the same mass dose, all nanoparticles produced higher levels of ROS than their microsized counterparts. Measurement of particle size in the SHE culture medium showed that primary nanoparticles and microparticles are present in the form of micrometric agglomerates of highly poly-dispersed size. Uptake of primary particles and agglomerates by SHE exposed for 24 h was observed for all samples. TiO(2) samples were found to be more cytotoxic than iron oxide samples. Concerning primary size effects, anatase TiO(2), rutile TiO(2), and Fe(2)O(3) nanoparticles induced higher cytotoxicity than their microsized counterparts after 72 h of exposure. Over this treatment time, anatase TiO(2) and Fe(2)O(3) nanoparticles also produced more intracellular ROS compared to the microsized particles. However, similar levels of DNA damage were observed in the comet assay after 24 h of exposure to anatase nanoparticles and microparticles. Rutile microparticles were found to induce more DNA damage than the nanosized particles. However, no significant increase in DNA damage was detected from nanosized and microsized iron oxides. None of the samples tested showed significant induction of micronuclei formation after 24 h of exposure. In agreement with previous size-comparison studies, we suggest that in vitro cytotoxicity and genotoxicity induced by metal oxide nanoparticles are not always higher than those induced by their bulk counterparts.

A Review of Rigid Polymeric Cellular Foams and Their Greener Tannin-Based Alternatives.

This review focuses on the description of the main processes and materials used for the formulation of rigid polymer foams. Polyurethanes and their derivatives, as well as phenolic systems, are described, and their main components, foaming routes, end of life, and recycling are considered. Due to environmental concerns and the need to find bio-based alternatives for these products, special attention is given to a recent class of polymeric foams: tannin-based foams. In addition to their formulation and foaming procedures, their main structural, thermal, mechanical, and fire resistance properties are described in detail, with emphasis on their advanced applications and recycling routes. These systems have been shown to possess very interesting properties that allow them to be considered as potential substitutes for non-renewable rigid polymeric cellular foams.

Electrical Resistivity and Microwave Properties of Carbon Fiber Felt Composites.

We present studies on the microwave properties, electrical resistivity, and low-frequency (10 Hz-20 kHz) noise characteristics in the temperature range of 78 K to 380 K of composite materials made from bisphenol A-based epoxy resin and carbon fiber felts. Two types of carbon fibers were used, derived from polyacrylonitrile or regenerated cellulose. We show that these structures are suitable for electromagnetic shielding applications, especially in the direction parallel to the carbon fibers. The low-frequency voltage fluctuations observed in these materials are of the 1/fα, and the noise intensity is proportional to the square of the voltage. The characteristics of the investigated materials show an instability in the temperature range from 307 K to 332 K. This effect is followed by an increase in resistivity and noise intensity, but it does not change the character of the noise, and this instability vanishes after a few repeated heating and cooling cycles.

Irreversible deformation of hyper-crosslinked polymers after hydrogen adsorption.

Hyper-crosslinked polymers (HCPs) have been produced by the Friedel-Crafts reaction using anthracene, benzene, carbazole or dibenzothiophene as precursors and dimethoxymethane as crosslinker, and the effect of graphene oxide (GO) addition has been studied. The resulting HCPs were highly microporous with BET areas (ABET) between 590 and 1120 m2g-1. The benzene-derived HCP (B1FeM2) and the corresponding composite with GO (B1FM2-GO) exhibited the highest ABET and were selected to study their hydrogen adsorption capacities in the pressure range of 0.1 - 14 MPa at 77 K. The maximum H2 excess uptake was 2.1 and 2.0 wt% for B1FeM2 and B1FeM2-GO, respectively, at 4 MPa and 77 K. The addition of GO reduced the specific surface area but increased the density of the resultant HCP-GO composites, which is beneficial for practical applications and proves that materials giving higher gravimetric storage capacities are not necessarily those that offer higher volumetric capacities. H2 adsorption-desorption cycles up to 14 MPa showed irreversible deformation of both HCP and HCP-GO materials, which calls into question their application for hydrogen adsorption at pressures above 4 MPa.

Bimodal activated carbons derived from resorcinol-formaldehyde cryogels.

Resorcinol-formaldehyde cryogels prepared at different dilution ratios have been activated with phosphoric acid at 450 °C and compared with their carbonaceous counterparts obtained by pyrolysis at 900 °C. Whereas the latter were, as expected, highly mesoporous carbons, the former cryogels had very different pore textures. Highly diluted cryogels allowed preparation of microporous materials with high surface areas, but activation of initially dense cryogels led to almost non-porous carbons, with much lower surface areas than those obtained by pyrolysis. The optimal acid concentration for activation, corresponding to stoichiometry between molecules of acid and hydroxyl groups, was 2 M l-1, and the acid-cryogel contact time also had an optimal value. Such optimization allowed us to achieve surface areas and micropore volumes among the highest ever obtained by activation with H3PO4, close to 2200 m2 g-1 and 0.7 cm3 g-1, respectively. Activation of diluted cryogels with a lower acid concentration of 1.2 M l-1 led to authentic bimodal activated carbons, having a surface area as high as 1780 m2 g-1 and 0.6 cm3 g-1 of microporous volume easily accessible through a widely developed macroporosity.

Biopolymer-based nanocomposites: effect of lignin acetylation in cellulose triacetate films.

We have prepared all-biopolymer nanocomposite films using lignin as a filler and cellulose triacetate (CTA) as a polymer matrix, and characterized them by several analytical methods. Three types of lignin were tested: organosolv, hydrolytic and kraft, with or without acetylation. They were used in the form of nanoparticles incorporated at 1 wt% in CTA. Self-supported films were prepared by vapor-induced phase separation at controlled temperature (35-55 °C) and relative humidity (10-70%). The efficiency of acetylation of each type of lignin was studied and discussed, as well as its effects on film structure, homogeneity and mechanical properties. The obtained results are explained in terms of intermolecular filler-matrix interaction at the nanometer scale, for which the highest mechanical resistance was reached using hydrolytic lignin in the nanocomposite.

An Evaluation of the Impact of the Amount of Potassium Hydroxide on the Porous Structure Development of Activated Carbons.

This paper presents the results of an evaluation of the impact of the amount of potassium hydroxide on the obtained porous structure of the activated carbons derived from the shells of pistachios, hazelnuts, and pecans by carbonization and subsequent chemical activation with potassium hydroxide by different adsorption methods: Brunauer-Emmett-Teller, Dubinin-Raduskevich, the new numerical clustering-based adsorption analysis, Quenched Solid Density Functional Theory, and 2D-Non-linear Density Functional Theory for Heterogeneous Surfaces, applied to nitrogen adsorption isotherms at -196 °C. Based on the conducted research, a significant potential for the production of activated carbons from waste materials, such as nut shells, has been demonstrated. All the activated carbons obtained in the present study at the activator/char mass ratio R = 4 exhibited the most developed porous structure, and thus very good adsorption properties. However, activated carbons obtained from pecan shells deserve special attention, as they were characterized by the most homogeneous surface among all the samples analyzed, i.e., by a very desirable feature in most adsorption processes. The paper demonstrates the necessity of using different methods to analyze the porous structure of activated carbons in order to obtain a complete picture of the studied texture. This is because only a full spectrum of information allows for correctly selecting the appropriate technology and conditions for the production of activated carbons dedicated to specific industrial applications. As shown in this work, relying only on the simplest methods of adsorption isotherm analysis can lead to erroneous conclusions due to lack of complete information on the analyzed porous structure. This work thus also explains how and why the usual characterizations of the porous structure of activated carbons derived from lignocellulosic biomass should not be taken at face value. On the contrary, it is advisable to cross reference several models to get a precise idea of the adsorbent properties of these materials, and therefore to propose the most suitable production technology, as well as the conditions of the preparation process.

Mechanical and Thermal Behavior of Fibrous Carbon Materials.

The ability of various commercial fibrous carbon materials to withstand stress and conduct heat has been evaluated through experimental and analytical studies. The combined effects of different micro/macro-structural characteristics were discussed and compared. Large differences in mechanical behavior were observed between the different groups or subgroups of fibrous materials, due to the different types of fibers and the mechanical and/or chemical bonds between them. The application of the Mooney-Rivlin model made it possible to determine the elastic modulus of soft felts, with a few exceptions, which were studied in-depth. The possible use of two different mechanical test methods allowed a comparison of the results in terms of elastic modulus obtained under different deformation regimes. The effective thermal conductivity of the same fibrous materials was also studied and found to be much lower than that of a single carbon fiber due to the high porosity, and varied with the bulk density and the fiber organization involving more or less thermal contact resistances. The thermal conductivity of most materials is highly anisotropic, with higher values in the direction of preferential fiber orientation. Finally, the combination of compression and transient thermal conductivity measurement techniques allowed the heat conduction properties of the commercial fibrous carbons to be investigated experimentally when compressed. It was observed that thermal conductivity is strongly affected under compression, especially perpendicular to the main fiber orientation.

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.