Band-gap engineering of zirconia by nitrogen doping in reactive HiPIMS: a step forward in developing innovative technologies for photocatalysts synthesis.

In the global context of climate change and carbon neutrality, this work proposes a strategy to improve the light absorption of photocatalytic water-splitting materials into the visible spectrum by anion doping. In this framework, reactive high power impulse magnetron sputtering (HiPIMS) of a pure Zr target in Ar/N2/O2 gas mixture was used for the deposition of crystalline zirconium oxynitride (ZrO2-xNx) thin films with variable nitrogen doping concentration and energy band-gap. The nitrogen content into these films was controlled by the discharge pulsing frequency, which controls the target surface poisoning and peak discharge current. The role of the nitrogen doping on the optical, structural, and photocatalytic properties of ZrO2-xNx films was investigated. UV-Vis-NIR spectroscopy was employed to investigate the optical properties and to assess the energy band-gap. Surface chemical analysis was performed using X-ray photoelectron spectroscopy, while structural analysis was carried out by X-ray diffraction. The increase in the pulse repetition frequency determined a build-up in the nitrogen content of the deposited ZrO2-xNx thin films from ∼10 to ∼25 at.%. This leads to a narrowing of the optical band-gap energy from 3.43 to 2.20 eV and endorses efficient absorption of visible light. Owing to its narrow bandgap, ZrO2-xNx thin films obtained by reactive HiPIMS can be used as visible light-driven photocatalyst. For the selected processing conditions (pulsing configuration and gas composition), it was found that reactive HiPIMS can suppress the hysteresis effect for a wide range of frequencies, leading to a stable deposition process with a smooth transition from compound to metal-sputtering mode.

Functional Surfaces via Laser Processing in Nickel Acetate Solution.

This study presents a novel laser processing technique in a liquid media to enhance the surface mechanical properties of a material, by thermal impact and micro-alloying at the subsurface level. An aqueous solution of nickel acetate (15% wt.) was used as liquid media for laser processing of C45E steel. A pulsed laser TRUMPH Truepulse 556 coupled to a PRECITEC 200 mm focal length optical system, manipulated by a robotic arm, was employed for the under-liquid micro-processing. The study's novelty lies in the diffusion of nickel in the C45E steel samples, resulting from the addition of nickel acetate to the liquid media. Micro-alloying and phase transformation were achieved up to a 30 µm depth from the surface. The laser micro-processed surface morphology was analysed using optical and scanning electron microscopy. Energy dispersive spectroscopy and X-ray diffraction were used to determine the chemical composition and structural development, respectively. The microstructure refinement was observed, along with the development of nickel-rich compounds at the subsurface level, contributing to an improvement of the micro and nanoscale hardness and elastic modulus (230 GPa). The laser-treated surface exhibited an enhancement of microhardness from 250 to 660 HV0.03 and an improvement of more than 50% in corrosion rate.

Multi-Parametric Exploration of a Selection of Piezoceramic Materials for Bone Graft Substitute Applications.

This work was devoted to the first multi-parametric unitary comparative analysis of a selection of sintered piezoceramic materials synthesised by solid-state reactions, aiming to delineate the most promising biocompatible piezoelectric material, to be further implemented into macro-porous ceramic scaffolds fabricated by 3D printing technologies. The piezoceramics under scrutiny were: KNbO3, LiNbO3, LiTaO3, BaTiO3, Zr-doped BaTiO3, and the (Ba0.85Ca0.15)(Ti0.9Zr0.1)O3 solid solution (BCTZ). The XRD analysis revealed the high crystallinity of all sintered ceramics, while the best densification was achieved for the BaTiO3-based materials via conventional sintering. Conjunctively, BCTZ yielded the best combination of functional properties-piezoelectric response (in terms of longitudinal piezoelectric constant and planar electromechanical coupling factor) and mechanical and in vitro osteoblast cell compatibility. The selected piezoceramic was further used as a base material for the robocasting fabrication of 3D macro-porous scaffolds (porosity of ~50%), which yielded a promising compressive strength of ~20 MPa (higher than that of trabecular bone), excellent cell colonization capability, and noteworthy cytocompatibility in osteoblast cell cultures, analogous to the biological control. Thereby, good prospects for the possible development of a new generation of synthetic bone graft substitutes endowed with the piezoelectric effect as a stimulus for the enhancement of osteogenic capacity were settled.

Room Temperature Deposition of Nanocrystalline SiC Thin Films by DCMS/HiPIMS Co-Sputtering Technique.

Due to an attractive combination of chemical and physical properties, silicon carbide (SiC) thin films are excellent candidates for coatings to be used in harsh environment applications or as protective coatings in heat exchanger applications. This work reports the deposition of near-stoichiometric and nanocrystalline SiC thin films, at room temperature, on silicon (100) substrates using a DCMS/HiPIMS co-sputtering technique (DCMS-direct current magnetron sputtering; HiPIMS-high-power impulse magnetron sputtering). Their structural and mechanical properties were analyzed as a function of the process gas pressure. The correlation between the films' microstructure and their mechanical properties was thoroughly investigated. The microstructure and morphology of these films were examined by appropriate microscopic and spectroscopic methods: atomic force microscopy (AFM), scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDX), X-ray diffraction (XRD), and Raman spectroscopy, while their mechanical and tribological properties were evaluated by instrumented indentation and micro-scratch techniques. The lowest value of the working gas pressure resulted in SiC films of high crystallinity, as well as in an improvement in their mechanical performances. Both hardness (H) and Young's modulus (E) values were observed to be significantly influenced by the sputtering gas pressure. Decreasing the gas pressure from 2.0 to 0.5 Pa led to an increase in H and E values from 8.2 to 20.7 GPa and from 106.3 to 240.0 GPa, respectively. Both the H/E ratio and critical adhesion load values follow the same trend and increase from 0.077 to 0.086 and from 1.55 to 3.85 N, respectively.

Surface, Structural, and Mechanical Properties Enhancement of Cr2O3 and SiO2 Co-Deposited Coatings with W or Be.

Direct current (DC) and radio frequency (RF) magnetron sputtering methods were selected for conducting the deposition of structural materials, namely ceramic and metallic co-depositions. A total of six configurations were deposited: single thin layers of oxides (Cr2O3, SiO2) and co-deposition configurations (50:50 wt.%) as structural materials (W, Be)-(Cr2O3, SiO2), all deposited on 304L stainless steel (SS). A comprehensive evaluation such as surface topology, thermal desorption outgassing, and structural/chemical state was performed. Moreover, mechanical characterization evaluating properties such as adherence, nano indentation hardness, indentation modulus, and deformation relative to yielding, was performed. Experimental results show that, contrary to SiO2 matrix, the composite layers of Cr2O3 with Be and W exhibit surface smoothing with mitigation of artifacts, thus presenting a uniform and compact state with the best microstructure. These results are relevant in order to develop future dense coatings to be used in the fusion domain.

Investigations Regarding the Addition of ZnO and Li2O-TiO2 to Phosphate-Tellurite Glasses: Structural, Chemical, and Mechanical Properties.

Phosphate and tellurite glasses can be used in optics, optoelectronics, magneto-optics, and nuclear and medical fields. Two series of phosphate-tellurite glasses, (50-x)ZnO-10Al2O3-40P2O5-xTeO2 and (40-x)Li2O-10Al2O3-5TiO2-45P2O5-xTeO2 (x = 5, 10), were synthesized by a non-conventional wet-route, and the mechanical properties as key performance measures for their application in optoelectronics were investigated. X-ray Diffraction (XRD) measurements revealed the vitreous nature of the investigated materials. Instrumented indentation tests allowed the calculation of hardness (H) and Young's modulus (E) using the Oliver and Pharr model. The influence of increasing the TeO2 content, as well as the substitution of ZnO by Li2O-TiO2, on the variation of hardness, Young's modulus, penetration depth (PD), and fracture toughness (FT) was evaluated in both series. As a general trend, there is a decrease in the hardness and Young's modulus with increasing penetration depth. The addition of Li2O and TiO2 instead of ZnO leads to improved hardness and elastic modulus values. Regarding the H/E ratio, it was found that the samples with lower TeO2 content should be significantly more crack-resistant compared to the higher TeO2 content samples. The H3/E2 ratio, being lower than 0.01, revealed a poor resistance of these glasses to plastic deformation. At the same time, a decrease of the fracture toughness with increasing TeO2 content was noticed for each glass series. Based on dilatometry measurements, the thermal expansion coefficient as well as the characteristic temperatures of the glasses were measured. Field Emission Scanning Electron Microscopy-Energy Dispersive X-ray analysis (FESEM-EDX) revealed a uniform distribution of the elements in the bulk samples. The mechanical properties of these vitreous materials are important in relation to their application as magneto-optical Faraday rotators in laser cavities.

Stainless Steel Surface Nitriding in Open Atmosphere Cold Plasma: Improved Mechanical, Corrosion and Wear Resistance Properties.

This work presents preliminary results regarding improving the mechanical, wear and protective properties (hardness, coefficient of friction, corrosion resistance) of AISI 304 stainless steel surfaces by open atmosphere cold plasma surface treatment method. Comparative evaluations of the morphological, corrosion resistance, mechanical and tribological properties for different periods of treatment (using N2 gas for cold plasma generation in an open atmosphere) were performed. AFM surface analyses have shown significant surface morphology modifications (average roughness, FWHM, surface skewness and kurtosis coefficient) of the treated samples. An improved corrosion resistance of the N2 treated surfaces in open atmosphere cold plasma could be observed using electrochemical corrosion tests. The mechanical tests have shown that the surface hardness (obtained by instrumented indentation) is higher for the 304 stainless steel samples than it is for the un-treated surface, and it decreases gradually for higher penetration depths. The kinetic coefficient of friction (obtained by ball-on-disk wear tests) is significantly lower for the treated samples and increases gradually to the value of the un-treated surface. The low friction regime length is dependent on the surface treatment period, with a longer cold plasma nitriding process leading to a significantly better wear behavior.

Evaluation of Heat-Treated AISI 316 Stainless Steel in Solar Furnaces to Be Used as Possible Implant Material.

The appropriate selection of implant materials is very important for the long-term success of the implants. A modified composition of AISI 316 stainless steel was treated using solar energy in a vertical axis solar furnace and it was subjected to a hyper-hardening treatment at a 1050 °C austenitizing temperature with a rapid cooling in cold water followed by three variants of tempering (150, 250, and 350 °C). After the heat treatment, the samples were analyzed in terms of hardness, microstructure (performed by scanning electron microscopy), and corrosion resistance. The electrochemical measurements were performed by potentiodynamic and electrochemical impedance spectroscopy in liquids that simulate biological fluids (NaCl 0.9% and Ringer's solution). Different corrosion behaviors according to the heat treatment type have been observed and a passivation layer has formed on some of the heat-treated samples. The samples, heat-treated by immersion quenching, exhibit a significantly improved pitting corrosion resistance. The subsequent heat treatments, like tempering at 350 °C after quenching, also promote low corrosion rates. The heat treatments performed using solar energy applied on stainless steel can lead to good corrosion behavior and can be recommended as unconventional thermal processing of biocompatible materials.

Tantalum Oxynitride Thin Films: Assessment of the Photocatalytic Efficiency and Antimicrobial Capacity.

Tantalum oxynitride thin films have been deposited by reactive magnetron sputtering, using a fixed proportion reactive gas mixture (85% N2 + 15% O2). To produce the films, the partial pressure of the mixture in the working atmosphere was varied. The characteristics of the produced films were analyzed from three main perspectives and correspondent correlations: the study of the bonding states in the films, the efficiency of photo-degradation, and the antibacterial/antibiofilm capacity of the coatings against Salmonella. X-ray Photoelectron Spectroscopy results suggest that nitride and oxynitride features agree with a constant behavior relative to the tantalum chemistry. The coatings deposited with a higher reactive gas mixture partial pressure exhibit a significantly better antibiofilm capacity. Favorable antibacterial resistance was correlated with the presence of dominant oxynitride contributions. The photocatalytic ability of the deposited films was assessed by measuring the level of degradation of an aqueous solution containing methyl orange, with or without the addition of H2O2, under UV or VIS irradiation. Degradation efficiencies as high as 82% have been obtained, suggesting that tantalum oxynitride films, obtained in certain configurations, are promising materials for the photodegradation of organic pollutants (dyes).

Ti-Zr-Si-Nb Nanocrystalline Alloys and Metallic Glasses: Assessment on the Structural Development, Thermal Stability, Corrosion and Mechanical Properties.

The development of novel Ti-based amorphous or ß-phase nanostructured metallic materials could have significant benefits for implant applications, due to potentially improved corrosion properties, and mechanical characteristics (lower Young's modulus, better wear performance, improved fracture toughness) in comparison to the standardized α+ß titanium alloys. Moreover, the devitrification phenomenon, occurring during heating, could contribute to lower input power during additive manufacturing technologies. Ti-based alloy ribbons were obtained by melt-spinning, considering the ultra-fast cooling rates this method can provide. The titanium alloys contain Zr, Nb, and Si (Ti60Zr10Si15Nb15, Ti64Zr10Si15Nb11, Ti56Zr10Si15Nb19) in various proportions. These elements were chosen due to their reported biological safety, as in the case of Zr and Nb, and the metallic glass-forming ability and biocompatibility of Si. The morphology and chemical composition were analyzed by scanning electron microscopy and energy-dispersive X-ray spectroscopy, while the structural features (crystallinity, phase attribution after devitrification (after heat treatment)) were assessed by X-ray diffraction. Some of the mechanical properties (hardness, Young's modulus) were assessed by instrumented indentation. The thermal stability and crystallization temperatures were measured by differential thermal analysis. High-intensity exothermal peaks were observed during heating of melt-spun ribbons. The corrosion behavior was assessed by electrocorrosion tests. The results show the potential of these alloys to be implemented as materials for biomedical applications.

Multi-scale mechanical investigation of stainless steel and cobalt-chromium stents.

In-stent restenosis (ISR) remains a significant limitation despite the considerable previous clinical and investigative emphasis on the problem. Complications arising from the interaction of stent materials with the surrounding vessel wall as well as from the mechanical forces developing after implantation, play an important role in the development of ISR. To investigate the relation between mechanical factors and stent structural integrity, and to identify any structural weakness points on the geometry of commercially available Stainless Steel and Cobalt-Chromium stents, accelerated pulsatile durability tests were carried out in a simulated physiological environment. Potential spatial variations in the mechanical properties on stent struts and their role in the observed premature failures of the stent devices during operation were also examined. Fretting wear and fatigue-induced fractures were found on stent surfaces after exposure to cyclic loading similar to that arising in vivo. Nanoindentation studies performed on various locations along the stent struts have shown that the hardness of specific stent locations significantly increases after mechanical expansion. The increase in hardness was associated with a reduction of the material's ability to dissipate energy in plastic deformations, therefore an increased vulnerability to fracture and fatigue. We conclude that the locations of fatigue fractures in stent struts are controlled not only by the geometrically-driven stress concentrations developing during cyclic loading but also by the local material mechanical changes that are imparted on various parts of the stent during the deployment process.