National Institute Of Materials Physics - Romania

(1) Background: The high-voltage anodic-plasma (HVAP) coating technique has a series of specificities that are not simultaneously met in other deposition methods. This paper aimed at assessing the potential of HVAP to synthesize quality multilayers for X-ray optics. (2) Methods: Nanolayers of W, Ta, B, and Si were deposited as mono-, bi-, and multilayers onto very smooth glass substrates by HVAP, and their thickness and density were analyzed by X-ray reflectometry. The minimal film thickness needed to obtain continuous nanolayers was also investigated. (3) Results: Nanolayer roughness did not increase with layer thickness, and could be lowered via deposition rate, with values as low as 0.6 for the W nanolayer. Minimal film thickness for continuous films for the studied metals was 4 nm (W), 6 nm (Ta), 2.5 nm (B), and 6 nm (Si). (4) Conclusions: The investigation revealed the range of parameters to be used for obtaining quality nanolayers and multilayers by HVAP. Advantages and possible improvements are discussed. This deposition technique can be tailored for demanding applications such as X-ray mirrors.

A new composite base on reduced graphene oxide (RGO) and poly(5-amino-1-naphthol) (P5A1N) was synthesized by the electrochemical polymerization of 5-amino-1-naphthol (5A1N) in the presence of HClO(4)and H(4)SiW(12)O(40)onto the surface of Au electrode covered with the RGO sheets. The linear dependence of the current densities of the anodic and cathodic peaks with the scan rate of the potential range (0; 0.8) V vs. SCE, reported during electropolymerization of 5A1N, indicates an electron transfer that is controlled by diffusion. A covalent functionalization of the RGO sheets with P5A1N is argued by: (i) the simultaneous disappearance of the IR band at 1584 cm(-1)and the appearance of the new IR bands at 812, 976 and 3744 cm(-1), and (ii) the appearance of two Raman lines at 738 and 1428 cm(-1). An application of the RGO sheets covalently functionalized with P5A1N is demonstrated to support 1,4-phenylene diisothiocyanate (PDITC), a compound used as a cross-linking agent for various biological applications. The chemical adsorption of PDITC onto the RGO sheets covalently functionalized with P5A1N, which involves the appearance of new functional groups of the type thiourea, was proven by Raman scattering and IR spectroscopy.

To improve the catalytic performance of an active layered double hydroxide (LDH)-derived CuCeMgAlO mixed oxide catalyst in the total oxidation of methane, it was promoted with different transition-metal cations. Thus, two series of multicationic mixed oxides were prepared by the thermal decomposition at 750 degrees C of their corresponding LDH precursors synthesized by coprecipitation at constant pH of 10 under ambient atmosphere. The first series of catalysts consisted of four M(3)CuCeMgAlO mixed oxides containing 3 at.% M (M = Mn, Fe, Co, Ni), 15 at.% Cu, 10 at.% Ce (at.% with respect to cations), and with Mg/Al atomic ratio fixed to 3. The second series consisted of four Co(x)CuCeMgAlO mixed oxides withx= 1, 3, 6, and 9 at.% Co, while keeping constant the Cu and Ce contents and the Mg/Al atomic ratio. All the mixed oxides were characterized by powder X-ray diffraction (XRD), transmission electron microscopy (TEM), scanning electron microscopy (SEM) coupled with X-ray energy dispersion analysis (EDX), X-ray photoelectron spectroscopy (XPS), nitrogen adsorption-desorption at -196 degrees C, temperature-programmed reduction under hydrogen (H-2-TPR), and diffuse reflectance UV-VIS spectroscopy (DR UV-VIS), while thermogravimetric and differential thermal analyses (TG-DTG-DTA) together with XRD were used for the LDH precursors. The catalysts were evaluated in the total oxidation of methane, a test reaction for volatile organic compounds (VOC) abatement. Their catalytic performance was explained in correlation with their physicochemical properties and was compared with that of a reference Pd/Al(2)O(3)catalyst. Among the mixed oxides studied, Co(3)CuCeMgAlO was found to be the most active catalyst, with a temperature corresponding to 50% methane conversion (T-50) of 438 degrees C, which was only 19 degrees C higher than that of a reference Pd/Al(2)O(3)catalyst. On the other hand, this T(50)value was ca. 25 degrees C lower than that observed for the unpromoted CuCeMgAlO system, accounting for the improved performance of the Co-promoted catalyst, which also showed a good stability on stream.

Issues related to the optimization of heat transfer mechanisms dominated by superparamagnetic relaxation are considered in the case of AC (alternating current) magnetic field hyperthermia procedures. The key role in the conversion of electromagnetic energy to the thermal one via the superparamagnetic relaxation mechanism is played by the magnetic anisotropy of nanoparticles, easily to be controlled via the shape anisotropy component. The optimization process has been discussed in the case of magnetite (Fe3O4) ellipsoidal nanoparticles with dominant shape anisotropy dispersed in different media. Nanoparticles of different sizes and aspect ratios have been considered in correlation with those specific parameters of the actuating AC magnetic field which respect an established biological safely criterion. It has been proven that the dissipated power can be maximized for a given set of biological compatible RF (radiofrequency) field parameters (frequency and field amplitude at the sample space) only for specific pairs of particle sizes and aspect ratios. For instance, it has been shown that ellipsoidal magnetite nanoparticles with 10 nm equatorial size and aspect ratio of 2 are optimal for a maximum transferred power under radiofrequency excitations of 250 kHz and field amplitude of 20 kA/m, if high viscosity dispersion media are used. The methodology for deriving the optimal shape (geometrical) parameters of a specific type of nanoparticles in conditions of using available radiofrequency excitations, or vice versa, for deriving the optimal radiofrequency working parameters in the case of ferrofluids with specific nanoparticles (type and geometry) is described and discussed in detail.

When the gas sensor active layer film thickness is decreased, increased sensitivity to changes in the adsorbate concentration is expected when measuring the resistance of the layer, in particular when this thickness is on the order of the Debye length of the material (one-tens of nanometers); however, this is demonstrated only for a limited number of materials. Herein, ultrathin NiO films of different thicknesses (8-21 nm) have been deposited via chemical vapor deposition to fabricate gas sensor devices. Sensor performance for a range of NO2 concentrations (800 part-per-billion to 7 part-per-million) was evaluated and an optimum operating temperature of 125 degrees C determined. The dependence of the potential relative changes with respect to the NO2 concentration and of the sensor signal with respect to the geometrical parameters was qualitatively evaluated to derive a transduction model capable of fitting the experimental results. The selective sensitivity toward NO2 was confirmed by the limited response for different reducing gases, CO, CH4, NH3, and SO2, under optimum operating conditions, and the sensor signal toward NO2 increased with decreasing thickness, demonstrating that the concept of a Debye length dependence of sensitivity is applicable for the p-type semiconductor NiO. In addition, these NiO sensors were exposed to different relative levels of humidity over a wide range of operating temperatures and were found to display humidity tolerance far superior to those in previous reports on SnO2 materials.

Palladium is one of the most efficient metals for the hydrogenation of organic compounds. However, when molecules, such as nitroaromatics, with several reducible functionalities, are hydrogenated, Pd, like any other very active metal, such as nickel or platinum, often behaves unselectively. One strategy to render Pd more selective is to choose the proper support. Herein, we show that MAX phase powders of Ti3SiC2, Ti2AlC, or Ti3AlC2 can chemoselectively hydrogenate 4-nitrostyrene to 4-aminostyrene, with 100% selectivity, at around 3-4% conversion. To boost the latter, we loaded Ti3SiC2 with 0.0005 wt % Pd and increased the conversion to 100% while maintaining the 4-AS selectivity at >90%. By optimizing the Pd loading, we were also able to increase the turnover frequency 100-fold relative to previous literature results. The identification of this highly efficient and chemoselective system has broad implications for the design of cost-effective, earth-abundant, nontoxic, metal catalysts, with ultralow noble metal loadings.

Hybrid bionanocomposite coating systems (HBCSs) are green polymer materials consisting of an interface between a coating matrix and nanoparticles. The coating matrix was prepared by using a nonisocyanate poly(hydroxyl urethane) (NIPHU) prepolymer crosslinked via 1,3-diaminopropane and epoxidized Jatropha curcas oil. TEMPO-oxidized cellulose nanoparticles (TARC) were prepared from microcrystalline cellulose, and (3-aminopropyl)trimethoxysilane (APTMS)-coated ZnO nanoparticles (APTMS-ZnO) and their suspensions were synthesized separately. The suspensions at different weight ratios were incorporated into the coating matrix to prepare a series of HBCSs. FT-IR, H-1-NMR, C-13-NMR, XRD, SEM, and TEM were used to confirm the chemical structures, morphology, and elements of the coating matrix, nanomaterials, and HBCSs. The thermomechanical properties of the HBCSs were investigated by TGA-DTG and pencil hardness analyses. The UV and IR absorption spectra of the HBCSs were obtained using UV-vis spectroscopy and FTIR spectroscopy, respectively. The HBCSs exhibited good thermal stability at about 200 degrees C. The degradation temperature at 5% mass loss of all samples was over around 280 degrees C. The HBCSs exhibited excellent UV block and IR active properties with a stoichiometric ratio of the NIPHU prepolymer and EJCO of 1:1 (wt/wt) containing 5 wt % TARC and 15 wt % APTMS-ZnO nanoparticles. It was observed that the sample with 5 wt % TARC and 15 wt % APTMS-ZnO (HBCS-2) exhibited a uniform crosslinking and reinforcement network with a T-onset of 282 degrees C. This sample has successfully achieved good coating hardness and excellent UV and IR absorption.

The aim of this paper is the study of the thermal behavior of the simonkolleite Zn-5(OH)(8)Cl-2 center dot H2O (ZHC) by electron paramagnetic resonance (EPR) spectroscopy, in particular. It is well known that during heating ZHC undergoes a complex transformation which involves several overlapping stages. However, with reference to the data reported on this subject, it can be concluded that there is still an ongoing debate regarding the intermediate stages of this process. The data presented in this study support a simple decomposition process of the ZHC prepared using the precipitation method. The EPR data correlated to the data obtained by other experimental techniques, such as XRD, TEM, SEM and EDX, indicate that during the thermal treatment the ZHC suffers a partial decomposition to ZnO with no intermediate products. After annealing at 500 degrees C for 1 h, a recombination process of ZHC is observed. Moreover, the kinetics associated to these decomposition steps were determined and the evolution of the paramagnetic centers was also followed and studied. This study offers new information related to the thermal behavior of ZHC, especially regarding the EPR data which is reported for the first time on this subject and material.

Germanium Metal-Ferroelectric-Semiconductor (MFS) capacitors based on ferroelectric Hf1-xZrxO2 (HZO) with clean, oxide free Ge/HZO interfaces emerge as an interesting layer structure for the fabrication of ferroelectric field effect transistor (FeFET) non-volatile memory devices. It is shown that, at low temperature (<160K), a semiconductor depletion forms in Ge near the interface, resulting in an increase in coercive voltage by about 2V, accompanied by a distortion of the ferroelectric hysteresis with subloop asymmetric behavior, which becomes more severe at higher frequencies of measurement. At higher temperatures, the Ge surface near the ferroelectric is easily inverted due to the low energy gap of Ge, providing sufficient screening of the polarization charge by minority free carriers, in which case, nearly ideal, symmetric hysteresis curves are recovered. The depolarization field is experimentally extracted from the coercive voltage and the capacitance measurements, is found to be 2.2MV/cm in the low temperature range, comparable to the coercive field, then rapidly decreases at higher temperatures, and effectively diminishes at room temperature. This makes Ge MFSs good candidates for FeFETs for low voltage non-volatile memory with improved reliability.

Formation of SiGe nanocrystals in an oxide matrix via deposition and subsequent annealing is a widely applied approach as it gives good control over optical properties by varying the Ge atomic fraction, the size, shape and crystallinity of the nanocrystals. A common drawback of annealing is a strain relaxation in the structure creating dislocations, point defects, dangling bonds, Ge clustering and altered interface morphology. All these phenomena are well-known to degrade the optoelectronic and electrical properties of the structure. As a proof of concept, in this study we have utilized a modern technique of high impulse power magnetron sputtering (HiPIMS) to obtain a crystalline TiO2/SiGe/TiO2 structure without any pre-/post-annealing. It is furthermore demonstrated how a control of the nano-crystallite size is obtained by altering the HiPIMS discharge power alone. Grazing incidence X-ray diffraction analysis was carried out for the structural characterization, while photocurrent measurements were utilized to access the role of TiO2 structural morphology over interface integrity in determining spectral feature and sensitivity. An increase of 1 - 2 orders magnitude in spectral intensity was achieved for as-grown structures fabricated via HiPIMS in comparison to annealed structure, sputtered with conventional direct current magnetron sputtering.