National Institute Of Materials Physics - Romania

Mg2Si thermoelectric compound was obtained by dry and wet (isohexane and benzene) mechanical alloying route. The Mg2Si compound was characterised by X-ray diffraction, scanning electron microscopy (SEM), differential scanning calorimetry (DSC), laser particle size analysis and thermoelectric measurements. After 14 h of milling, the complete reaction of the elements is achieved by both routes. The powders particle size distribution obtained after 14 h of dry or wet milling (using benzene) reveals a bimodal curve. The wet milling moves the particle size distribution towards smaller particle sizes. The SEM analysis confirms the results of particles size analysis. DSC analyses performed for samples milled up to 14 h present stress relief and recrystallisation thermal events. For the benzene wet-milled sample, the DSC curve shows an additional thermal event at 350'C, associated with benzene removal. Thermoelectric properties were determined on spark plasma sintered compacts. The milling process with benzene leads to a higher value of Seebeck coefficient (z580 mV/K). The electrical conductivity is low at room temperature and increases exponentially with temperature. (c) 2023 The Author(s). Published by Elsevier B.V. This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).

In this work, polyvinylidene fluoride (PVDF) fibres loaded with mineral powders, such as titanium dioxide (TiO2), barium titanate (BaTiO3), and calcium magnesium silicate (CaxMgSi2Oy), were prepared by electrospinning polymeric suspensions containing 20 wt.% PVDF and 3 wt.% powder. The piezoelectric polymer was combined with powders having antibacterial, piezoelectric, or bioactive properties, respectively, in the desire to obtain multifunctional materials compatible with the requirements of the medical field. All powders were characterized in terms of morphology and crystalline structure, which confirmed the nanometric character of TiO2 samples and micrometric one for the other two, as well as the lower crystallite size for TiO2 specimens as against BaTiO3 and CaxMgSi2Oy. The final fibrous scaffolds were homogeneous, composed of individual fibres with a diameter below 1 mu m and decorated with aggregates of inorganic particles, placed either inside the fibres or attached to their surface. The biological evaluation demonstrated the superiority of the composites towards the plain polymer in terms of cell viability.

Dynamic hysteresis effects have been long known to occur in the current density-voltage characteristics of perovskite solar cells, with the ionic migration being identified as the primary factor. The hysteretic effects impacted early studies by the uncertainty in the evaluation of the power conversion efficiency, while currently, potential links to degradation mechanisms are the focus. Therefore, understanding ion migration is a central goal, typically addressed by performing a combined large and small signal analysis. The reported large capacitive and inductive effects created controversies with respect to the underlying mechanisms, yielding essentially two classes of models, one based on the large accumulation capacitances and the other based on the ionic modulation of the collected current. We introduce here an equivalent circuit model and interpret these phenomena in terms of recombination current modulation, identifying the distinct contributions from ion current and ionic charge accumulations. These contributions to the recombination current are associated with capacitive and inductive effects, respectively, and we corroborate the numerical simulations with electrochemical impedance spectroscopy measurements. These show the role of the recombination currents of photogenerated carriers in producing both capacitive and inductive effects as the illumination is varied. Moreover, we provide a bridging point between the two classes of models and suggest a framework of investigation of defect states based on the observed inductive behavior, which would further aid the mitigation of the degradation effects.

The evaluation of corrosion inhibition of mild steel (M-S) in 1.0 M HCl solution in the absence and the presence of different concentrations of (E)-3-(5-bromo-2-hydroxystyryl)quinoxalin-2(1H)-one (FR178) and (E)-3-(5-fluoro-2-hydroxystyryl)quinoxalin-2(1H)-one (FR179) was studied by electrochemical,and theoretical measurements. These organic inhibitors have proven to be effective corrosion inhibitors for the protection of mild steel. Increasing concentrations of inhibitors contributed to high inhibition efficiencies, which were attributed to the simple blocking action of the anodic and cathodic sites by adsorption of the inhibitors molecules onto the M-S surface. Their inhibition efficiencies can reach about 90.9 % and 91.5 % when the optimal concentration is 10-3M for the two inhibitors FR178 and FR179 respectively.On the other hand, as the temperature rises, the anticorrosion capability of both FR178 and FR179 diminishes slightly and attains 82 % and 84 % respectively at the temperature of 328 K.Potentiodynamique polarization (PDP) and electrochemical impedance spectroscopy (EIS) demonstrated that both inhibitors examined act as mixed-type inhibitors.Furthermore, X-ray diffraction (XRD) and scanning electron microscopy coupled to energy dispersive spectroscopy (SEM/EDS) measurements indicated the formation of a protective layer adsorbed on the mild steel surface. The density functional theory (DFT) and molecular dynamics (MD) simulations were carried out to examine the correlation between molecular and chemical reactivity. The obtained results were found to be consistent with the experimental findings.

A multi-step ion-exchange methodology was developed for the fabrication of Cu(LaTa2O7)(2) lamellar architectures capable of wastewater depollution. The (001) diffraction line of RbLaTa2O7 depended on the guest species hosted by the starting material. SEM and TEM images confirmed the well-preserved lamellar structure for all intercalated layered perovskites. The UV-Vis, XPS, and photocurrent spectroscopies proved that Cu intercalation induces a red-shift band gap compared to the perovskite host. Moreover, the UV-Vis spectroscopy elucidated the copper ions environment in the Cu-modified layered perovskites. H-2-TPR results confirmed that Cu species located on the surface are reduced at a lower temperature while those from the interlayer occur at higher temperature ranges. The photocatalytic degradation of phenol under simulated solar irradiation was used as a model reaction to assess the performances of the studied catalysts. Increased photocatalytic activity was observed for Cu-modified layered perovskites compared to RbLaTa2O7 pristine. This behavior resulted from the efficient separation of photogenerated charge carriers and light absorption induced by copper spacer insertion.

Two novel fluorescent mesoporous silica-based hybrid materials were obtained through the covalent grafting of [4-hydrazinyl-7-nitrobenz-[2,1,3-d]-oxadiazole (NBDH) and N-1-(7-nitrobenzo[c][1,2,5]-oxadiazol-4-yl) benzene-1,2-diamine (NBD-PD), respectively, inside the channels of mesoporous silica SBA-15. The presence of fluorescent organic compounds (nitrobenzofurazan derivatives) was confirmed by infrared spectroscopy (IR), X-ray photoelectron spectroscopy (XPS), thermal analysis (TG), and fluorescence spectroscopy. The nitrogen physisorption analysis showed that the nitrobenzofurazan derivatives were distributed uniformly on the internal surface of SBA-15, the immobilization process having a negligible effect on the structure of the support. Their antioxidant activity was studied by measuring the ability to reduce free radicals DPPH (free radical scavenging activity), in order to formulate potential applications of the materials obtained. Cytotoxicity of the newly synthesized materials, SBA-NBDH and SBA-NBD-PD, was evaluated on human B16 melanoma cells. The morphology of these cells, internalization and localization of the investigated materials in melanoma and fibroblast cells were examined through fluorescence imaging. The viability of B16 (3D) spheroids after treatment with SBA-NBDH and SBA-NBD-PD was evaluated using MTS assay. The results showed that both materials induced a selective antiproliferative effect, reducing to various degrees the viability of melanoma cells. The observed effect was enhanced with increasing concentration. SBA-NBD-PD exhibited a higher antitumor effect compared to SBA-NBDH starting with a concentration of 125 mu g/mL. In both cases, a significantly more pronounced antiproliferative effect on tumor cells compared to normal cells was observed. The viability of B16 spheroids dropped by 40% after treatment with SBA-NBDH and SBA-NBD-PD at 500 mu g/mL concentration, indicating a clear cytotoxic effect of the tested compounds. These results suggest that both newly synthesized biomaterials could be promising antitumor agents for applications in cancer therapy.

In this work, we report the synthesis of calcium phosphate-chitosan composite layers. Calcium phosphate layers were deposited on titanium substrates by radio-frequency magnetron sputtering technique by varying the substrate temperature from room temperature (25 degrees C) up to 100 and 300 degrees C. Further, chitosan was deposited by matrix-assisted pulsed laser evaporation technique on the calcium phosphate layers. The temperature at the substrate during the deposition process of calcium phosphate layers plays an important role in the embedding of chitosan, as scanning electron microscopy analysis showed. The degree of chitosan incorporation into the calcium phosphate layers significantly influence the physico-chemical properties and the adherence strength of the resulted layers to the substrates. For example, the decreases of Ca/P ratio at the addition of chitosan suggests that a calcium deficient hydroxyapatite structure is formed when the CaP layers are generated on Ti substrates kept at room temperature during the deposition process. The Fourier transform infrared spectroscopy analysis of the samples suggest that the PO43-/CO32- substitution is possible. The X-ray diffraction spectra indicated that the crystalline structure of the calcium phosphate layers obtained at the 300 degrees C substrate temperature is disturbed by the addition of chitosan. The adherence strength of the composite layers to the titanium substrates is diminished after the chitosan deposition. However, no complete exfoliation of the layers was observed.

A quaternary Fe-Pt-Nb-B alloy has been fabricated by the melt spinning method with the purpose of the formation of crystallographically coherent multiple magnetic phases, emerging from the same metastable precursor, as well as to investigate the phase interactions and the influence of their coupling on magnetic performances. For this purpose, extended structural and magnetic investigations were undertaken by making use of X-ray diffraction, transmission electron microscopy, and Fe-57 Mossbauer spectroscopy, as well as magnetic measurements using SQUID magnetometry. It was documented that intermediate metastable phases formed during primary crystallization, in intermediate stages of annealing, and a growth-dominated mode was encountered for the secondary crystallization stage upon annealing at 700 degrees C and 800 degrees C where fcc Fe3Pt and fct Fe2B polycrystalline were formed. The Mossbauer investigations have documented rigorously the hyperfine parameters of each of the observed phases. The fcc A1 FePt phase was shown to exhibit a peculiar ferromagnetic transition, and this transition has been proven to occur gradually between 300 K and 77 K. The magnetic measurements allowed us to identify the annealing at 700 degrees C as optimal for obtaining good magnetic features. Coercive field dependence shows similarities to the random anisotropy model for samples annealed at 500 degrees C to 700 degrees C which are nanocrystalline. These results show good perspectives for use in applications where different magnetic states are required at different operating temperatures.

High density (94-98% of the theoretical density) MgB2 samples added with C6H10Ge2O7 and cubic BN with compositions (MgB2)(1-x)(Ge2C6H10O7)(0.0028)(cBN)(x) (x = 0.003, 0.005, 0.007, 0.01) and (MgB2)(1-y)(Ge2C6H10O7)(y)(cBN)(0.005) (y = 0.0014, 0.0028, 0.005, 0.0075) were obtained by spark plasma sintering technique. For optimum doped samples with x = 0.005-0.007 and y = 0.0028-0.005, a weak enhancement of zero-field critical current density J(c0), irreversibility field H-irr, and volume pinning force F-p,F-max was determined. This behavior is very different from similar samples added with a single additive for which H-irr has a large enhancement. Consequently, it suggests the presence of opposite structural and microstructural effects induced by the additives. These effects, on the one hand, are discussed to decrease the sensitivity of MgB2 superconducting properties in the co-added samples comparative to samples added with C6H10Ge2O7, and, on the other hand, they contribute to anomalies that were found when assessing the pinning force-related parameters by the universal scaling law.

We report on hydroxyapatite (HA) of biological-origin doped with lithium carbonate (LiC) and lithium phosphate (LiP) coatings synthesized by Pulsed laser deposition onto Ti6Al4V substrates fabricated by the Additive manufacturing technique. A detailed comparison from the structural, morphological, chemical composition, wetting behavior and bonding strength standpoints of as-deposited (NTT) and post-deposition thermal-treated (TT) coatings at temperatures ranging from 400 to 700 degrees C (i.e., TT400-TT700), was performed. Structural investigations indicated a complete crystallization of the initially amorphous HA-based layers at temperatures in excess of 500 degrees C. The morphological analyses emphasized the rough appearance of the film surfaces, consisting of particulates whose dimensions increased at higher temperatures, with an emphasis on LiC coatings. AFM investigations evidenced rough surfaces, with a clear tendency to increase in corrugation with the applied temperature, in the case of LiC coatings. A hydrophobic behavior was observed for control, NTT and TT400 samples, whilst a radical shift towards hydrophilicity was demonstrated for both types of structures at higher temperatures. In the case of TT500-TT700 coatings, the pull-out adherence values increased considerably compared to control ones. Taking into consideration the obtained results, the positive influence of post-deposition thermal treatments (performed at higher temperatures) on the physical-chemical and mechanical properties of LiC and LiP coatings was indicated. Alongside these improved characteristics observed at elevated temperatures, the sustainable nature of the used BioHA materials should recommend them as viable alternatives to synthetic HA ones for bone implant applications.