National Institute Of Materials Physics - Romania

The present work proposes the simultaneous removal of these classes of pollutants by a catalytic hydrotreatment processes. For this purpose, bimetallic Pd-Cu catalysts (with mass ratio Pd:Cu of 4:1) supported on macroporous strong base anion resin were prepared by different methods. The catalysts were characterized (by XRD, SEMEDX, XPS, AAS and H-2 chemisorption) and tested in a continuous flow system. The selected catalyst preparation protocol consists in a two-step method, which implies the deposition of palladium by ion exchange and the subsequent deposition of copper by controlled reaction on the surface of the pre-reduced palladium. The effectiveness of the catalyst in the simultaneous reduction of nitrate and hydrodechlorination of 4-chlorophenol was demonstrated. By adjusting the initial pH and the flow rate of the aqueous solution, nearly complete hydrodechlorination of 4-chlorophenol can occur together with selective nitrate reduction at a conversion of 95% and a selectivity to N-2 of 92% (this value contains the contribution of all gaseous products, including the eventually formed NOx). The bimetallic catalyst was found to remains relatively stable after 100 h of test time.

The properties of ferroelectric materials, which were discovered almost a century ago(1), have led to a huge range of applications, such as digital information storage(2), pyroelectric energy conversion(3) and neuromorphic computing(4,5). Recently, it was shown that ferroelectrics can have negative capacitance(6-11), which could improve the energy efficiency of conventional electronics beyond fundamental limits(12-14). In Landau-Ginzburg-Devonshire theory(15-17), this negative capacitance is directly related to the double-well shape of the ferroelectric polarization-energy landscape, which was thought for more than 70 years to be inaccessible to experiments(18). Here we report electrical measurements of the intrinsic double-well energy landscape in a thin layer of ferroelectric Hf0.5Zr0.5O2. To achieve this, we integrated the ferroelectric into a heterostructure capacitor with a second dielectric layer to prevent immediate screening of polarization charges during switching. These results show that negative capacitance has its origin in the energy barrier in a double-well landscape. Furthermore, we demonstrate that ferroelectric negative capacitance can be fast and hysteresis-free, which is important for prospective applications(19). In addition, the Hf0.5Zr0.5O2 used in this work is currently the most industry-relevant ferroelectric material, because both HfO2 and ZrO2 thin films are already used in everyday electronics(20). This could lead to fast adoption of negative capacitance effects in future products with markedly improved energy efficiency.

The aim of the present paper is to develop ceramic thin films by laser ablation in order to improve the biological behaviour of metallic implants dedicated to hard tissue restoration. The composition of the coatings was selected within SiO2-P2O5-CaO-MgO-ZnO-CaF2 system, while their processing has gone through two stages: target preparation via a wet chemistry approach and films deposition through a physical deposition method, on titanium substrates. The characteristics of the final layered structures were evaluated by X-ray diffraction, Fourier-transform infrared spectroscopy, scanning and transmission electron microscopy, energy-dispersive X-ray spectroscopy and selected area electron diffraction. In vitro investigation techniques were employed for the bioactivity and biocompatibility assessment. The results indicated the growth of nanostructured akermanite-based thin films with an excellent bioactivity and a good effect on stem-type cells, which validates the suitability of such structures for medical implant applications.

Spirobifluorene-based porous organic polymers (POP) were synthesized following two different protocols; the acetylenic coupling reaction conditions and the Sonogashira cross-coupling reaction. These were utilized as support for the hydrogenation of a series of species containing unsaturated C=C and C=O bonds (4-nitrostyrene, 4-bromobenzophenone, acetophenone, 7-nitro-1-tetralone and 1,2-naphtoquinone confirmed their efficiency). POP1 prepared via a copper-catalysis protocol was completely inactive, while POP2-4 containing residual Pd exhibited different activities in accordance to the accessibility of the substrates to the metal. Further deposition of 0.5wt% Pd led to active and stable catalysts. They were easily separated by filtration, and after re-dispersion, afforded the same performances for ten successive cycles. This study also evidenced the specific role of the support in these reactions by comparing the behavior of Pd/POP with that of a Pd/C catalyst with the same loading of palladium. The deposition of Pt on these supports led to sub-nanometric particles and, in accordance, to a different catalytic behavior reflected merely by differences in the selectivity.

We have investigated the effect of thermal annealing on the structure of single and stacked phase change memory films based on SnSe and GaSb. Samples were prepared by pulsed laser deposition and investigated by X-ray absorption spectroscopy (XAS) and X-ray diffraction (XRD) methods. Electrical resistance versus temperature investigations showed crystallisation temperatures of 292 degrees C and 198 degrees C for SnSe and GaSb single films, respectively. Above the transition temperature, GaSb crystallises into a face-centered cubic structure, whereas SnSe has an orthorhombic arrangement. Annealing at three temperatures (160 degrees C, 250 degrees C and 350 degrees C) of the SnSe\GaSb stacked films promotes bond breaking, atom diffusion between the two layers and formation of new phases. At 160 degrees C, GaSb films crystallise partially and no effect is observed on the crystallinity of SnSe films. After 250 degrees C, rhombohedral SnSb emerges in addition to GaSb complete crystallisation. A major, completely new, body-centered orthorhombic unindexed quaternary Ga-Sn-Sb-Se phase formation was observed in the samples annealed at 350 degrees C. The GaSb crystallites are fully dissolved and we have observed the formation of a minor hexagonal SnSe2 phase. The analysis of EXAFS data, measured at Se and Ga K-edges, revealed changes in the local atomic environment as a function of the annealing temperature. A tetrahedral configuration is obtained for the Ga atoms in both as-deposited and annealed samples, whereas Se is mostly bivalent in the amorphous samples and has an octahedral arrangement in crystalline SnSe. Our results show that inter-layer diffusion should always be considered and evaluated when designing memory cells composed of stacked phase change chalcogenide films.

Manganese is deposited at high temperature on (001) oriented ferroelectric lead zirco-titanate prepared in two different ways: sputter-annealed or just simply annealed in ultrahigh vacuum. Room temperature ferromagnetism (FM) is obtained for Mn deposited on sputter-annealed substrates, while for the other sample preparation a paramagnetic behaviour is obtained. Also, for the first case a clear inwards component of the polarization P( - ) is observed by X-ray photoelectron spectroscopy and piezoresponse force microscopy. Composition analysis evidenced formation of Pb vacancies in the case of FM - P(( - ) )sample, consistent with hole formation near the surface, needed both to stabilize the inwards polarization state and to intermediate ferromagnetism between Mn2+ ions. The indirect exchange ferromagnetism mediated by holes is stronger, most probably because the interaction energy is proportional with the carrier effective mass. Also, whereas in the case of unsputtered substrate a stable surface Mn oxide is formed, defect formation by sputtering seems to favor Mn migration inside the sample. This also induces the formation of a thin film where ferromagnetism and the orientation of ferroelectric polarization might have the same origin, i. e. holes accumulated near the outer surface.

Our study reports the fabrication and characterization (surface morphology, hydrophobicity/hydrophilicity, photocatalytic efficiency) of cotton fibers treated by various methods with graphene oxide decorated with Fe, N-doped TiO2 nanoparticles. Designed as prospective industrial self-cleaning, antimicrobial and biocompatible textiles, microbiological and cytotoxicity tests were performed on these particles-treated fibers to validate their qualities. The photocatalytic effect was dependent on chemicals used to disperse the nanoparticles, the parameters of the treatment, the fiber structure and composition of the material. The double and triple treatment of the textiles with the same particle dispersion resulted in a relatively uniform coverage of cotton fibers with relatively large amounts of particles. A larger amount of doped TiO2 particles demonstrated a better photo - catalytic effect under visible light. The material's hydrophobicity increased with the number of treatments due to the deposition of successive layers of reduced graphene, ensuring self-cleaning properties. The photocatalyst-treated cotton fabrics exhibited an increased resistance to Enterococcus faecalis and Escherichia coli colonization, and also high biocompatibility, as they did not affect the cell viability, membrane integrity and morphology, nor induce inflammation. All these data confirm the improved properties of cotton fibers treated with graphene oxide decorated with Fe, N-doped TiO2 particles in order to be used as industrial self-cleaning and biocompatible textiles.

Indium tin oxide (ITO) thin films were grown on nanopatterned glass substrates by the pulsed laser deposition (PLD) technique. The deposition was carried out at 1.2 J/cm(2) laser fluence, low oxygen pressure (1.5 Pa) and on unheated substrate. Arrays of periodic pillars with widths of similar to 350 nm, heights of similar to 250 nm, and separation pitches of similar to 1100 nm were fabricated on glass substrates using UV nanoimprint lithography (UV-NIL), a simple, cost-effective, and high throughput technique used to fabricate nanopatterns on large areas. In order to emphasize the influence of the periodic patterns on the properties of the nanostructured ITO films, this transparent conductive oxide (TCO) was also grown on flat glass substrates. Therefore, the structural, compositional, morphological, optical, and electrical properties of both non-patterned and patterned ITO films were investigated in a comparative manner. The energy dispersive X-ray analysis (EDX) confirms that the ITO films preserve the In2O3:SnO2 weight ratio from the solid ITO target. The SEM and atomic force microscopy (AFM) images prove that the deposited ITO films retain the pattern of the glass substrates. The optical investigations reveal that patterned ITO films present a good optical transmittance. The electrical measurements show that both the non-patterned and patterned ITO films are characterized by a low electrical resistivity (<2.8 x 10(-4)). However, an improvement in the Hall mobility was achieved in the case of the nanopatterned ITO films, evidencing the potential applications of such nanopatterned TCO films obtained by PLD in photovoltaic and light emitting devices.

Boron carbide added with 0-20 wt% carbon fibers was subject to Si infiltration. Samples mainly consist of B13C2, beta-SiC and unreacted Si. Some amount of SiB6 and alpha-SiC was also detected, while formation of B-12(B,C,Si)(3) phase was suppressed due to short infiltration time. The carbon fibers react with Si and result in formation of a composite core-shell fiber with SiC-shell and C-core. Theoretical estimations suggest that these composite fibers have a strong influence on the enhancement of the bending strength. Although apparently in good agreement with experimental data showing an increase of bending strength up to 510 +/- 27 MPa in the sample with 10 wt% carbon fiber, the implications of phase changes with the carbon fiber amount has to be carefully considered. At higher amounts of carbon fibers, bending strength decreases.

In this work, we report on the synthesis and characterization of BNT-BT0.08/CoFe2O4 biphasic composite with core-shell structure. This artificial core (BNT-BT0.08/shell (CoFe2O4) heterostructure was prepared by sol-gel method and the resulting composite was characterized in term of microstructure, dielectric, piezoelectric and magnetic properties. BNT-BT0.08/CoFe2O4 sintered ceramic shows high permittivity (epsilon' >= 30) and high dielectric losses (tan delta >= 10) in the low frequency range (nu <= 10(4) Hz), remnant polarization (Pr) of similar to 7.7 mu C/cm(2) and, remanent magnetization (Mr) of 24 emu/g at 5 K and of 14 emu/g, at room temperature. The present study reveals that the ferroelectric, piezoelectric and magnetic properties of this new architectured composite depend on the amount of each component and, can be tailored by adjusting their synthesis conditions. BNT-BT0.08/CoFe2O4 core-shell material investigated in this work provides a novel way to exploit new applications for the multifunctional composite, such as piezoelectric sensor, magnetoelectronic sensors and data storage devices.