National Institute Of Materials Physics - Romania

A novel high-entropy perovskite powder with the composition Bi0.2K0.2Ba0.2Sr0.2Ca0.2TiO3 was successfully synthesized using a modified Pechini method. The precursor powder underwent characterization through Fourier Transform Infrared Spectroscopy and thermal analysis. The resultant Bi0.2K0.2Ba0.2Sr0.2Ca0.2TiO3 powder, obtained post-calcination at 900 C-degrees, was further examined using a variety of techniques including X-ray diffraction, Raman spectroscopy, X-ray fluorescence, scanning electron microscopy, and transmission electron microscopy. Ceramic samples were fabricated by conventional sintering at various temperatures (900, 950, and 1000 C-degrees). The structure, microstructure, and dielectric properties of these ceramics were subsequently analyzed and discussed. The ceramics exhibited a two-phase composition comprising cubic and tetragonal perovskites. The grain size was observed to increase from 35 to 50 nm, contingent on the sintering temperature. All ceramic samples demonstrated relaxor behavior with a dielectric maximum that became more flattened and shifted towards lower temperatures as the grain size decreased.

Fine-tuning of grain sizes can significantly influence the interaction between different dielectric phenomena, allowing the development of materials with tailored dielectric resistivity. By virtue of various synthesis mechanisms, a pathway to manipulate grain sizes and, consequently, tune the material's dielectric response is revealed. Understanding these intricate relationships between granulation and dielectric properties can pave the way for designing and optimizing materials for specific applications where tailored dielectric responses are sought. The experimental part involved the fabrication of dense BCT-BZT ceramics with different grain sizes by varying the synthesis (conventional solid-state reaction route and sol-gel) and consolidation methods. Both consolidation methods produced well-crystallized specimens, with Ba0.85Ca0.15O3Ti0.9Zr0.1 (BCTZ) perovskite as the major phase. Conventional sintering resulted in microstructured and submicron-structured BCT-BZT ceramics, with average grain sizes of 2.35 mu m for the solid-state sample and 0.91 mu m for the sol-gel synthesized ceramic. However, spark plasma sintering produced a nanocrystalline specimen with an average grain size of 67.5 nm. As the grain size decreases, there is a noticeable decrease in the maximum permittivity, a significant reduction in dielectric losses, and a shifting of the Curie temperature towards lower values.

The aim of this work is to highlight the influence of UV light on the hydrolysis reaction of nifedipine (NIF) in the presence of alkaline solutions. In this context, the photodegradation of NIF in the absence of alkaline solutions caused (a) a change in the ratio between the absorbances of three bands in the UV-VIS spectra localized at 224-240 nm, 272-276 nm and 310-340 nm, assigned to the electronic transitions of -COOCH3 groups, -NO2 groups and a heterocycle with six atoms; (b) a red-shift of the photoluminescence (PL) band from 458 nm to 477 nm, simultaneous with an increase in its intensity; (c) a decrease in the ratio of the Raman line intensities, which peaked at 1224 cm-1 and 1649 cm-1, associated with the vibrational modes of -C-C-O in the ester group and C=C stretching; and (d) a decrease in the ratio between the absorbances of the IR bands, which peaked at 1493 cm-1 and 1223 cm-1, associated with the vibrational modes of the -NO2 group and C-N stretching. These changes were explained considering the NIF photodegradation reaction, which leads to the generation of the compound 4-(2-nitrosophenyl)-2.6-dimethyl-3.5-dimethoxy carbonyl pyridine. The interaction of NIF with NaOH in the absence of UV light was demonstrated to induce changes in the vibrational mode of the -C-C-O bond in the ester group. The photodegradation of NIF after its reaction with NaOH induces significant changes highlighted in its (a) UV-VIS spectra, by the shift of the absorption band at 238 nm; (b) PL spectra, by the supraunitary value of the ratio between the emission band intensities at 394-396 nm and 450 nm; (c) Raman spectra, by the change in the ratio between the intensities of the lines that peaked at 1224 cm-1 and 1649 cm-1 from 0.61 to 0.49; and (d) FTIR spectra, by the lowered absorbance of the IR band at 1493 cm-1 assigned to the vibrational mode of the -NO2 group as a result of the generation of the nitroso compound. These changes were explained considering the hydrolysis reaction products of NIF, as the nitroso compound is converted to a lactam-type compound. The photodegradation reaction rate constants of NIF and NIF after interaction with NaOH were also reported. The decrease in thermal stability of NIF samples after interaction with NaOH, as well as of NIF after exposure to UV light compared to NIF prior to exposure to UV light, was demonstrated by thermogravimetry, and the key fragments were confirmed by mass spectrometry.

A magnesium-doped hydroxyapatite in chitosan matrix (MgHApC) sample was developed as a potential platform for numerous applications in the pharmaceutical, medical, and food industries. Magnesium-doped hydroxyapatite suspensions in the chitosan matrix were obtained by the coprecipitation technique. The surface shape and morphological features were determined by scanning electron microscopy (SEM). The hydrodynamic diameter of the suspended particles was determined by Dynamic light scattering (DLS) measurements. The stability of MgHApC suspensions was evaluated by ultrasonic measurements. The hydrodynamic diameter of the MgHApC particles in suspension was 29.5 nm. The diameter of MgHApC particles calculated from SEM was 12.5 +/- 2 nm. Following the SEM observations, it was seen that the MgHApC particles have a spherical shape. The Fourier-transform infrared spectroscopy (FTIR) studies conducted on MgHApC proved the presence of chitosan and hydroxyapatite in the studied specimens. In vitro antimicrobial assays were performed on Escherichia coli ATCC 25922, Staphylococcus aureus ATCC 25923, Pseudomonas aeruginosa ATCC 27853, and Candida albicans ATCC 10231 microbial strains. The antimicrobial experiments showed that MgHApC exhibited very good antimicrobial properties against all the tested microorganisms. More than that, the results of the in vitro studies revealed that the antimicrobial properties of the samples depend on the incubation time. The evaluation of the sample's cytotoxicity was performed using the human colon cancer (HCT-8) cell line. Our results suggested the great potential of MgHApC to be used in future applications in the field of biomedical applications (e.g., dentistry, orthopedics, etc.).

Herewith, we investigated the capacitive properties of hybrid nanometric architectures consisting of tungsten oxide nanoparticles deposited on graphite (WOx/G) and graphite coated with highly-porous carbon nanowall layers (WOx/CNW/G). The deposition of the nanostructured oxide was performed by a plasma-assisted sublimation, vapor transport and condensation technique. The samples containing the CNW interlayer show superior areal capacitances making this architecture and its fabrication route promising approaches for supercapacitor applications. Thus, areal capacitances of WOx/CNW/G and WOx/G, estimated from galvanostatic chargedischarge tests (GCD) at an applied density current of 1 mA cm-2, are 1247.2 mF cm-2 and 527.3 mF cm-2, respectively. From SEM and XPS investigations, it was observed that CNW promotes the formation of a high amount of small tungsten oxide particles, homogeneously distributed on electrode surface, and facilitates the formation of highly conductive tungsten nitride species, resulting in electrodes with remarkable charge-storage capacity.

This work reports the design and synthesis of novel oxadiazole-decorated azobenzenes, structural analysis of the resulting compounds and behavior under light irradiation. The synthetic strategy involved constructing amino functionalized heterocyclic key intermediates which were used either to yield electrophilic diazonium salts able to react with phenol moieties or as nucleophilic partners in Bayer-Mills reaction with nitroso-substituted derivatives. The amino-derived oxadiazole intermediates were investigated by absorption and emission spectroscopy providing blue and green emitted light. The target oxadiazole-decorated azobenzenes were structurally characterized, including solid-state structures, and subsequently used in irradiation experiments in order to take advantage of the azo group known to provide photoswitching abilities. We noticed quenching of the emissive properties in presence of the azo group; however, all compounds were very stable to repeated cycles of light irradiation. In addition, according to structural diversification we could obtain half-lives of the meta stable isomers within hours to hundreds of hours range. The experimental results were very well correlated with DFT calculations. The synthesis of novel oxadiazole-decorated azobenzenes using amino functionalised heterocyclic intermediates used either to provide electrophilic diazonium salts able to react with phenols or as nucleophilic partners in Bayer-Mills reaction is reported in this work. The oxadiazole-decorated azobenzenes were used in irradiation experiments to determine the parameters that characterize a photoswitch, yielding appealing results. The experimental results were very well correlated with DFT calculations.+image

A critical brief review of the evolution of the ideas describing the matter, with emphasis on concepts relevant to the journal's goals: surfaces, interfaces, and interphases is presented. The complex relationship between interphase and interface, including the role of the submicron confinement on the physical and chemical properties of matter are analyzed from both theoretical and experimental standpoints. The most important consequences triggered by the recognition of interphases are briefly discussed. Most matter (at a macroscopic scale) is dominated by bulk behavior. The rapid advances in materials and especially the accelerated progress in the synthesis and characterization of submicron materials and associated technologies, labeled as the "nano revolution", revived the research on interfaces and interphases at atomic and molecular scales. It is suggested that interphase ignites a new kind of material, whose "bulk physical features" have been distorted by the submicron confinement. Such an "interphase surface" (for example a drop of gold with a diameter smaller than a few nanometers, or a few layers of graphene), may exist free standing and be stable. These materials, which no more exhibit the bulk properties will be tentatively referred to as "Sutter" ("Sutter" defines an abbreviation that involves both surface and matter concepts). Sutter is characterized by the fact that its physical and chemical properties are controlled by the interphase. It is concluded that Sutter is essentially a submicron phase of the matter, that exhibits size-dependent features. Sutter materials may be embedded in various materials (such as polymers, metals, and alloys) as nanocomposites, thus projecting specific features at the macroscopic scale. Most free standing interphases may be considered as Sutter materials or phases. The interface does not qualify as a Sutter material.

This study focuses on the properties of the BiOi (interstitial Boron-interstitial Oxygen) and CiOi (interstitial Carbon-interstitial Oxygen) defect complexes by 5.5MeV electrons in low resistivity silicon. Two different types of diodes manufactured on p-type epitaxial and Czochralski silicon with a resistivity of about 10 Omega center dot cm were irradiated with fluence values between 1x10(15) cm(-2) and 6x10(15) cm(-2). Such diodes cannot be fully depleted and thus the accurate evaluation of defect concentrations and properties (activation energy, capture cross-section, concentration) from Thermally Stimulated Currents (TSC) experiments alone is not possible. In this study we demonstrate that by performing Thermally Stimulated Capacitance (TS-Cap) experiments in similar conditions to TSC measurements and developing theoretical models for simulating both types of BiOi signals generated in TSC and TS-Cap measurements, accurate evaluations can be performed. The changes of the position-dependent electric field, the effective space charge density N-eff profile as well as the occupation of the BiOi defect during the electric field dependent electron emission, are simulated as a function of temperature. The macroscopic properties (leakage current and..eff) extracted from current-voltage and capacitance-voltage measurements at 20 degrees C are also presented and discussed.

Because of their significant magnetocaloric properties, Ca and Pb-doped LaMnO3 can be employed in magnetic refrigeration systems. The partial substitution effect of Ca2+ by Pb2+ cations on the structural, magnetocaloric properties, and critical behavior of mixed valence perovskites La0.8Ca0.2-xPbxMnO3 (0 <= x <= 0.15), synthesized by the flash combustion route, was studied in this work. The presence of structural transformations of the prepared ceramics from an orthorhombic structure (Pbnm space group) for samples with x <= 0.05 to a rhombohedral system (R (3) over barc space group) for x >= 0.1 was detected by X-ray diffraction analysis, which is related to the A-site disorder. The field-cooled (FC) magnetization indicated a second-order ferromagnetic-paramagnetic transition for the investigated samples when the temperature was increased. Due to the change in the Mn3+/Mn4+ ratio, substituting Ca2+ with larger Pb2+ ions increases the Curie temperature (T-C) by increasing Pb doping content from 90 K for x = 0 to 205 K for x = 0.15. The magnetization isotherms of all samples showing a second-order phase transition were studied, where an applied magnetic field of 5 T, the value of maximum magnetic entropy variation /Delta S-M(max)/ for the sample with x = 0.15 was estimated to be 2.73 Jkg(-1) K-1. In addition, it has a significant relative cooling power of about 276 Jkg(-1) under the same applied magnetic field strength. The critical behavior of the samples was investigated close to T-C. The exponent values were identical to the mean-field method, indicating a large disorder of spin magnetic moments in the perovskite compounds.

In this study, a sol-gel film based on lead sulfide (PbS) quantum dots incorporated into a host network was synthesized as a special nanostructured composite material with potential applications in temperature sensor systems. This work dealt with the optical, structural, and morphological properties of a representative PbS quantum dot (QD)-containing thin film belonging to the Al2O3-SiO2-P2O5 system. The film was prepared using the sol-gel method combined with the spin coating technique, starting from a precursor solution containing a suspension of PbS QDs in toluene with a narrow size distribution and coated on a glass substrate in a multilayer process, followed by annealing of each deposited layer. The size (approximately 10 nm) of the lead sulfide nanocrystallites was validated by XRD and by the quantum confinement effect based on the band gap value and by TEM results. The photoluminescence peak of 1505 nm was very close to that of the precursor PbS QD solution, which demonstrated that the synthesis route of the film preserved the optical emission characteristic of the PbS QDs. The photoluminescence of the lead sulfide QD-containing film in the near infrared domain demonstrates that this material is a promising candidate for future sensing applications in temperature monitoring.