Laser-Induced Reactions of 4-Aminobenzenthiol Species Adsorbed on Ag, Au, and Cu Plasmonic Structures Followed by SERS Spectroscopy. The Role of Substrate and Excitation Energy - Surface-Complex Photochemistry and Plasmonic Catalysis.

This study focuses on investigating the laser-induced reactions of various surface complexes of 4-aminobenzenethiol on Ag, Au, and Cu surfaces. By utilizing different excitation wavelengths, the distinct behavior of the molecule species on the plasmonic substrates was observed. Density functional theory (DFT) calculations were employed to establish the significant role of chemical enhancement mechanisms in determining the observed behavior. The interaction between 4-aminobenzenethiol (4-ABT) molecules and plasmonic surfaces led to the formation of surface complexes with absorption bands red-shifted into the visible and near-infrared regions. Photochemical transformations were induced by excitation wavelengths from these regions, with the nature of the transformations varying based on the excitation wavelength and the plasmonic metal. Resonance with the electronic absorption transitions of these complexes amplifies surface-enhanced Raman scattering (SERS), enabling the detailed examination of ongoing processes. A kinetic study on the Ag surface revealed processes governed by both first- and second-order kinetics, attributed to the dimerization process and transformation processes of individual molecules interacting with photons or plasmons. The behavior of the molecules was found to be primarily determined by the position and variability of the band between 1170 and 1190 cm-1, with the former corresponding to molecules in the monomer state and the latter to dimerized molecules. Notably, laser-induced dimerization occurred most rapidly on the Cu surface, followed by Ag, and least on Au. These findings highlight the influence of plasmonic surfaces on molecular behavior and provide insights into the potential applications of laser-induced reactions for surface analysis and manipulation.

Ultra-High Molecular Weight Polyethylene Modifications Produced by Carbon Nanotubes and Fe2O3 Nanoparticles.

Thin sheets of ultra-high molecular weight polyethylene (UHMWPE), both in pristine form and containing carbon nanotubes (CNTs) or Fe2O3 nanoparticles (NPs) at different concentrations, were prepared. The CNT and Fe2O3 NP weight percentages used ranged from 0.01% to 1%. The presence of CNTs and Fe2O3 NPs in UHMWPE was confirmed by transmission and scanning electron microscopy and by energy dispersive X-ray spectroscopy analysis (EDS). The effects of the embedded nanostructures on the UHMWPE samples were studied using attenuated total reflectance Fourier transform infrared (ATR-FTIR) spectroscopy and UV-Vis absorption spectroscopy. The ATR-FTIR spectra show the characteristic features of the UHMWPE, CNTs, and Fe2O3. Concerning the optical properties, regardless of the type of embedded nanostructures, an increase in the optical absorption was observed. The allowed direct optical energy gap value was determined from the optical absorption spectra: in both cases, it decreases with increasing CNT or Fe2O3 NP concentrations. The obtained results will be presented and discussed.

Overview of Polyethylene Terephthalate Foils Patterned Using 10 MeV Carbon Ions for Realization of Micromembranes.

Polymer membranes are conventionally prepared using high-energy particles from radioactive decay or by the bombardment of hundreds of MeVs energy ions. In both circumstances, tracks of damage are produced by particles/ions passing through the polymer, and successively, the damaged material is removed by chemical etching to create narrow pores. This process ensures nanosized pore diameter but with random placement, leading to non-uniform local pore density and low membrane porosity, which is necessary to reduce the risk of their overlapping. The present study is focused on the use of polyethylene terephthalate (PET) foils irradiated by 10.0 MeV carbon ions, easily achievable with ordinary ion accelerators. The ion irradiation conditions and the chemical etching conditions were monitored to obtain customized pore locations without pore overlapping in PET. The quality, shape, and size of the pores generated in the micromembranes can have a large impact on their applicability. In this view, the Scanning Transmission Ion Microscopy coupled with a computer code created in our laboratory was implemented to acquire new visual and quantitative insights on fabricated membranes.

Universal Capacitance Boost-Smart Surface Nanoengineering by Zwitterionic Molecules for 2D MXene Supercapacitor.

Two-dimensional nanomaterials, as one of the most widely used substrates for energy storage devices, have achieved great success in terms of the overall capacity. Despite the extensive research effort dedicated to this field, there are still major challenges concerning capacitance modulation and stability of the 2D materials that need to be overcome. Doping of the crystal structures, pillaring methods and 3D structuring of electrodes have been proposed to improve the material properties. However, these strategies are usually accompanied by a significant increase in the cost of the entire material preparation process and also a lack of the versatility for modification of the various types of the chemical structures. Hence in this work, versatile, cheap, and environmentally friendly method for the enhancement of the electrochemical parameter of various MXene-based supercapacitors (Ti3 C2 , Nb2 C, and V2 C), coated with functional and charged organic molecules (zwitterions-ZW) is introduced. The MXene-organic hybrid strategy significantly increases the ionic absorption (capacitance boost) and also forms a passivation layer on the oxidation-prone surface of the MXene through the covalent bonds. Therefore, this work demonstrates a new, cost-effective, and versatile approach (MXene-organic hybrid strategy) for the design and fabrication of hybrid MXene-base electrode materials for energy storage/conversion systems.

Microstructural Characteristics of Al-Ti-B Inoculation Wires and Their Addition to the AlSi7Mg0.3 Alloy.

Commercially supplied inoculation wires have a guaranteed chemical composition but not the size and distribution of individual phases, which are very important for nucleation. Therefore, two commercial alloys used for the inoculation of Al-Si alloys (AlTi3B1 and AlTi5B1) are investigated in this paper. The emphasis is placed on their structural analysis and the size and distribution of individual intermetallic phases. Furthermore, the grain refinement effect will be tested by adding these alloys to the AlSi7Mg0.3 alloy and testing the optimal amount of added inoculation wires. The results showed that the size and distribution of the individual phases in AlTi3B1 and AlTi5B1 meet the requirements for the successful inoculation of aluminum alloys, the intermetallic phases based on the TiAl3 phase are fine enough, and there is no agglomeration that would reduce the number of nuclei. This assumption was confirmed by adding these inoculants to the AlSi7Mg0.3 alloy, and it was found that the most ideal amount of inoculants added is 0.01 wt % when the structure was refined by approximately 32%.

Compositional and Structural Modifications by Ion Beam in Graphene Oxide for Radiation Detection Studies.

In the present study, graphene oxide foils 10 µm thick have been irradiated in vacuum using same charge state (one charge state) ions, such as protons, helium and oxygen ions, at the same energies (3 MeV) and fluences (from 5 × 1011 ion/cm2 to 5 × 1014 ion/cm2). The structural changes generated by the ion energy deposition and investigated by X-ray diffraction have suggested the generation of new phases, as reduced GO, GO quantum dots and graphitic nanofibers, carbon nanotubes, amorphous carbon and stacked-cup carbon nanofibers. Further analyses, based on Rutherford Backscattering Spectrometry and Elastic Recoil Detection Analysis, have indicated a reduction of GO connected to the atomic number of implanted ions. The morphological changes in the ion irradiated GO foils have been monitored by Transmission Electron, Atomic Force and Scanning Electron microscopies. The present study aims to better structurally, compositionally and morphologically characterize the GO foils irradiated by different ions at the same conditions and at very low ion fluencies to validate the use of GO for radiation detection and propose it as a promising dosimeter. It has been observed that GO quantum dots are produced on the GO foil when it is irradiated by proton, helium and oxygen ions and their number increases with the atomic number of beam gaseous ion.

Heat Treatment of Aluminum Alloys with the Natural Combination of Dopants.

Aluminothermic reduction without the separation of individual metals is currently considered as a possible method for processing ferromanganese sea nodules and creating new alloys. In this study, the product of their reduction-a manganese-based polymetallic mixture-was added to pure aluminum, as a mixture of alloying elements in their natural ratios. After extrusion, two new aluminum alloys with a total percentage of metallic additives ranging from 1 to 6 percent were prepared. The possibilities of the precipitation strengthening of these aluminum alloys, especially those containing Mn, Fe, Si, Ni, and Cu, were investigated under a wide range of heat treatment conditions. After each tested combination of annealing and artificial aging temperatures, the phase composition and the microstructure changes were recorded by X-ray diffraction, optical, and scanning electron microscopy with EDS analysis. Under none of the tested heat treatment conditions is a significant hardening effect observed, even though the precipitate phases are observed by TEM. However, the changes in the morphology of the present intermetallic phases caused by the heat treatment are revealed, which highlights the further possible development of these multicomponent alloys.

Annealing Response of Additively Manufactured High-Strength 1.2709 Maraging Steel Depending on Elevated Temperatures.

The present work describes the influence of different temperatures on mechanical properties and microstructure of additively manufactured high-strength 1.2709 maraging steel. For this purpose, samples produced by selective laser melting technology were used in their as-printed as well as their heat-treated state. Both samples were than exposed to temperatures ranging between 100 °C to 900 °C with a total dwell time of 2 h followed by water-cooling. The microhardness of the as-printed material reached its maximum (561 ± 6 HV0.1) at 500 °C, which corresponded to the microstructural changes. However, the heat-treated material retained its initial mechanical properties up to 500 °C. As the temperature increased, the microhardness of both the materials reduced, reaching their minimum at 900 °C. This phenomenon was accompanied by a change in the microstructure by forming coarse-grained martensite. This also resulted in a significant decrease in the ultimate tensile strength and an increase in the plasticity. TEM analysis confirmed the formation of Ni3Mo intermetallic phases in the as-printed material when exposed to a temperature of 500 °C. It was found that the same phase was present in the heat-treated sample and it remained stable up to a temperature of 500 °C.

Microstructure and Mechanical Properties of Ti-25Nb-4Ta-8Sn Alloy Prepared by Spark Plasma Sintering.

As the commercially most-used Ti-6Al-4V alloy has a different modulus of elasticity compared to the modulus of elasticity of bone and contains allergenic elements, ß-Ti alloy could be a suitable substitution in orthopedics. The spark plasma sintering (SPS) method is feasible for the preparation of materials, with very low porosity and fine-grained structure, leading to higher mechanical properties. In this study, we prepared quaternary Ti-25Nb-4Ta-8Sn alloy using the spark plasma sintering method. The material was also heat-treated in order to homogenize the structure and compare the microstructure and properties in as-sintered and annealed states. The SPS sample had a modulus of elasticity of about 63 ± 1 GPa, which, after annealing, increased to the value of 73 ± 1 GPa. The tensile yield strength (TYS) of the SPS sample was 730 ± 52 MPa, ultimate tensile strength (UTS) 764 ± 10 MPa, and ductility 22 ± 9%. Annealed samples reached higher values of TYS and UTS (831 ± 60 MPa and 954 ± 48 MPa), but the ductility decreased to the value of 3 ± 1%. The obtained results are discussed considering the observed microstructure of the alloy.

Nanostructural synergism as MnNC channels in manganese (IV) oxide and fluffy g-C3N4 layered composite with exceptional catalytic capabilities.

The avenues of catalysis and material science are always accepted and it is hoped that a state-of-the-art catalyst with exceptional intrinsic redox characteristics would be produced. This study focused on developing a multi-featured catalyst of high economical and commercial standards to meet the multi-directional applications of environmental and energy demands. Manganese (IV) oxide nanosheets made of fluffy-sheet-like g-C3N4 material were successfully synthesized by pyrolysis method. The electron-rich g-C3N4 network and semiconducting metallic oxides of MnO2 nanosheets generated high electron density interfaces within the intra-composite structure. The input of active interfaces along with strong metal-to-support interactions achieved between two parallel nanosheets in MnO2/g-C3N4 catalyst intrinsically boosted up its electrochemical and optical characteristics for it to be used in multi-catalytic fields. Successful trails of catalysts' performance have been made in three major catalytic fields with enhanced activities such as heterogeneous catalysis (reduction of nitrobenzene with rate constant of "K = 0.734 min-1" and hydrogenation of styrene with "100% conversion" efficiency, including negligible change in five consecutive cycles), photocatalysis (degradation of methylene blue dye model within 20 min with negligible change in five consecutive cycles) and electrocatalysis (oxygen reduction reactions having comparable "diffusion-limited-current density" behaviour with that of the commercial Pt/C catalyst). The enhanced performance of catalysts in transforming chemicals, degrading organic pollutant species and producing sustainable energy resources from air oxygen can mitigate the challenges faced in environmental and energy crises, respectively.

Hydrogen Embrittlement of the Additively Manufactured High-Strength X3NiCoMoTi 18-9-5 Maraging Steel.

The main aim of this study was to determine the susceptibility of the additively manufactured high strength X3NiCoMoTi 18-9-5 maraging steel to hydrogen embrittlement. For this purpose, samples produced by selective laser melting technology, before and after heat treatment, were used. The examined samples were electrochemically charged with hydrogen in NaCl + NH4SCN solution at a current density of 50 mA/cm2 for 24 h. The H content increased from about 1 to 15 ppm. Heat treatment did not affect the amount of H trapped in the maraging steel. Tensile testing revealed that the tensile strength of the H-charged samples was much lower than that of the uncharged samples. Moreover, the material became brittle after charging compared to the ductile as-printed and heat-treated samples with elongation values of 7% and 2%, respectively. The loss of plasticity was confirmed by fractography, which revealed transformation of the fracture surface morphology from dimple-like in the as-produced state to a brittle one with smooth facets in the H-charged state.

PEGylated Gold Nanoparticles Grafted with N-Acetyl-L-Cysteine for Polymer Modification.

The subjects of this work were the enhancement and determination of the stability and other properties of gold nanoparticles (AuNPs) in an aqueous solution, gold nanoparticle immobilization, and further surface grafting on polyethylene naphthalate (PEN). Gold nanoparticles in PEG with a subsequent water solution addition were prepared using cathode sputtering; for the subsequent surface activation, two different solutions were used: (i) sodium citrate dihydrate (TCD) and (ii) N-acetyl-L-cysteine (NALC). The aim of this work was to study the effect of the concentration of these solutions on AuNPs stability, and further, the effect of the concentration of gold nanoparticles and their morphology, and to describe the aging process of solutions, namely, the optical properties of samples over 28 days. Stabilized AuNPs were prepared in an N-acetyl-L-cysteine (NALC) system and subsequently immobilized with NALC. The surface chemistry modification of AuNPs was confirmed using HRTEM/EDS. Gold nanoparticles were successfully immobilized with NALC. Grafting of the modified PEN from a solution of colloidal gold stabilized in the PEG-H2O-NALC system led to the polymer surface functionalization.

Microplastic fibers influence Ag toxicity and bioaccumulation in Eisenia andrei but not in Enchytraeus crypticus.

Microplastic fibers (MF) are released from synthetic textiles during washing and end up in the wastewater. Similarly, silver nanoparticles (AgNP), incorporated in textiles as antimicrobial agents, are released in washing machines, also reaching the wastewater treatment plants. Therefore, both MF and AgNP co-exist in the environment and enter the soil compartment mainly via the application of biosolids. Yet, the combined effect of MF and AgNP has not been studied. Here, we assessed the effects of polyester MF on the toxicity of AgNP and AgNO3 to the earthworm Eisenia andrei and the enchytraeid Enchytraeus crypticus. The organisms were exposed to a range of concentration of AgNP (32, 100, 320, 1000, 3200 mg Ag/kg) and AgNO3 (12.8, 32, 80, 200, 500 mg Ag/kg) in LUFA 2.2 soil in the absence or presence of MF (0.01% DW). Reproduction tests were conducted and the toxicity outcomes compared between soils with and without MF. The exposure to MF caused a decrease in the number of juveniles and changed the biochemical composition of earthworms. Moreover, the presence of MF increased the toxicity of AgNP to earthworm reproduction (EC50 = 165 mg Ag/kg) when compared to AgNP exposure alone (EC50 = 450 mg Ag/kg), but did not alter the toxicity of AgNO3 (EC50 = 40 mg Ag/kg). For enchytraeids, no significant difference in Ag toxicity could be detected when MF was added to the soil for both AgNP and AgNO3. Overall, Ag bioaccumulation was not affected by MF, except for a decrease in earthworm body concentration at the highest Ag soil concentration (3200 mg Ag/kg). Our results suggest that the presence of MF in the soil compartment may be a cause of concern, and that the joint exposure to Ag may be deleterious depending on the Ag form, organism, and endpoint. The present work provides the first evidence that a realistic MF concentration in soil lowers AgNP concentration necessary to provoke reproductive impairment in earthworms. The influence of MF on the risk assessment of AgNP should be considered.

In vitro cellular activity of maghemite/cerium oxide magnetic nanoparticles with antioxidant properties.

Magnetic γ-Fe2O3/CeO2 nanoparticles were obtained by precipitation of Ce(NO3)3 with ammonia in the presence of γ-Fe2O3 seeds. The formation of CeO2 nanoparticles on the seeds was confirmed by transmission electron microscopy linked with selected area electron diffraction, energy-dispersive X-ray spectroscopy, electron energy loss spectroscopy, and dynamic light scattering. The γ-Fe2O3/CeO2 particle surface was functionalized with PEG-neridronate to improve the colloidal stability in PBS and biocompatibility. Chemical and in vitro biological assays proved that the nanoparticles, due to the presence of cerium oxide, effectively scavenged radicals, thus decreasing oxidative stress in the model cell line. PEG functionalization of the nanoparticles diminished their in vitro aggregation and facilitated lysosomal cargo degradation in cancer cells during autophagy, which resulted in concentration-dependent cytotoxicity of the nanoparticles. Finally, the iron oxide core allowed easy magnetic separation of the particles from liquid media and may enable monitoring of nanoparticle biodistribution in organisms using magnetic resonance imaging.

Structure and Properties of Alloys Obtained by Aluminothermic Reduction of Deep-Sea Nodules.

This paper brings an innovative processing route of manganese deep-sea nodules, which results in completely new grades of alloys. Deep-sea nodules were processed by aluminothermic method without the extraction of individual elements, producing complexly alloyed manganese-based "natural alloys". Three levels of the amount of aluminum were used for the aluminothermic reduction, and hence the alloys differ strongly in the amount of aluminum, which has a significant effect on their phase composition. The alloys have very high wear resistance, comparable with tool steel. The disadvantage of low-aluminum alloy is the susceptibility to local thermal cracking during friction, which occurs especially in the case of a dry sliding wear against the static partner with low thermal conductivity.

Creation of Gold Nanoparticles in ZnO by Ion Implantation-DFT and Experimental Studies.

Three different crystallographic orientations of the wurtzite ZnO structure (labeled as c-plane, a-plane and m-plane) were implanted with Au+ ions using various energies and fluences to form gold nanoparticles (GNPs). The ion implantation process was followed by annealing at 600 °C in an oxygen atmosphere to decrease the number of unwanted defects and improve luminescence properties. With regard to our previous publications, the paper provides a summary of theoretical and experimental results, i.e., both DFT and FLUX simulations, as well as experimental results from TEM, HRTEM, RBS, RBS/C, Raman spectroscopy and photoluminescence. From the results, it follows that in the ZnO structure, implanted gold atoms are located in random interstitial positions -experimentally, the amount of interstitial gold atoms increased with increasing ion implantation fluence. During ion implantation and subsequent annealing, the metal clusters and nanoparticles with sizes from 2 to 20 nm were formed. The crystal structure of the resulting gold was not cubic (confirmed by diffraction patterns), but it had a hexagonal close-packed (hcp) arrangement. The ion implantation of gold leads to the creation of Zn and O interstitial defects and extended defects with distinct character in various crystallographic cuts of ZnO, where significant O-sublattice disordering occurred in m-plane ZnO.

Study of Natural and Artificial Aging on AlSi9Cu3 Alloy at Different Ratios of Returnable Material in the Batch.

Aluminum alloys currently play an important role in the production of castings in various industries, where important requirements include low component weight, reduction of the environmental impact and, above all, reduction of production costs of castings. One way to achieve these goals is to use recycled aluminum alloys. The effect of natural and artificial aging of AlSi9Cu3 alloy with different ratios of returnable material in the batch was evaluated by a combination of optical, scanning, transmission microscope and mechanical tests. An increase in the returnable material in the batch above 70% resulted in failure to achieve the minimum value required by the standard for tensile strength and ductility. The application of artificial aging had a positive effect on the microstructure and thus on the mechanical properties of experimental alloys. By analyzing the results from TEM, it can be stated that in the given cases there is a reduced efficiency of θ'-Al2Cu precipitate formation with an increase of the returnable material in the batch and in comparison with artificial aging, which is manifested by low mechanical properties.

The Influence of Powder Milling on Properties of SPS Compacted FeAl.

The Fe-28 at.% Al alloy was studied in this article. The aim was to describe the influence of gas atomized powder pre-milling before SPS (Spark Plasma Sintering) sintering on the structure and properties of the bulk materials. The initial powder was milled for 0.5, 1, and 8 h. It was proven that 1 h milling leads to the change in size and morphology of the particles, B2→A2 phase transformation, and to the contamination with the material from a milling vessel. Powder materials were compacted by the SPS process at 900, 1000, and 1100 °C. The differences between the bulk materials were tested by LM, SEM, and TEM microscopy, XRD, and neutron diffraction methods. It was proven that, although the structures of initial powder (B2) and milled powder (A2) were different, both provide after-sintering material with the same structure (D03) with similar structural parameters. Higher hardness and improved ductility of the material sintered from the milled powder are likely caused by the change in chemical composition during the milling process.

Structure and Properties of High­Strength Ti Grade 4 Prepared by Severe Plastic Deformation and Subsequent Heat Treatment.

Severe plastic deformation represented by three passes in Conform SPD and subsequent rotary swaging was applied on Ti grade 4. This process caused extreme strengthening of material, accompanied by reduction of ductility. Mechanical properties of such material were then tuned by a suitable heat treatment. Measurements of in situ electrical resistance, in situ XRD and hardness indicated the appropriate temperature to be 450 °C for the heat treatment required to obtain desired mechanical properties. The optimal duration of annealing was stated to be 3 h. As was verified by neutron diffraction, SEM and TEM microstructure observation, the material underwent recrystallization during this heat treatment. That was documented by changes of the grain shape and evaluation of crystallite size, as well as of the reduction of internal stresses. In annealed state, the yield stress and ultimate tensile stress decreased form 1205 to 871 MPa and 1224 to 950 MPa, respectively, while the ductility increased from 7.8% to 25.1%. This study also shows that mechanical properties of Ti grade 4 processed by continual industrially applicable process (Conform SPD) are comparable with those obtained by ECAP.

The red and blue luminescence in silicon nanocrystals with an oxidized, nitrogen-containing shell.

Traditionally, two classes of silicon nanocrystals (SiNCs) are recognized with respect to their light-emission properties. These are usually referred to as the "red" and the "blue" emitting SiNCs, based on the spectral region in which the larger part of their luminescence is concentrated. The origin of the "blue" luminescence is still disputed and is very probably different in different systems. One of the important contributions to the discussion about the origin of the "blue" luminescence was the finding that the exposure of SiNCs to even trace amounts of nitrogen in the presence of oxygen induces the "blue" emission, even in originally "red"-emitting SiNCs. Here, we obtained a different result. We show that the treatment of "red" emitting, already oxidized SiNCs in a water-based environment containing air-related radicals including nitrogen-containing species as well as oxygen, diminishes, rather than induces the "blue" luminescence.