Search Results (94)

Calcium phosphate–poly(methyl-methacrylate) composite layers have been synthetized on silicon substrates in magnetron sputtering discharge by adjusting the radio-frequency power. The electron energy distribution function measured at holder substrate position shifts to lower energies when the radio-frequency power applied to the magnetron source increases from 50 to 150 W and the poly(methyl-methacrylate) molecule dissociation is augmented. The optical emission spectral analysis indicated the dynamics of the excitation and ionization processes in the Ar–calcium phosphate–poly(methyl-methacrylate) plasma mixture, as well as the dissociation patterning of the polymer molecules. The Ca I, P I, and H_α atomic lines and CaO, PO, POH, CO, CH and C₂ molecular bands characteristic to the calcium phosphate and poly(methyl-methacrylate) decomposition were evidenced. At 150 W radio-frequency power a reduction in the polymer content in the composite layer volume was observed even if the α-CH₃ main chain and the C=O molecular bands are still present. More C-C/C-H, C-OH/C-O-C polymeric bonds were revealed at the layer surface, indicating the formation of plasma polymers. The Ca/P ratio changes from 1.72 to 1.9 at 50 to 150 W, respectively, maintaining the amorphous structure of the layers. In this power range, the transition of layer surface morphologies from grain-like to worm-like plasma polymer characteristics is connected to an increase in plasma ion density and layer thickness. Full article

Deicing salt effectively melts ice and snow to maintain traffic flow in seasonal freezing zones, but its erosion effect compromises the water stability and structural integrity of asphalt pavements. To comprehensively explore the impacts of salt erosion on the interfacial behaviors of rubber asphalt–aggregate systems, this study developed a multiscale characterization method integrating a macroscopic mechanical test, microscopic tests, and molecular dynamics (MD) simulations. Firstly, laboratory-controlled salt–freeze–thaw cycles were employed to simulate field conditions, followed by quantitative evaluation of interfacial bonding properties through pull-out tests. Subsequently, the atomic force microscopy (AFM) and Fourier transform infrared spectrometer (FTIR) tests were conducted to characterize the microscopic morphology evolution and chemical functional group transformations, respectively. Moreover, by combining the diffusion coefficients of water molecules, salt solution ions, and asphalt components, the mechanism of interfacial salt erosion was elucidated. The results demonstrate that increasing NaCl concentration and freeze–thaw cycles progressively reduces interfacial pull-out strength and fracture energy, with NaCl-induced damage becoming limited after twelve salt–freeze–thaw cycles. In detail, with exposure to 15 freeze–thaw cycles in 6% NaCl solution, the pull-out strength and fracture energy of the rubber asphalt–limestone aggregate decrease by 50.47% and 51.57%, respectively. At this stage, rubber asphalt exhibits 65.42% and 52.34% increases in carbonyl and sulfoxide indexes, respectively, contrasted by 49.24% and 42.5% decreases in aromatic and aliphatic indexes. Long-term exposure to salt–freeze–thaw conditions promotes phase homogenization, ultimately reducing surface roughness and causing rubber asphalt to resemble matrix asphalt morphologically. At the rubber asphalt–NaCl solution–aggregate interface, the diffusion of Na⁺ is faster than that of Cl⁻. Meanwhile, compared with other asphalt components, saturates exhibit notably enhanced mobility under salt erosion conditions. The synergistic effects of accelerated aging, salt crystallization pressure, and enhanced ionic diffusion jointly induce the deterioration of interfacial bonding, which accounts for the decrease in macroscopic pull-out strength. This multiscale investigation advances understanding of salt-induced deterioration while providing practical insights for developing durable asphalt mixtures in cold regions. Full article

In the present work, we describe the use of the potentially tridentate ligand pyridine-2-amidoxime (NH₂paoH) in Fe-Co chemistry. The 1:1:3 Fe^III(NO₃)₃·9H₂O/Co^II(ClO₄)₂·6H₂O/NH₂paoH reaction mixture in MeOH gave complex [Co^III₂Fe^III(NH₂pao)₆](ClO₄)₂(NO₃) (1) in ca. 55% yield, the cobalt(II) being oxidized to cobalt(III) under the aerobic conditions. The same complex was isolated using cobalt(II) and iron(II) sources, the oxidation now taking place at both metal sites. The structure of 1 contains two structurally similar, crystallographically independent cations [Co^III₂Fe^III(NH₂pao)₆]³⁺ which are strictly linear by symmetry. The central high-spin Fe^III ion is connected to each of the terminal low-spin Co^III ions through the oximato groups of three 2.1110 (Harris notation) NH₂pao⁻ ligands, in such a way that the six O atoms are bonded to the octahedral Fe^III center ({Fe^IIIO₆} coordination sphere). Each terminal octahedral Co^III ions is bonded to six N atoms (three oximato, three 2-pyridyl) from three NH₂pao⁻ groups ({Co^IIIN₆} coordination sphere). The IR and Raman spectra of the complex are discussed in terms of the coordination mode of the organic ligand, and the non-coordinating nature of the inorganic ClO₄⁻ and NO₃⁻ counterions. The UV/VIS spectrum of the complex in EtOH shows the two spin-allowed d-d transitions of the low-spin 3d⁶ cobalt(III) and a charge-transfer NH₂pao⁻ → Fe^III band. The δ and ΔΕ_Q ⁵⁷Fe-Mössbauer parameter of 1 at 80 K show the presence of an isolated high-spin Fe^III center. Variable-temperature (1.8 K–300 K) and variable-field (0–7 T) magnetic studies confirm the isolated character of Fe^III. A critical discussion of the importance of NH₂paoH and its anionic forms (NH₂pao⁻, NHpao²⁻) in homo- and heterometallic chemistry is also attempted. Full article

Surface nanopatterning induced by ion beam irradiation allows for the creation of patterns on large areas of a wide variety of materials. However, surface composition plays a crucial role in the process. In this study, we investigate the bombardment of a metallic alloy, specifically an Au-Cu system with different compositions, discussing differences in the formation of patterns compared to pure materials. Mixtures with compositions ranging from 35 to 65 at.% Cu exhibit a dampening effect on ripple height and depth. At intermediate angles of incidence, horizontal displacement is minimized and sputtering maximized; conversely, at grazing angles, sputtering is minimized and horizontal displacement becomes dependent on material mobility. It is, therefore, evident that sputtering determines the patterning for intermediate angles. However, an analysis of the redistribution factor as a function of the angle of incidence shows that the weight of the redistribution is much lower than that of sputtering in alloys of similar composition at grazing angles due to the amorphization process. This point is confirmed by the data on displaced atoms obtained from the relocation cross-sections. Full article

Gas evolution in lithium-ion batteries represents a pivotal yet underaddressed concern, significantly compromising long-term cyclability and safety through complex interfacial dynamics and material degradation across both normal operation and extreme thermal scenarios. While extensive research has focused on isolated gas generation mechanisms in specific components, critical knowledge gaps persist in understanding cross-component interactions and the cascading failure pathways it induced. This review systematically decouples gas generation mechanisms at cathodes (e.g., lattice oxygen-driven CO₂/CO in high-nickel layered oxides), anodes (e.g., stress-triggered solvent reduction in silicon composites), electrolytes (solvent decomposition), and auxiliary materials (binder/separator degradation), while uniquely establishing their synergistic impacts on battery stability. Distinct from prior modular analyses, we emphasize that: (1) emerging systems exhibit fundamentally different gas evolution thermodynamics compared to conventional materials, exemplified by sulfide solid electrolytes releasing H₂S/SO₂ via unique anionic redox pathways; (2) gas crosstalk between components creates compounding risks—retained gases induce electrolyte dry-out and ion transport barriers during cycling, while combustible gas–O₂ mixtures accelerate thermal runaway through chain reactions. This review proposes three key strategies to suppress gas generation: (1) oxygen lattice stabilization via dopant engineering, (2) solvent decomposition mitigation through tailored interphases engineering, and (3) gas-selective adaptive separator development. Furthermore, it establishes a multiscale design framework spanning atomic defect control to pack-level thermal management, providing actionable guidelines for battery engineering. By correlating early gas detection metrics with degradation patterns, the work enables predictive safety systems and standardized protocols, directly guiding the development of reliable high-energy batteries for electric vehicles and grid storage. Full article

Aspergillus spp. and their produced aflatoxins are responsible for contaminating 25–30% of the global food supply, including many grains, and nuts which when consumed are detrimental to human and animal health. Despite regulatory frameworks, Aspergillus spp. and aflatoxin contamination is still a global challenge, especially in cereal-based matrices and their derived by-products. The methods for reducing Aspergillus spp. and aflatoxin contamination involve various approaches, including physical, chemical, and biological control strategies. Recently, a novel technology, atmospheric cold plasma (ACP), has emerged which can reduce mold populations and also degrade these toxins. ACP is a non-thermal technology that operates at room temperature and atmospheric pressure. It can reduce mold and toxins from grains and seeds without affecting food quality or leaving any chemical residue. ACP is the conversion of a gas, such as air, into a reactive gas. Specifically, an electrical charge is applied to the “working” gas (air) leading to the breakdown of diatomic oxygen, diatomic nitrogen, and water vapor into a mixture of radicals (e.g., atomic oxygen, atomic nitrogen, atomic hydrogen, hydroxyls), metastable species, and ions (e.g., nitrate, nitrite, peroxynitrate). In a cold plasma process, approximately 5% or less of the working gas is ionized. However, cold plasma treatment can generate over 1000 ppm of reactive gas species (RGS). The final result is a range of bactericidal and fungicidal molecules such as ozone, peroxides, nitrates, and many others. This review provides an overview of the mechanisms and chemistry of ACP and its application in inactivating Aspergillus spp. and degrading aflatoxins, serving as a novel treatment to enhance the safety and quality of grains and nuts. The final section of the review discusses the commercialization status of ACP treatment. Full article

In this study, three dinuclear copper(II) complexes of ligand 2,6-bis[(N-methyl-piperazine-1-yl)methyl]-4-formyl phenol (L1) and one of 2,6-bis[(N-methylpiperazine-1-yl)methyl]-4-formyl phenol dimethylacetal (L2) with copper(II) ions have been investigated as new types of biomimetic catalysts for the oxidative transformation of different aminophenols and phenyldiamines. All the complexes of interest were newly synthesized and further characterized by IR spectroscopy, UV-Vis and mass spectrometry, X-ray diffraction, and selected electrochemical measurements. Crystal structures of these dinuclear copper(II) complexes have revealed that the coordination-shell geometry of copper atoms is close to a tetragonal pyramid. Catecholase, phenoxazinone synthase, and horseradish peroxidase-like activities were observed in pure methanol and water–methanol mixtures in the presence of molecular oxygen. The potential applicability of the complexes under study is discussed with respect to their possibilities and limitations in the replacement of natural copper-containing oxidoreductases in the oxidative degradation of water-insoluble chlorinated aminophenols in the dye industry or in the production of phenoxazine-based drugs. Full article

Reactions of 2,2′-bipyridine-6,6′-dicarbonyl-bis(N,N-diethylthiourea), H₂L^bipy, with a mixture of thorium nitrate hydrate and nickel acetate hydrate in methanol with NEt₃ as a supporting base yield brown single crystals of the bimetallic complex [ThNi(L^bipy)₂(CH₃COO)₂(MeOH)]. Two 2,2′-bipyridine-centered bis(aroylthioureato) ligands connect the metal atoms in a way that the thorium atom is coordinated by two O,N,N,O donor atom sets, while the nickel atom establishes two S,O chelate rings in its equatorial coordination plane. The metal atoms are connected by a bridging acetato ligand, and their coordination spheres are completed by one methanol ligand (nickel) and a monodentate acetato ligand (thorium). A distorted octahedral coordination environment is established around the Ni²⁺ ion, while the Th⁴⁺ ion is in first approximation a 10-coordinate with a diffusely defined coordination polyhedron. Full article

2,8-Dithia-5-aza-2,6-pyridinophane (L1) has been used as a receptor unit in the construction of the conjugated redox chemosensor 5-ferrocenylmethyl-2,8-dithia-5-aza-2,6-pyridinophane (L3). In order to further explore the coordination chemistry of L1, and comparatively, that of its structural analogue 2,11-dithia-5,8-diaza-2,6-pyridinophane (L2), featuring two secondary nitrogen atoms in the macrocyclic unit, the crystal structures of the new synthesised complexes [Pb(L1)(ClO₄)₂]·½CH₃CN, [Cu(L2)](ClO₄)₂·CH₃CN and [Cd(L2)(NO₃)]NO₃ were determined by X-ray diffraction analysis. The electrochemical response of L3 towards the metal ions Cu²⁺, Zn²⁺, Cd²⁺, Hg²⁺, and Pb²⁺ was investigated by cyclic voltammetry (CV) in CH₂Cl₂/CH₃CN 0.25:1 (v/v) mixture. Upon addition to L3 of increasing amounts of the aforementioned metal cations, the wave corresponding to the Fc⁺/Fc redox couple of the un-complexed L3 was gradually replaced by a new reversible wave at more positive potentials and corresponding to the Fc⁺/Fc redox couple of the complexed ligand. The maximum anodic shift of the ferrocene oxidation wave is observed in the presence of Pb²⁺ (230 mV), to which corresponds a reaction coupling efficiency (RCE) value as large as 7.9 × 10³. The response selectivity of L3 is discussed in reference to the optical selectivity observed for conjugated chemosensors featuring L1 as receptor unit and different fluorogenic fragments as signalling units. Full article

In this work, within the framework of a self-consistent model of arc discharge, a simulation of plasma parameters in a mixture of argon and methane was carried out, taking into account the evaporation of the electrode material in the case of a refractory and non-refractory cathode. It is shown that in the case of a refractory tungsten cathode, almost the same methane conversion rate is observed, leading to similar values in the density of the main methane conversion products (C, C₂, H) at different values of the discharge current density. However, with an increase in the current density, the evaporation rate of copper atoms from the anode increases, and a jump in the I–V characteristic is observed, caused by a change in the plasma-forming ion. This is due to the lower ionization energy of copper atoms compared to argon atoms. In this mode, an increase in metal–carbon nanoparticles is expected. It is shown that, in the case of a cathode made of non-refractory copper, the discharge characteristics and the component composition of the plasma depend on the field enhancement factor near the cathode surface. It is demonstrated that increasing the field enhancement factor leads to more efficient thermal field emission, lowering the cathode’s surface temperature and the gas temperature in the discharge gap. This leads to the fact that, in the arc discharge mode with a cathode made of non-refractory copper, the dominant types of particles from which the synthesis of a nanostructure can begin are, in descending order, copper atoms (Cu), carbon clusters (C₂), and carbon atoms (C). Full article

Microwave technology in geopolymer synthesis offers a transformative, sustainable alternative to traditional methods, enhancing material properties and production efficiency. However, the effects of microwave-induced changes on pore structure and their relationship with mechanical strength and environmental performance, such as heavy metal leachability, are not fully understood. This study investigates the impact of microwave pre-curing on geopolymers, focusing on how microwave power and duration influence their pore structure and environmental performance. A total of 48 mixtures were prepared using sodium silicate and sodium hydroxide as alkali activators, with metakaolin and fly ash as raw materials. The modulus was adjusted to 1.5, and the liquid-to-solid ratio was set at 1.6 for metakaolin and 0.7 for fly ash. Microwave irradiation power settings of 100 W, 300 W, 440 W, 600 W, and 800 W were tested. The heating times ranged from 30 s to 90 s at intervals of 15 s. Our findings reveal that optimal microwave settings (100 watts for 45 s) can significantly enhance mechanical properties, with compressive strengths reaching 15.9 MPa for fly ash-based and 9.094 MPa for metakaolin-based geopolymers. However, excessive microwave energy leads to increased porosity, with adverse effects on structural integrity. Moreover, microwave pre-curing effectively reduces heavy metal leachability. Chromium (III) was used in leaching tests and it was demonstrated that ion concentrations as low as 0.097 mg/L enhance environmental safety. Advanced techniques like Fourier-transform infrared spectroscopy (FT-IR), X-ray diffraction (XRD) and X-ray CT were applied for the analysis of the atomic bonding, phases and pore structure of the studied geopolymers along with their ability to withstand compression (MPa). Chromium (III) was encapsulated and its leached concentration was measured by ICP-MS to evaluate the performance of the synthesized geopolymers. These results underscore the need for precise control over microwave irradiation parameters to maximize the benefits while mitigating negative impacts. This study provides valuable insights into the controlled use of microwave technology for geopolymer synthesis, recommending optimal irradiation conditions for improved performance and sustainability and advancing sustainable construction materials. The developed geopolymers show promise for applications in construction, waste stabilization, and heavy metal immobilization, contributing to more sustainable and environmentally friendly materials in these industries. Full article

The production of olive oils implies the generation of high quantities of solid residues and/or wastewater that may have a great impact on terrestrial and aquatic environments because of their phytotoxicity. Alperujo is a combination of liquid and solid waste from olive oil processing. Few studies are known that show their high biological potential. Indeed, wastes remaining after the production of olive oil are a heterogeneous mixture of many chemical components, such as metal ions, carbohydrates, and polyphenols, that may exert different biological activities, primarily acting as antioxidants. The samples of “alperujo” were obtained as waste from industries that work on olive oil production. Three ethanolic organic extracts were prepared using solvent maceration, ultrasound and reflux extraction methods. Yields of each extract were determined and evaluated for their ability to trap free radicals, using the DPPH and ABTS assays contributing to the calculation of SC₅₀ (free radical scavenging). The extracts were subjected to preliminary phytochemical testing, analyzing phenolic content by the Folin method and heavy metal concentration using atomic absorption spectrometry. The extraction method was decisive for the yield obtained, with the reflux system being highly efficient, and the antioxidant activity shows the potential of these wastes as a source of bioactive compounds of interest for possible reuse. Full article

Carbon-based electrodes have recently been most widely used in P-MFC due to their desirable properties such as biocompatibility, chemical stability, affordable price, corrosion resistance, and ease of regeneration. In general, carbon-based electrodes, particularly graphite, are produced using a complex process based on petroleum derivatives at very high temperatures. This study aims to produce electrodes from bio-pitch and charcoal powder as an alternative to graphite electrodes. The carbons used to manufacture the electrodes were obtained by the carbonisation of Robinia pseudoacacia and Azadirachta indica wood. These carbons were pulverised, sieved to 50 µm, and used as the raw materials for electrode manufacturing. The binder used was bio-pitch derived from coconut shells as the raw materials. The density and coking value of the bio-pitch revealed its potential as a good alternative to coal-tar pitch for electrode manufacturing. The electrodes were made by mixing 66.50% of each carbon powder and 33.50% of bio-pitch. The resulting mixture was moulded into a cylindrical tube 8 mm in diameter and 80 mm in length. The raw electrodes obtained were subjected to heat treatment at 800 °C or 1000 °C in an inert medium. The electrical resistivity obtained by the four-point method showed that N1000 has an electrical resistivity at least five times lower than all the electrodes developed and two times higher than that of G. Fourier-transform infrared spectroscopy (FTIR) was used to determine the compositional features of the samples and their surface roughness was characterised by atomic force microscopy (AFM). Charge transfer was determined by electrical impedance spectroscopy (EIS). The FTIR of the electrodes showed that N1000 has a spectrum that is more similar to that of G compared to the others. The EIS showed the high ionic mobility of the ions and therefore that N1000 has a higher charge transfer compared to G and the others. AFM analysis revealed that N1000 had the highest surface roughness in this study. Full article

The presented research is the seed of a vision for the development of a waste-for-product strategy. Following this concept, various synthetic solutions containing low concentrations of platinum group metals were used to model their recovery and to produce catalysts. This is also the first report that shows the method for synthesis of a pyramid-like structure deposited on activated carbon composed of Pd and Pt. This unique structure was obtained from a mixture of highly diluted aqueous solutions containing both metals and chloride ions. The presence of functional groups on the carbon surface and experimental conditions allowed for: the adsorption of metal complexes, their reduction to metal atoms and enabled further hierarchical growth of the metal layer on the carbon surface. During experiments, spherical palladium and platinum nanoparticles were obtained. The addition of chloride ions to the solution promoted the hierarchical growth and formation of palladium nanopyramids, which were enriched with platinum nanoparticles. The obtained materials were characterized using UV–Vis, Raman, IR spectroscopy, TGA, SEM/EDS, and XRD techniques. Moreover, Pd@ROY, Pt@ROY, and Pd-Pt@ROY were tested as possible electrocatalysts for hydrogen evolution reactions. Full article

Dye-sensitized solar cells with synthesized phenothiazine derivative 3,7′-bis(2-cyano-1-acrylic acid)-10-ethyl-phenothiazine (PTZ) and commercial di-tetrabutylammonium cis-bis(isothiocyanato)bis(2,2′-bipyridyl-4,4′-dicarboxylato)ruthenium(II) (N719) dyes were fabricated and characterized based on current–voltage measurements. The effect of the utilization of individual dyes and its mixture, chenodeoxycholic acid as co-adsorbent addition, replacement of I⁻/I₃⁻ by Co^2+/3+ ions in electrolyte and platinum by semiconducting polymer mixture poly(3,4-ethylenedioxythiophene) polystyrene sulfonate in counter electrode was studied. Additionally, the effect of polymer thickness on the photovoltaic performance of the device was evaluated. Prepared photoanodes were characterized by UV–Vis spectroscopy and atomic force microscopy. The further modification of DSSCs involving the fabrication of tandem solar cells was carried out. The higher power conversion efficiency 7.60% exhibited tandem photovoltaic cell sensitized with dyes mixture containing co-adsorbent, I⁻/I₃⁻ ions in the electrolyte, and platinum in the electrode. Full article