In-Depth Characterization of Two Bioactive Coatings Obtained Using MAPLE on TiTaZrAg.

TiZrTaAg alloy is a remarkable material with exceptional properties, making it a unique choice among various industrial applications. In the present study, two types of bioactive coatings using MAPLE were obtained on a TiZrTaAg substrate. The base coating consisted in a mixture of chitosan and bioglass in which zinc oxide and graphene oxide were added. The samples were characterized in-depth through a varied choice of methods to provide a more complete picture of the two types of bioactive coating. The analysis included Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), ellipsometry, and micro-Raman. The Vickers hardness test was used to determine the hardness of the films and the penetration depth. Film adhesion forces were determined using atomic force microscopy (AFM). The corrosion rate was highlighted by polarization curves and by using electrochemical impedance spectroscopy (EIS). The performed tests revealed that the composite coatings improve the properties of the TiZrTaAg alloy, making them feasible for future use as scaffold materials or in implantology.

Boosting Supercapacitor Efficiency with Amorphous Biomass-Derived C@TiO2 Composites.

Carbon materials are readily available and are essential in energy storage. One of the routes used to enhance their surface area and activity is the decoration of carbons with semiconductors, such as amorphous TiO2, for application in energy storage devices.

Fabrication of Co-Sb Junction Nanowires by Galvanostatic Electrodeposition.

This work presents the synthesis of CoSb3 one-dimensional (1D) thermoelectric nanomaterials using electrodeposition under galvanostatic conditions and polycarbonate membranes as a template (50 nm diameter pores). Cyclic voltammetry measurements have been performed to get preliminary information on the electrochemical reduction process of the involved species. Different current density values in the range 1-4 mA cm-2 have been applied, leading to the formation of nanowires (NWs) and micro- and nanomushroom caps, as evidenced by the scanning electron microscopy and scanning transmission electron microscopy investigations. Through fine-tuning of the current density the desired Co/Sb atomic ratio could be achieved. Energy-dispersive X-ray spectroscopy analysis showed the formation of CoSb3 at 1.4 mA cm-2, and it has also been confirmed by high-resolution transmission electron microscopy and micro-Raman spectroscopy. In this work, we present for the first time the fabrication of a CoSb3-CoxSby heterojunction on the same NW exhibiting Sb-rich and Co-rich alloy segments, prepared by electrodeposition from the same electrolyte by simply varying the applied current density.

The Influence of Reflowing Process on Electrodeposited Sn-Cu-Ni Lead-Free Solder Alloy.

Sn-Cu-Ni lead-free solder alloy electrodeposited on copper substrate from a deep eutectic solvent (DES)-based electrolyte under direct current (DC) and pulsed current (PC) was subjected to a reflowing process at the industrial company MIBATRON S.R.L. (Otopeni, Romania). The alteration of the alloy's composition and anti-corrosive properties upon exposure to the reflow process were investigated via Scanning Electron Microscopy (SEM-EDX), X-ray diffraction (XRD), linear sweep voltammetry (LSV) and electrochemical impedance spectroscopy (EIS). Corrosion studies conducted in sodium chloride solution revealed that the system obtained under the DC plating mode (Sn-Cu-Ni-DC) exhibited enhanced anti-corrosive properties compared to the system obtained under PC (Sn-Cu-Ni-PC) after reflowing. However, prior to reflowing, the opposite effect was observed, with Sn-Cu-Ni-PC showing improved anti-corrosive properties. These changes in anti-corrosive behavior were attributed to the modification of the alloy's composition during the reflowing process.

Renewable Carbon Materials as Electrodes for High-Performance Supercapacitors: From Marine Biowaste to High Specific Surface Area Porous Biocarbons.

Waste, in particular, biowaste, can be a valuable source of novel carbon materials. Renewable carbon materials, such as biomass-derived carbons, have gained significant attention recently as potential electrode materials for various electrochemical devices, including batteries and supercapacitors. The importance of renewable carbon materials as electrodes can be attributed to their sustainability, low cost, high purity, high surface area, and tailored properties. Fish waste recovered from the fish processing industry can be used for energy applications and prioritizing the circular economy principles. Herein, a method is proposed to prepare a high surface area biocarbon from glycogen extracted from mussel cooking wastewater. The biocarbon materials were characterized using a Brunauer-Emmett-Teller surface area analyzer to determine the specific surface area and pore size and by scanning electron microscopy coupled with energy-dispersive X-ray analysis, Raman analysis, attenuated total reflectance Fourier transform infrared spectroscopy, X-ray diffraction, X-ray photoelectron spectroscopy, and transmission electron microscopy. The electrochemical characterization was performed using a three-electrode system, utilizing a choline chloride-based deep eutectic solvent (DES) as an eco-friendly and sustainable electrolyte. Optimal time and temperature allowed the preparation of glycogen-based carbon materials, with a specific surface area of 1526 m2 g-1, a pore volume of 0.38 cm3 g-1, and an associated specific capacitance of 657 F g-1 at a current density of 1 A g-1, at 30 °C. The optimal material was scaled up to a two-electrode supercapacitor using a DES-based solid-state electrolyte (SSE@DES). This prototype delivered a maximum capacitance of 703 F g-1 at a 1 A g-1 of current density, showing 75% capacitance retention over 1000 cycles, delivering the highest energy density of 0.335 W h kg-1 and power density of 1341 W kg-1. Marine waste can be a sustainable source for producing nanoporous carbon materials to be incorporated as electrode materials in energy storage devices.

Activated carbons with extremely high surface area produced from cones, bark and wood using the same procedure.

Activated carbons have been previously produced from a huge variety of biomaterials often reporting advantages of using certain precursors. Here we used pine cones, spruce cones, larch cones and a pine bark/wood chip mixture to produce activated carbons in order to verify the influence of the precursor on properties of the final materials. The biochars were converted into activated carbons with extremely high BET surface area up to ∼3500 m2 g-1 (among the highest reported) using identical carbonization and KOH activation procedures. The activated carbons produced from all precursors demonstrated similar specific surface area (SSA), pore size distribution and performance to electrodes in supercapacitors. Activated carbons produced from wood waste appeared to be also very similar to "activated graphene" prepared by the same KOH procedure. Hydrogen sorption of AC follows expected uptake vs. SSA trends and energy storage parameters of supercapacitor electrodes prepared from AC are very similar for all tested precursors. It can be concluded that the type of precursor (biomaterial or reduced graphene oxide) has smaller importance for producing high surface area activated carbons compared to details of carbonization and activation. Nearly all kinds of wood waste provided by the forest industry can possibly be converted into high quality AC suitable for preparation of electrode materials.

Chitins from Seafood Waste as Sustainable Porous Carbon Precursors for the Development of Eco-Friendly Supercapacitors.

Carbon materials derived from marine waste have been drawing attention for supercapacitor applications. In this work, chitins from squid and prawn marine wastes were used as carbon precursors for further application as electrodes for energy storage devices. Chitins were obtained through a deproteinization method based on enzymatic hydrolysis as an alternative to chemical hydrolysis as commonly presented in the literature. The obtained porous carbons were characterized using a BET surface area analyzer to determine the specific surface area and pore size, as well as scanning electron microscopy (SEM) with energy dispersive X-ray analysis (EDX), transmission electron microscopy (TEM), Raman spectroscopy, attenuated total reflectance Fourier transform infrared (ATR-FTIR) spectroscopy, X-ray diffraction (XRD), and X-ray photoelectron spectroscopy (XPS), to characterize their morphology, composition, and structure. The electrochemical characterization was performed using a glassy carbon (GC) electrode modified with marine waste-based porous carbons as the working electrode through cyclic voltammetry and galvanostatic charge/discharge using ethaline, a choline chloride-based deep eutectic solvent (DES), as an eco-friendly and sustainable electrolyte. Squid and prawn chitin-based carbons presented a surface area of 149.3 m2 g-1 and 85.0 m2 g-1, pore volume of 0.053 cm3 g-1 and 0.029 cm3 g-1, and an associated specific capacitance of 20 and 15 F g-1 at 1 A g-1, respectively. Preliminary studies were performed to understand the effect of -OH groups on the chitin-based carbon surface with DES as an electrolyte, as well as the effect of aqueous electrolytes (1 mol L-1 sulphuric acid (H2SO4) and 1 mol L-1 potassium hydroxide (KOH)) on the capacitance and retention of the half-cell set up. It is provided, for the first time, the use of chitin-based carbon materials obtained through a one-step carbonization process combined with an eco-friendly DES electrolyte for potential application in energy storage devices.

Synthesis of Copper Nanostructures for Non-Enzymatic Glucose Sensors via Direct-Current Magnetron Sputtering.

In this paper, Cu nanocolumnar structure electrodes are synthetized using a clean and easy-to-scale-up direct-current magnetron sputtering (DC-MS) technique for non-enzymatic glucose sensing. The nanocolumnar structure increases the active surface area of the deposit, with the nanocolumns showing a mean size diameter of 121.0 nm ± 27.2 and a length of 2.52 µm ± 0.23. A scanning transmission electron (STEM) analysis shows the presence of Cu and a small amount of Cu2O. The behavior of the electrodes in alkaline environments and the electrochemical affinity of the Cu nanocolumns (CuNCs) towards the electro-oxidation of glucose are investigated using cyclic voltammetry (CV). After performing CV in NaOH solution, the columnar structures present corrosion products containing Cu2O, as revealed by STEM and X-ray diffraction (XRD) analyses. The amperometric responses of the CuNCs to the successive addition of glucose show a linear range up to 2 mM and a limit of detection of 5.2 µM. Furthermore, the electrodes are free from chloride poisoning, and they are insensitive to dopamine, uric acid, ascorbic acid, and acetaminophen at their physiological concentrations.

Antibacterial and Photocatalytic Coatings Based on Cu-Doped ZnO Nanoparticles into Microcellulose Matrix.

The paper presents a successful, simple method for the preparation and deposition of new hybrid Cu-doped ZnO/microcellulose coatings on textile fibers, directly from cellulose aqueous solution. The morphological, compositional, and structural properties of the obtained materials were investigated using different characterization methods, such as SEM-EDX, XRD, Raman and FTIR, as well as BET surface area measurements. The successful doping of ZnO NPs with Cu was confirmed by the EDX and Raman analysis. As a result of Cu doping, the hybrid NPs experienced a phase change from ZnO to (Zn0.9Cu0.1)O, as shown by the XRD results. All the hybrid NPs exhibited a high degree of crystallinity, as revealed by the very sharp reflections in XRD patterns and suggested also by the Raman results. The evaluation of the very low copper-doping (0.1-1 at.%) effect has shown different behavior trends of the hybrid coatings compared with the starting oxide NPs, for MB and MO photodegradation. Continuous increases up to 92% and 60% for MB and MO degradation, respectively, were obtained at maximum 1 at.%-Cu doping coatings. Strong antibacterial activity against S. aureus and E. coli were observed.

Electrochemical Deposition of Ferromagnetic Ni Nanoparticles in InP Nanotemplates Fabricated by Anodic Etching Using Environmentally Friendly Electrolyte.

Porous InP templates possessing a thickness of up to 100 µm and uniformly distributed porosity were prepared by anodic etching of InP substrates exhibiting different electrical conductivities, involving an environmentally friendly electrolyte. Ni nanoparticles were successfully directly deposited by pulsed electroplating into prefabricated InP templates without any additional deposition of intermediary layers. The parameters of electrodeposition, including the pulse amplitude, pulse width and interval between pulses, were optimized to reach a uniform metal deposition covering the inner surface of the nanopores. The electrochemical dissolution of n-InP single crystals was investigated by measuring the current-voltage dependences, while the Ni-decorated n-InP templates have been characterized by scanning electron microscopy (SEM) and energy-dispersive X-ray spectroscopy (EDX). The proposed technology is expected to be of interest for sensing and photocatalytic applications, as well as for the exploration of their plasmonic and magnetic properties.

Synthesis and Characterization of Coordination Compound [Eu(µ2-OC2H5)(btfa)(NO3)(phen)]2phen with High Luminescence Efficiency.

A high-luminescent, blue-light excitable europium(III) coordination complex, [Eu(µ2-OC2H5)(btfa)(NO3)(phen)]2phen (1) {btfa = benzoyl trifluoroacetone, phen = 1,10-phenantroline}, has been synthesized and investigated. The complex was characterized by infrared (IR) and photoluminescence (PL) spectroscopy. The PL emission spectra of powder samples registered in a range of 10.7-300 K exhibit characteristic metal-centered luminescence bands, assigned to internal radiative transitions of the Eu3+ ion, 5D1→7Fj and 5D0→7Fj (j = 0-4). The high-resolution spectrum of the transition 5D0→7F0 shows that it consists of two narrow components, separated by 0.96 meV, which indicates the presence in the matrix of two different sites of the Eu3+ ion. The splitting pattern of 5D0→7Fj (j = 0-4) transitions indicates that europium ions are located in a low-symmetry environment. The absolute quantum yield and the sensitization efficiency were determined to be 49.2% and 89.3%, respectively. The complex can be excited with low-cost lasers at around 405 nm and is attractive for potential applications in optoelectronics and biochemistry.

Interaction of Mg Alloy with PLA Electrospun Nanofibers Coating in Understanding Changes of Corrosion, Wettability, and pH.

A modified biodegradable magnesium alloy (AZ31, 96 wt% Mg, 3 wt% Al, and 1 wt% Zn) with polylactic acid (PLA) nanofibers was obtained by the electrospinning technique. The presence of PLA nanofibers was evidenced using Fourier transform infrared spectroscopy (FT-IR) and using an scanning electronic microscope (SEM) equipped with an energy dispersive X-ray spectroscopy (EDX) module. The degradation behavior of an uncoated Mg alloy and a Mg alloy coated with PLA was evaluated through hydrogen evolution, pH, and electrochemical measurements in simulated body fluid. Contact angle measurements showed a shift from hydrophilic towards the hydrophobic character of the alloy after its coating with PLA nanofibers. Furthermore, the electrochemical measurement results show that the Mg based alloy coated with PLA inhibits hydrogen evolution, thus being less prone to degradation. The aim of this research is not only to reduce the corrosion rate of Mg alloy and to improve its properties with the help of polylactic acid coating, but also to provide a study to understand the hydrophilic-hydrophobic balance of biodegradable magnesium based on surface energy investigations. Taking into account corrosion rate, wettability, and pH changes, an empiric model of the interaction of Mg alloy with PLA nanofibers is proposed.

The Water-Based Synthesis of Platinum Nanoparticles Using KrF Excimer Laser Ablation.

Our work presents, for the first time, a comprehensive study of the synthesis of fully metallic platinum nanoparticles (Pt-NPs) involving the ablation process in double distilled water using a KrF excimer laser. To obtain detailed information on Pt-NP morphology and optical properties, prepared colloids were characterized using High Resolution Scanning Transmission Electron Microscopy (HR-STEM) with advanced capabilities for Energy Dispersive X-ray Analysis (EDX), UV/Vis optical spectroscopy, and Direct Analysis in Real Time-Mass Spectrometry (DART-MS). The influence of the applied laser fluence and laser repetition rate (RR) values on the characteristics of the obtained Pt-NPs and the ablation process, respectively, were also analyzed. Spherical and spherical-like nanoparticles exhibiting aggregation were produced. The Pt-NP mean size values were between 2.2 ± 1.2 nm and 4.0 ± 1.0 nm, while their interplanar distance measurements showed a face-centered cubic (FFC) Pt lattice (111), as revealed by HR-STEM measurements, for all investigated samples. The smallest mean size of 2.2 nm of the Pt-NPs was obtained using a 2.3 J cm-2 laser fluence at a 10 Hz RR, and the narrowest size distribution of the NPs was obtained with a 2.3 J cm-2 laser fluence at a 40 Hz RR. A linear dependence of the Pt-NP diameters versus the laser repetition rate was found at a constant fluence of 2.3 J cm-2. The proposed eco-friendly synthesis route of Pt-NPs, because of its relative simplicity, has the potential for use in industrial production.

Preliminary Study on Light-Activated Antimicrobial Agents as Photocatalytic Method for Protection of Surfaces with Increased Risk of Infections.

Preventing and controlling the spread of multidrug-resistant (MDR) bacteria implicated in healthcare-associated infections is the greatest challenge of the health systems. In recent decades, research has shown the need for passive antibacterial protection of surfaces in order to reduce the microbial load and microbial biofilm development, frequently associated with transmission of infections. The aim of the present study is to analyze the efficiency of photocatalytic antimicrobial protection methods of surfaces using the new photocatalytic paint activated by light in the visible spectrum. The new composition is characterized by a wide range of analytical methods, such as UV-VIS spectroscopy, electron microscopy (SEM), X-ray powder diffraction (PXRD) or X-ray photoelectron spectroscopy (XPS). The photocatalytic activity in the UV-A was compared with the one in the visible light spectrum using an internal method developed on the basis of DIN 52980: 2008-10 standard and ISO 10678-2010 standard. Migration of metal ions in the composition was tested based on SR EN1186-3: 2003 standard. The new photocatalytic antimicrobial method uses a type of photocatalytic paint that is active in the visible spectral range and generates reactive oxygen species with inhibitory effect against all tested microbial strains.

Simulations of the Ultra-Fast Kinetics in Ni-Si-C Ternary Systems under Laser Irradiation.

We present a method for the simulation of the kinetic evolution in the sub µs timescale for composite materials containing regions occupied by alloys, compounds, and mixtures belonging to the Ni-Si-C ternary system. Pulsed laser irradiation (pulses of the order of 100 ns) promotes this evolution. The simulation approach is formulated in the framework of the phase-field theory and it consists of a system of coupled non-linear partial differential equations (PDEs), which considers as variables the following fields: the laser electro-magnetic field, the temperature, the phase-field and the material (Ni, Si, C, C clusters and Ni-silicides) densities. The model integrates a large set of materials and reaction parameters which could also self-consistently depend on the model variables. A parameter calibration is also proposed, specifically suited for the wavelength of a widely used class of excimer lasers (λ = 308 nm). The model is implemented on a proprietary laser annealing technology computer-aided design (TCAD) tool based on the finite element method (FEM). This integration allows, in principle, numerical solutions in systems of any dimension. Here we discuss the complex simulation trend in the one-dimensional case, considering as a starting state, thin films on 4H-SiC substrates, i.e., a configuration reproducing a technologically relevant case study. Simulations as a function of the laser energy density show an articulated scenario, also induced by the variables' dependency of the materials' parameters, for the non-melting, partial-melting and full-melting process conditions. The simulation results are validated by post-process experimental analyses of the microstructure and composition of the irradiated samples.

Fabrication of Optical Fibers with Multiple Coatings for Swelling-Based Chemical Sensing.

We discuss distributed chemical sensing based on the swelling of coatings of optical fibers. Volume changes in the coating induce strain in the fiber's glass core, provoking a local change in the refractive index which is detectable by distributed fiber optical sensing techniques. We describe methods to realize different coatings on a single fiber. Simultaneous detection of swelling processes all along the fiber opens the possibility to interrogate thousands of differently functionalized sections on a single fiber. Principal component analysis is used to enable sensors for environmental monitoring, food analysis, agriculture, water quality monitoring, or medical diagnostics.

Joining Caffeic Acid and Hydrothermal Treatment to Produce Environmentally Benign Highly Reduced Graphene Oxide.

Reduced graphene oxide (rGO) is a promising graphene-based material, with transversal applicability to a wide range of technological fields. Nevertheless, the common use of efficient-but hazardous to environment and toxic-reducing agents prevents its application in biological and other fields. Consequently, the development of green reducing strategies is a requirement to overcome this issue. Herein, a green, simple, and cost-effective one-step reduction methodology is presented. Graphene oxide (GO) was hydrothermally reduced in the presence of caffeic acid (CA), a natural occurring phenolic compound. The improvement of the hydrothermal reduction through the presence of CA is confirmed by XRD, Raman, XPS and TGA analysis. Moreover, CA polymerizes under hydrothermal conditions with the formation of spherical and non-spherical carbon particles, which can be useful for further rGO functionalization. FTIR and XPS confirm the oxygen removal in the reduced samples. The high-resolution scanning transmission electron microscopy (HRSTEM) images also support the reduction, showing rGO samples with an ordered graphitic layered structure. The promising rGO synthesized by this eco-friendly methodology can be explored for many applications.

Pulsed Laser Deposition of SWCNTs on Carbon Fibres: Effect of Deposition Temperature.

Single wall carbon nanotubes (SWCNTs) were grown on either sized or desized carbon fabric in a self-designed reactor by Pulsed Laser Deposition (PLD). The uniqueness of the PLD system lies, among other things, in the ability to keep the substrate at a low temperature, compared to the 1100 °C needed for the SWCNTs synthesis, thus, rendering it undamaged. Samples were placed at different positions on a cold finger (CF), where a temperature gradient develops, in the range 25-565 °C. The chemical composition and morphology of desized and surface treatments, as well as SWCNTs grown on carbon fibres, were verified by Scanning Electron Microscopy (SEM) equipped with Energy Dispersive X-Ray Spectroscopy (EDX), while the quality of SWCNTs was proven by confocal micro-Raman Spectroscopy and High-Resolution Scanning Transmission Electron Microscopy (HR-STEM). Fibres covered with SWCNTs by PLD were characterized using contact angle and the surface free energy was calculated. A micro-droplet pull-out test was used to evaluate the effect of SWCNTs over interfacial properties of a carbon-epoxy composite. A 20% increase in interfacial shear strength (IFSS) was observed by deposition at 290 °C, compared to the commercial carbon fibre sizing. The carbon fibres kept their tensile properties due to the low deposition temperatures.

Assessing the Functional Properties of TiZr Nanotubular Structures for Biomedical Applications, through Nano-Scratch Tests and Adhesion Force Maps.

In this work we present the results of a functional properties assessment via Atomic Force Microscopy (AFM)-based surface morphology, surface roughness, nano-scratch tests and adhesion force maps of TiZr-based nanotubular structures. The nanostructures have been electrochemically prepared in a glycerin + 15 vol.% H2O + 0.2 M NH4F electrolyte. The AFM topography images confirmed the successful preparation of the nanotubular coatings. The Root Mean Square (RMS) and average (Ra) roughness parameters increased after anodizing, while the mean adhesion force value decreased. The prepared nanocoatings exhibited a smaller mean scratch hardness value compared to the un-coated TiZr. However, the mean hardness (H) values of the coatings highlight their potential in having reliable mechanical resistances, which along with the significant increase of the surface roughness parameters, which could help in improving the osseointegration, and also with the important decrease of the mean adhesion force, which could lead to a reduction in bacterial adhesion, are providing the nanostructures with a great potential to be used as a better alternative for Ti implants in dentistry.

Swelling-Based Distributed Chemical Sensing with Standard Acrylate Coated Optical Fibers.

Distributed chemical sensing is demonstrated using standard acrylate coated optical fibers. Swelling of the polymer coating induces strain in the fiber's silica core provoking a local refractive index change which is detectable all along an optical fiber by advanced distributed sensing techniques. Thermal effects can be discriminated from strain using uncoated fiber segments, leading to more accurate strain readings. The concept has been validated by measuring strain responses of various aqueous and organic solvents and different chain length alkanes and blends thereof. Although demonstrated on a short range of two meters using optical frequency-domain reflectometry, the technique can be applied to many kilometer-long fiber installations. Low-cost and insensitive to corrosion and electromagnetic radiation, along with the possibility to interrogate thousands of independent measurement points along a single optical fiber, this novel technique is likely to find applications in environmental monitoring, food analysis, agriculture, water quality monitoring, or medical diagnostics.