Publications

Developing new materials to be applied in extreme environments is an opportunity and a challenge for the future. High entropy alloys are new materials that seem promising approaches to work in nuclear fusion reactors. In this work, FeTaTiVW high entropy alloys were developed and characterized with Molecular Dynamic and Hybrid Molecular Dynamic Monte Carlo simulations. The simulation results show that phase separation originates a lower potential energy per atom and a high level of segregation compared to those of a uniform solid solution. Moreover, the experimental diffractogram of the milled powder shows the formation of a body-centred cubic-type structure and the presence of TiO2. In addition, the microstructure of the consolidated material evidenced three phases: W-rich, Ti-rich, and a phase with all the elements. This phase separation observed in the microstructure agrees with the Hybrid Molecular Dynamic Monte Carlo simulation. Moreover, the consolidated material's thermal conductivity and specific heat are almost constant from 25 degrees C to 1000 degrees C, and linear expansion increases with increasing temperature. On the other hand, specific heat and thermal expansion values are in between CuCrZr and W values (materials chosen for the reactor walls). The FeTaTiVW high entropy alloy evidences a ductile behaviour at 1000 degrees C. Therefore, the promising thermal properties of this system can be attributed to the multiple phases and systems with different compositions of the same elements, which is exciting for future developments.

Tungsten is the primary candidate armour material for the divertor target of the European demonstration fusion power plant. During operation at high temperature, pure tungsten is subject to fracture and recrystallization which results in a loss of strength and worsening of the thermal properties. Additionally, loss-of-coolant accidents with simultaneous air ingress can generate volatile and radioactive tungsten oxides. Advanced W-alloys were developed as alternative and upgrading armour materials of pure tungsten, such as potassium-doped tungsten laminates and self-passivating tungsten alloys. Three mock-ups were manufactured using potassium-doped tungsten laminates, W-10Cr-0.5Y and W-10Cr-0.5Y-0.5Zr as armour materials, each of them consisting of n degrees 4 blocks. The fabrication required optimization and upscaling of the ITER-like process which foresees oxygen-free high conductivity copper as interlayer joined to W-alloy armour block and CuCrZr ITER grade pipe welded to the Cu/W-alloy blocks by hot radial pressing. For quality control of the fabrication steps, non-destructive examination by ultrasonic testing was done on the monoblocks as received, after casting, after hot radial pressing and after high heat flux testing. The results demonstrated that these W-alloys can be used as armour materials of the European demonstration fusion power plant divertor target.

Antidepressant drugs play a crucial role in the treatment of mental health disorders, but their efficacy and safety can be compromised by drug degradation. Recent reports point to several drugs found in concentrations ranging from the limit of detection (LOD) to hundreds of ng/L in wastewater plants around the globe; hence, antidepressants can be considered emerging pollutants with potential consequences for human health and wellbeing. Understanding and implementing effective degradation strategies are essential not only to ensure the stability and potency of these medications but also for their safe disposal in line with current environment remediation goals. This review provides an overview of degradation pathways for amitriptyline, a typical tricyclic antidepressant drug, by exploring chemical routes such as oxidation, hydrolysis, and photodegradation. Connex issues such as stability-enhancing approaches through formulation and packaging considerations, regulatory guidelines, and quality control measures are also briefly noted. Specific case studies of amitriptyline degradation pathways forecast the future perspectives and challenges in this field, helping researchers and pharmaceutical manufacturers to provide guidelines for the most effective degradation pathways employed for minimal environmental impact.

Structurally disordered Pr3+-doped Ca-3(Ta,Ga)(5)O-12 - Pr:CTGG single crystal was grown by the Czochralski technique for the first time and its spectroscopic properties were investigated. Modified Judd-Ofelt analysis was applied to determine spectroscopic and laser emission characteristics. Based on low-temperature absorption and emission spectra, the partial energy levels of Pr3+ ions have been obtained and a multicenter structure of the optical spectra was highlighted. The electron-phonon interactions were also observed in the emission spectra corresponding to the P-3(0) -> H-3(4) transition under different excitation wavelengths. The fluorescence decays of the P-3(0) and D-1(2) levels were measured. The emission cross-sections corresponding to the P-3(0) -> H-3(4) (486.5 nm) and P-3(0) -> F-3(2) (652.7 nm) transitions were found to be sigma(em) = 19 x 10(-20) cm(2) and crem = 15 x 10(-20) cm(2), respectively. The values for other parameters that may predict the possibility of achieving efficient laser emission, especially at 486.5 nm, such as quantum efficiency (eta = 50 %), gain bandwidth (sigma(em) x Iota lambda(eff), = 32.2 x 10(-26) cm(3)), and optical gain (sigma(em) x tau(meas) = 12.86 x 10(-25) cm(2) s) were determined. The obtained results indicate that the Pr:CTGG crystal has a high potential for obtaining efficient laser emission in the blue domain.

In this work, the formation of the orthorhombic phase of ZrO2 together with the minor monoclinic phase were elucidated by X-ray diffraction and transmission electron microscopy. Moreover, oxidized W can be responsible for the formation of oxygen vacancies in the ZrO2 through oxygen scavenging. The ferroelectric properties of the W/ZrO2/W film capacitors were investigated through piezoresponse force microscopy (PFM) and polarizationvoltage measurements. A second-order phase transition from the polar orthorhombic phase to the non-polar tetragonal phase was observed. Density functional theory calculations confirm our experimental results and propose that oxygen vacancies are responsible for the Curie-Weiss temperature of 130 degrees C, significantly lower than the theoretical value for the bulk.

In this work, a ZnO nanowires/graphene nanohybrid was synthesized by a three steps approach. Copper substrates were covered with graphene by chemical vapor deposition, further ZnO nanowires were electrochemically deposited on the as grown graphene on copper and finally a transfer process was employed for moving the heterostructure onto a different substrate. A comprehensive structural analysis which included scanning electron microscopy, X-ray diffraction and Raman measurements revealed that the ZnO nanowires crystallize in wurtzite structure perpendicular to graphene, the process leading to the formation of a nanohybrid heterostructure. The band gap energy of the ZnO nanowires deposited on graphene was estimated to be 3.11 eV, as calculated from the reflectance spectrum analysis. The GGA-PBE+U within Grimme (DFT-D) approach was used to provide an accurate description of the interface structure in terms of electronic and optical properties, confirming that the decrease in the band gap energy of ZnO nanowires is caused by the interaction with the graphene surface. The findings of this study could serve as an experimental and theoretical reference for upcoming studies on ZnO NWs/Graphene nanohybrid-based optoelectronic applications.

Bulk nanocrystalline La0.67Ba0.33_xKxMnO3 (with x = 0, 0.05, 0.1, and 0.2) manganites have been prepared by the modified sol-gel method (Pechini). The single-phase rhombohedral crystal structure with the R-3c (no. 167) space group was verified by X-ray diffraction (XRD) and sustained by Rietveld refinement. As follows from the results of XRD structural analyses, the increase in K-doping triggers an increase in the distortion of the MnO6 octahedra, which eventually causes the narrowing of the eg bandwidth. Mn is in a mixed valence state of Mn4+/ Mn3+ as inferred by X-ray photoelectron spectroscopy. Magnetic measurements confirm that the Curie tem-perature decreases from 348 K for La0.67Ba0.33MnO3 to 316 K for La0.67Ba0.13K0.20MnO3. The increasing of the Mn4+ ion concentration at the B-site sublattice and A-site ionic disorder (sigma 2) breaks up the double exchange interaction between the Mn3+ and Mn4+ ions. The ferromagnetic to paramagnetic second-order magnetic phase transition at TC is also confirmed by electron paramagnetic resonance. According to magnetic field-dependent magnetization isotherms at different temperatures, La0.67Ba0.13K0.20MnO3 shows a relatively large magneto -caloric effect (1400 mJ cm_ 3 K_ 1 at 316 K under 5 T applied magnetic field), which raises the possibility of using this material for room-temperature micro-scale magnetic cooling.

The development of new materials for short-wavelength infrared (SWIR) optical sensors is of high importance for the fast development of different applications, as, for example, Internet of Things, road safety, and pollution monitoring. Group IV SiGe provides more sustainable As-, Cd-, and Pb-free nanomaterials that are cheaper and ecologic and offer easy integration with CMOS technology. This Review is on Ge and SiGe quantum dots/nanocrystals (QDs/NCs) embedded in dielectrics for VIS-SWIR photodetection, in which we highlight and discuss photocurrent mechanisms, correlation of photodetection parameters and characteristics with crystalline structure, morphology and energy bandgap, and applications as photodetectors, optical sensors, phototransistors, and solar cells. The embedding matrix induces NC surface passivation, stress field, and nanocrystallization effects and brings specific advantages depending on the matrix material. SiGe NCs in oxides for VIS-SWIR sensing represents a niche domain, showing high photosensitivity (photocurrent) in SWIR up to 1.8 mu m at room temperature and 2 mu m at 100 K, deeper in SWIR than Ge. By alloying Ge with a small content of Si, NC thermal stability is much improved as the detrimental Ge fast diffusion in oxides is hindered and SWIR photosensing is enhanced due to light absorption in Ge-rich SiGe NCs.

Magnesium ions, MgO nanoparticles and thin films, magnesium alloys and cerium compounds are materials intensively studied due to their corrosion protection, antibacterial and pharmacological properties. In this work, we have designed, prepared and investigated, novel thin films of MgO doped with cerium, deposited on Mg alloy (AZ31) for temporary implants, in order to enhance their life time. More precisely, we report on microstructure and corrosion behavior of MgO pure and doped with 0.1 at % Ce films, fabricated by sol-gel route coupled with spin-coating technique, on AZ31 alloy substrate. A modified sol-gel method that start from magnesium acetylacetonate, cerium nitrate and 2-methoxyethanol (as a stabilizer for the sol) was been used successfully for cerium doped MgO sol precursor preparation. The structure and morphology of the surface of the coatings, before and after immersion for 7-30 d in Hank's solution at 37 degrees C, were characterized by x-ray diffraction (XRD), scanning electron microscopy, high-resolution transmission electron microscope, x-ray photoelectron spectroscopy and Fourier infrared transmittance spectrum (FT-IR). A comparison between the corrosion protection of undoped MgO and MgO doped with 0.1 at % Ce coatings on the AZ31 alloy substrate is performed by electrochemical tests and immersion tests using open circuit potential and electrochemical impedance spectroscopy in Hank's solution, at 37 degrees C. The electrochemical results showed that the protection of the AZ31 alloy substrate against corrosion was better with the doped with 0.1 at % Ce MgO film deposited than with pure MgO coting. The investigations of the films after immersion in Hank's solution, at 37 degrees C, for 7, 21 and 30 d indicated that the grown layer on the film is bone like apatite that suggests a good bioactivity of 0.1 at % Ce-doped MgO coating. Our work demonstrates that the performance corrosion protection of the biodegradable magnesium alloys used for orthopedic applications, in simulated physiological environments (Hank and Ringer) can be enhanced through coating with Ce3+ doped MgO sol-gel thin film.

When a severe plastic deformation (SPD) process is performed at high temperatures, it becomes more versatile. Designed originally for the bulk nanoconstruction of hard-to-deform alloys, high-speed high-pressure torsion (HSHPT) is an SPD method used in this research for assembling multiple layers of shape memory nanocomposites. Three hard-to-deform magnetic alloys in the cast state were used. Soft magnetic shape memory alloys, NiFeGa and FePdMn, and a potentially hard magnetic alloy, CoZr, were assembled in various composites. Both grain refinement and strong layer bonding were achieved in ZrCo/FePdMn and ZrCo/NiFeGa composites in seconds. The very short SPD time is specific to HSHPT because of the intense friction that occurs under high pressures, which generates huge amounts of heat. After SPD, the temperature rises in bulk material like a pulse, being dissipated mostly through heat conduction. The SPD parameters were carefully controlled with an advanced automation system using a programmable logic controller. Nevertheless, the major drawbacks of high-pressure torsion were overcome, and large SPD discs were obtained. Various investigation techniques (optical microscopy, scanning electron microscopy, energy dispersive spectroscopy and atomic force microscopy) show well-defined interfaces as well as a fine and ultrafine structure.