National Institute Of Materials Physics - Romania

Sesquipedalian mud and burnt bricks (second to third century AD) were excavated from the Roman city of Romula located in the Lower Danube Region (Olt county, Romania). Along with local soils, bricks are investigated by petrographic analysis, X-ray fluorescence (XRF), X-ray diffraction (XRD), Fourier transformed infrared spectroscopy (FT-IR), electron microscopy (SEM/EDX), X-ray microtomography (XRT), thermal analysis (DTA-TG), M.ssbauer spectroscopy, magnetometry, colorimetry, and mechanical properties assessment. The results correlate well with each other, being useful for conservation/restoration purposes and as reference data for other ceramic materials. Remarkably, our analysis and comparison with literature data indicate possible control and wise optimization by the ancient brickmakers through the recipe, design (size, shape, and micro/ macrostructure), and technology of the desired physical-chemical-mechanical properties. We discuss the Roman bricks as materials that can adapt to external factors, similar, to some extent, to modern "smart" or "intelligent" materials. These features can explain their outstanding durability to changes of weather/climate and mechanical load.

Flexible composites containing BaTiO3 nanoparticles into Gelatin bio-polymer matrix were designed and investigated. Following the idea that the electric field concentration in corners/edges at the interfaces between dissimilar materials give rise to enhanced effective permittivity in composites, cuboid-like BaTiO3 nanoparticles have been employed as nanofillers into Gelatin matrix by using an inexpensive solution-based processing method. As predicted by finite element method simulations developed for cubic-like inclusions into a homogeneous polymer matrix, the experimental permittivity of xBT-(1-x)Gelatin composites increases when increasing the high-permittivity filler addition. For the composition x = 40 wt% (corresponding to 12 vol% BaTiO3 addition), permittivity reaches epsilon r -15.7 with respect to epsilon r -9.8 of pure Gelatine (measured at 105 Hz), while the average piezoelectric coefficient d33 as determined by piezoelectric force microscopy shows a remarkable increase up to 21 pm/V in composites with x = 40 wt%, in comparison to -7 pm/V in pure Gelatin. By using the experimentally determined material constants, the simulated piezoelectric voltage output vs. time has shown a similar increase (about a doubling of its amplitude) of the harvesting signal in the composite with x = 40 wt% BT, with respect to one of the polymer matrix, thus demonstrating the beneficial role of embedding BT nanoparticles into the biopolymer for increasing the mechanical harvesting response.

Shikonin, a natural compound with pharmaceutical properties, has attracted interest due to its anti-oxidant properties, potential anti-cancer activity and activity over several biological pathways, such as dsDNA transcription/replication of cancer cells and inhibition of pyruvate kinase M2. The electrochemical behavior of shikonin in aqueous media was investigated at glassy carbon electrodes by cyclic and differential pulse voltammetry. The reduction involves the quinone moiety and formation of a semiquinone intermediate. In the absence of dissolved oxygen, the reduction is reversible while in normal atmosphere leads to formation of superoxide cation. The oxidation occurs at the dihydroxy moiety and reversibility was only observed in acid electrolytes. A redox mechanism was proposed. The interaction between shikonin and dsDNA was evaluated in incubated solutions and in situ with the dsDNA-electrochemical biosensor. The mechanism of interaction is time-dependent and follows an initial binding step at the grooves of the double strand leading to conformational modifications recognized through the variation of guanine and adenine oxidation peaks. The in-situ electrochemical production of the semiquinone intermediate leads to a preferential interaction with guanine residues, promoting their oxidation and consequently occurrence 8-oxo-guanine. An interaction mechanism was proposed.

The effectiveness of the electrochemical WO3-modification as a method for improving the photoactivity of native air-formed TiO2 layers was assessed. The way in which a mild laser treatment influences the photo-electrochemical performances of the thus obtained WO3/TiO2 systems was also investigated. At laser-treated electrodes (L-WO3/TiO2), the melting-solidification process induced by the treatment led to a smaller size of the deposited WO3 particles and to their better dispersion on the surface. The treatment also enhanced the surface oxygen deficiency and ensured better relative absorptivity of the oxygenated species on the surface. These features, together with the intrinsic narrower bandgap of the WO3/TiO2 composites, the higher donor density and the lower flat band potential of L-WO3/TiO2 enabled faster kinetic of the oxygen photoanodic evolution. Importantly, the same process exhibited a cathodic shift of its onset potential. The laser treatment also strongly enhanced the photoelectrocatalytic performances for UV-assisted methanol anodic oxidation.

A non-conventional, bioinspired device based on polypyrrole coated electrospun fibrous microstructures, which simultaneously works as artificial muscle and mechanical sensor is reported. Fibrous morphology is preferred due to its high active surface which can improve the actuation/sensing properties, its preparation still being challenging. Thus, a simple fabrication algorithm based on electrospinning, sputtering deposition and electrochemical polymerization produced electroactive aligned ribbon meshes with analogous characteristics as natural muscle fibers. These can simultaneously generate a movement (by applying an electric current/potential) and sense the effort of holding weights (by measuring the potential/current while holding objects up to 21.1 mg). Electroactivity was consisting in a fast bending/curling motion, depending on the fiber strip width. The amplitude of the movement decreases by increasing the load, a behavior similar with natural muscles. Moreover, when different weights were hung on the device, it senses the load modification, demonstrating a sensitivity of about 7 mV/mg for oxidation and - 4 mV/mg for reduction. These results are important since simultaneous actuation and sensitivity are essential for complex activity. Such devices with multiple functionalities can open new possibilities of applications as e.g. smart prosthesis or lifelike robots.

Magnetic nanoparticles (MNPs) have evolved tremendously during recent years, in part due to the rapid expansion of nanotechnology and to their active magnetic core with a high surface-to-volume ratio, while their surface functionalization opened the door to a plethora of drug, gene and bioactive molecule immobilization. Taming the high reactivity of the magnetic core was achieved by various functionalization techniques, producing MNPs tailored for the diagnosis and treatment of cardiovascular or neurological disease, tumors and cancer. Superparamagnetic iron oxide nanoparticles (SPIONs) are established at the core of drug-delivery systems and could act as efficient agents for MFH (magnetic fluid hyperthermia). Depending on the functionalization molecule and intrinsic morphological features, MNPs now cover a broad scope which the current review aims to overview. Considering the exponential expansion of the field, the current review will be limited to roughly the past three years.

The remarkable properties of Eu2+-activated phosphors, related to the broad and intense luminescence of Eu2+ ions, showed a high potential for a wide range of optical-related applications. Oxy-fluoride glass-ceramic containing Europium (II)-doped CaF2 nanocrystals embedded in silica matrix were produced in two steps: glass-ceramization in air at 800 degrees with Eu3+-doped CaF2 nanocrystals embedded followed by Eu3+ to Eu2+ reduction during annealing in reducing atmosphere. The broad, blue luminescence band at 425 nm and with the long, weak tail in the visible range is assigned to the d -> f type transition of the Eu2+ located inside the CaF2 nanocrystals in substitutional and perturbed sites, respectively; the photoluminescence quantum yield was about 0.76. The X-ray photoelectron spectroscopy and Electron paramagnetic spectroscopy confirmed the presence of Eu2+ inside the CaF2 nanocrystals. Thermoluminescence curves recorded after X-ray irradiation of un-doped and Eu2+-doped glass-ceramics showed a single dominant glow peak at 85 degrees C related to the recombination between F centers and Eu2+ related hole within the CaF2 nanocrystals. The applicability of the procedure can be tested to obtain an oxy-fluoride glass-ceramic doped with other divalent ions such as Sm2+, Yb2+, as nanophosphors for radiation detector or photonics-related applications.

Cu2ZnSnS4 (CZTS) functional thin films have been successfully synthesized using the spray pyrolysis method in a single deposition process and under atmospheric pressure. The samples have been deposited on glass substrates under different growth temperatures ranging from 350 ? to 450 ?. The solution has been prepared using Copper chloride dihydrate, Zinc chloride, Tin chloride dihydrate, and Thiourea as Copper, Zinc, Tin and Sulfur sources respectively. The structural, optical, morphological and electrical properties of CZTS films have been investigated. X-ray diffraction (XRD) and Raman spectroscopy have confirmed the kesterite structure of all samples without any secondary phase. The surface morphology and topography of the samples have been examined by scanning electron microscopy (SEM) and atomic force microscopy (AFM). Data from UV-Vis spectroscopy analysis and Hall effect measurement showed that CZTS films elaborated at 400 ? have an optimum band gap (Eg = 1.5 eV), low resistivity (1.7239 x 10(-2) omega.cm), and high conductivity (58.00 (omega.cm)(-1)). Copyright (c) 2022 Elsevier Ltd. All rights reserved.

The high-k-based MOS-like capacitors are a promising approach for the domain of non-volatile memory devices, which currently is limited by SiO2 technology and cannot face the rapid downsizing of the electronic device trend. In this paper, we prepare MOS-like trilayer memory structures based on high-k ZrO2 by magnetron sputtering, with a 5% and a 10% concentrations of Zr in the Zr-ZrO2 floating gate layer. For crystallization of the memory structure, rapid thermal annealing at different temperatures between 500 degrees C and 700 degrees C was performed. Additionally, Al electrodes were deposited in a top-down configuration. High-resolution transmission electron microscopy reveals that ZrO2 has a polycrystalline-columnar crystallization and a tetragonal crystalline structure, which was confirmed by X-ray diffraction measurements. It is shown that the tetragonal phase is stabilized during the crystallization by the fast diffusion of oxygen atoms. The capacitance-voltage characteristics show that the widest memory window (Delta V = 2.23 V) was obtained for samples with 10% Zr annealed at 700 degrees C for 4 min. The charge retention characteristics show a capacitance decrease of 36% after 10 years.

Antiferroelectric random access memory (AFERAM) is one of the newest alternative non-volatile memory technologies to emerge in recent years. ZrO2-based antiferroelectric films are exceptionally well-suited for memory applications with very high cycling endurance (>10(10)) and low operating voltages (< 2 V). Lightly alloying ZrO2 with HfO2 is performed to assess AFERAM device performance with back-end-of-line compatible thin film Zr1-xHfxO2 (x <= 0.13) capacitors. The transition fields associated with antiferroelectric behavior are reduced with more Hf incorporation, yielding a larger magnitude switching polarization and memory window. Cycling endurance beyond 10(10) cycles is conducted on thin film capacitors where wake-up in AFERAM first leads to an increase, then a decrease in the memory window at a cumulative cycle number found to be dependent on the amount of Hf-incorporation. Hf-incorporation into ZrO2 is demonstrated to be a feasible way to improve the memory window in ZrO2-based AFERAM.