Dr. Ionel MERCIONIU

Composites based on TiO2 and single-walled carbon nanotubes (SWCNTs), highly separated in semiconducting tubes (S-SWCNTs) and as a mixture of metallic and semiconducting tubes (M + S-SWCNTs), were obtained by the interaction in the solid state. This interaction induces a change in the size of TiO2 particles from 23.67 nm to 28.2 and 150 nm, respectively, accompanied by an increase in the disorder state of the graphitic lattice of SWCNTs. We demonstrate by UV-VIS spectroscopy that the best performance in terms of rhodamine 6G (Rh6G) photodegradation is obtained in the case of the TiO2/S-SWCNT composite. The highest values of the Rh6G photodegradation efficiency were equal to 92% for an S-SWCNT concentration in the photocatalyst mass of 10 wt% and 94% for a 0.1 mM Rh6G solution with a pH equal to 1. We demonstrate that an important role is played by the O2(center dot)- and (OH)-O-center dot species in the photodegradation mechanism of Rh6G. This study contributes to a better understanding of the role of metallic and semiconducting carbon nanotubes in the photocatalysis field, highlighting that composites based on semiconducting SWCNTs and semiconducting metallic oxides are those that contribute essentially to the removal of dyes by exposure to the light emitted by a halogen lamp.

Polymorphism determines significant variations in materials' properties by lattice symmetry variation. If they are stacked together into multilayers, polymorphs may work as an alternative approach to the sequential deposition of layers with different chemical compositions. However, selective polymorph crystallization during conventional thin film synthesis is not trivial; changes of temperature or pressure when switching from one polymorph to another during synthesis may cause degradation of the structural quality. The present work reports on the single-step ion-beam-assisted fabrication of multilayered polymorph structures while applying the disorder-induced ordering approach. The dynamic annealing of disorder may be tuned, during ion irradiation, toward self-assembling of several polymorph interfaces. Gallium oxide multilayers with two polymorph interface repetitions are obtained. The single-crystal structure of the polymorphs is maintained between interfaces, exhibiting repeatable crystallographic relationships and optical properties. These data pave the way for enhancing materials' functionalities using not previously conceived capabilities of ion beam technology.

We explored the possibility to guide the forming process in a Ta/TiO2/Pt memristive device using an X-ray nanopatterning procedure, which enables the manipulation of the oxygen content at the nanoscale. The irradiation of selected areas of the sample by a 65 x 58 nm2 synchrotron X-ray nanobeam locally generated oxygen vacancies which resulted in the formation of a conductive filament in the desired position in the material. The subsequent application of an electric field between the electrodes was exploited to achieve reversible bipolar resistive switching. A multitechnique characterization was then performed, highlighting a local increase in the height of the crystal and the formation of a dislocation network, associated with the presence of Wadsley defects. Our results show that X-ray nanopatterning could open new avenues for a more deterministic implementation of electroforming in oxide-based memristive devices. We tuned the oxygen content in a Ta/TiO2/Pt memristive device at the nanoscale by a synchrotron X-ray nanobeam. We obtained a conductive filament of oxygen vacancies in the desired position in the material to achieve a controlled resistive switching.

This work presents the ability of WO3-based sensors to detect low traces of acetone, specifically within the range of 0.25-5 ppm, specific to the in -field atmosphere. The WO3 powder was synthesised through the hydrothermal method. Morpho-structural investigations showed a monoclinic structure and a good crystallization of the WO3 powder, containing well -grown and faceted grains along low -index crystallographic planes. The paste obtained by mixing the powder with propanediol was screen -printed as a thick layer onto commercial alumina substrates, obtaining the chemical sensors. A dynamic computer -controlled Gas Mixing System was utilized to ensure controlled airflow with variable relative humidity and acetone concentrations. The sensor response was explained based on physico-chemical equations, taking into consideration pre -adsorbed species of oxygen and water, both of which are relevant constituents of atmospheric conditions. The results highlight the applicative potential of WO3, having a good signal-to-noise ratio in relative humidity conditions up to 90% and a pronounced sensitive selectivity to acetone.

Zn1-xFexO nanoparticles with the iron concentrations level in the dilute regime (x = 0.001---0.01) were produced by a sol-gel route from acetate precursors along with an un-doped and 3 at.% Fe-doped reference. The X-ray diffraction of the un-doped and 0.1-1 at.% Fe-doped samples reveal the reflections for only the ZnO wurtzite structure. Fe doping enhances the a-axis lattice constant, the unit cell volume and the microstrain. Iron doping reduces the average crystallite/particle size (confirmed by Scanning Electron Microscopy), improving the surface-to-volume ratio or the concentration of defective surface sites. XPS identifies the iron in both Fe3+ and Fe2+ states. XPS and Fe-57 Mossbauer spectroscopy indicate a broad distribution (distortion) of Fe3+ sites on the surface of ZnO nanoparticles. The blue shift and broadening of the UV emission, and quenching of defect-related photoluminescence in the Fe-doped samples verify the presence of iron in the ZnO lattice and surface intrinsic defects. 0.1-1 at.% Fe-doped ZnO show room temperature ferromagnetism, RTFM, characteristic of dilute magnetic semiconductors, DMS. The magnetization measurements with temperature evidence an antiferromagnetic alignment and an increase of ferromagnetic contribution with Fe doping up to 1 at.%. Zn0.97Fe0.3O reference is a superparamagnetic ZnO/ZnFe2O4 nanocomposite with a blocking temperature of 20 K; HRTEM shows (ultra)fine ZnFe2O4 particles at the surface of ZnO nanoparticles. The analysis of experimental data of 0.1-1 at.% Fe-doped ZnO was done in terms of iron coupling with intrinsic defects, which can generate surface Fe3+ states with geometries similar to the Fe3+ in inverse spinel ZnFe2O4. The superexchange interaction (resembling that in the inverse spinel ZnFe2O4) between the Fe3+ sites with distorted configuration resulting in ferrimagnetism was hypothesised as a possible mechanism of RTFM. Experimental (structural, local chemical, magnetic, optical) and interpretation results can be used to optimize the processing conditions for Fe-doped ZnO to serve as an effective DMS, e.g. for spintronic applications.

In this study, we report the performance improvement of wound dressings by covering them with magnetite-based nanostructured coatings. The magnetite nanoparticles (Fe3O4 NPs) were functionalized with Nigella sativa (N. sativa) powder/essential oil and dicloxacillin and were synthesized as coatings by matrix assisted pulsed laser evaporation (MAPLE). The expected effects of this combination of materials are: (i) to reduce microbial contamination, and (ii) to promote rapid wound healing. The crystalline nature of core/shell Fe3O4 NPs and coatings was determined by X-ray diffraction (XRD). Differential Scanning Calorimetry (DSC) and Thermo Gravimetric Analysis (TGA) have been coupled to investigate the stability and thermal degradation of core/shell nanoparticle components. The coatings' morphology was examined by scanning electron microscopy (SEM). The distribution of chemical elements and functional groups in the resulting coatings was evidenced by Fourier transform infrared (FTIR) spectrometry. In order to simulate the interaction between wound dressings and epithelial tissues and to evaluate the drug release in time, the samples were immersed in simulated body fluid (SBF) and investigated after different durations of time. The antimicrobial effect was evaluated in planktonic (free-floating) and attached (biofilms) bacteria models. The biocompatibility and regenerative properties of the nanostructured coatings were evaluated in vitro, at cellular, biochemical, and the molecular level. The obtained results show that magnetite-based nanostructured coatings functionalized with N. sativa and dicloxacillin are biocompatible and show an enhanced antimicrobial effect against Gram positive and Gram negative opportunistic bacteria.

Nano-nitride reinforcement of Fe-Cr alloys are under intense investigations, e.g., along with oxide-strengthened, nitride-strengthened reduced activation steels with superior high temperature mechanical properties are developed as materials for nuclear energy applications. Fe14Cr alloy powders were produced by mechanical milling for up to 170 h under a nitrogen atmosphere followed by heating under an Ar5%H-2 atmosphere to 600 degrees C-1120 degrees C. The samples were investigated by means of X-ray diffraction, DTA/TG and magnetic measurements. CrN, detected after milling for 58 h, reached 39 wt % (5.3 wt.% total N) at 170 h milling. The ferrite supersaturated with nitrogen shows a strong decrease in grain size and saturation magnetization, an increase in lattice constant, microstrain and coercivity, H-c. Upon heating, the metastable ultrafine alpha-ferrite and CrN in the as-milled samples undergo transformations and recrystallization into ferrite grains free of super-saturation, whose microstructure follows a continuous relaxation. The supersaturation with nitrogen was retained upon heating in the relatively stable ferrite crystalized at the milling stage. This microstructure undergoes a discontinuous relaxation in the 800 degrees C-1120 degrees C region: a pronounced decrease of grain size (down to similar to 25 nm), an increase of lattice constant, microstrain and H-c. These improvements were associated with features of discontinuous precipitation reaction of coherent nitride precipitates (involving a new alpha ''-phase with expanded lattice), in connection with the heating in the austenite phase field. Such microstructure refinement or (nitride) strengthening of Fe14Cr alloys can be achieved on powders milled for much less time as compared to previously reported (oxide dispersion) strengthening of Fe14Cr-W-Ti ferritic steels. (C) 2022 The Authors. Published by Elsevier B.V.

Zn-Fe-O nanoparticle systems (Z3F, Z20F and Z60F) were produced by changing the Zn:Fe ratio (0.97 : 0.03, 0.8 : 0.2 and 0.4 : 0.6 in at%, respectively) in Zn(ii)-Fe(iii)-carboxylate precursors. According to X-ray diffraction, Z60F is nearly single-phase ZnFe2O4 (5.9 nm crystallite size), Z20F is a ZnO/ZnFe2O4 nanocomposite consisting of 48.8% ZnFe2O4 (4.7 nm crystallite size), and Z3F is apparently pure ZnO (9.5 nm). We found evidence for a ZnFe2O4 spinel of high inversion degree (80-100%) and with superparamagnetic (SPM) behaviour at room temperature in all three samples by a remarkable correlation between HRTEM, FTIR, XPS, Mossbauer and magnetization analyses. Iron modifies the decomposition process of the precursor and enhances its viscosity, which appears to favour the separation of Zn- and Fe-rich phases. As a consequence, two-phase systems of individual nanocrystals/nanoparticles (ZnO and ZnFe2O4) are formed. The large anisotropy constant, 10(6)-10(7) erg cm(-3), of the ZnFe2O4 nanoparticles and the concentration dependence of their magnetic energy barrier are explained in terms of interparticle interactions interlinked with finite size effects and high inversion degree; these factors also control the other parameters of importance for applications, including the blocking temperature (13-111 K), saturation magnetization (1.08-17.7 emu g(-1) at 300 K, 4.6-44.8 emu g(-1) at 5 K) and coercivity (85.4-491 Oe at 5 K). Magnetic dynamic results, particularly modelled by the Neel-Brown and Vogel-Fulcher laws, yield fitting parameters which validate the presence of concentration-dependent dipole-like interactions between ZnFe2O4 nanoparticles. A fraction of iron was found in the Fe2+ state, presumably substituting for Zn2+ in zinc oxide; however, the samples behave like ZnFe2O4 SPM nanoclusters/nanoparticles dispersed in a nonmagnetic ZnO particle assembly, rather than Zn(Fe)O dilute magnetic semiconductors. The relevance of the properties of the investigated material for specific applications is highlighted throughout the manuscript.

We report a novel strategy to enhance the dielectric breakdown strength and the energy storage performance of lead-free relaxor ferroelectric ceramics through the fabrication of semiconductor/relaxor 0-3 type composites based on 0.6Ba(Zr0.2Ti0.8)O-3-0.4(Ba0.7Ca0.3)TiO3 [BZCT] and ZnO. X-ray diffraction (XRD), Raman spectroscopy, and scanning electron microscopy (SEM) measurements confirm the formation of semiconductor/relaxor 0-3 type composites, in which ZnO particles are randomly distributed at the grain boundaries of BZCT. Further, the XRD analysis suggests a structural phase change from a tetragonal to a pseudocubic phase as the ZnO content increases from 0 to 5 wt. % in BZCT/ZnO composites. The pseudocubic phase favors the relaxor behavior of the composites as is evident from dielectric studies. The polarization-electric field (P-E) loops reveal the ferroelectric nature of the BZCT/ZnO composites. The energy storage properties of BZCT/ZnO composite ceramics as a function of different wt. % of ZnO are found to be optimum at 1 wt. % with a recoverable energy density of 2.61 J/cm(3) and an efficiency of 74.2%, at an electric field of 282 kV/cm. Besides, an enhancement of 166% in the electric breakdown and 220% in the recoverable energy density was achieved compared to the BZCT ceramics due to the improved density and the large value of Delta P = P-m - P-r (25.55 mu C/cm(2)). Therefore, this work evidences that the formation of the semiconductor/relaxor 0-3 type composites can be an effective way to significantly improve the energy storage performance of lead-free relaxor ferroelectric ceramics. (C) 2020 The Authors. Publishing services by Elsevier B.V. on behalf of Vietnam National University, Hanoi.

In this work, new results concerning the potential of mixtures based on nitrogen doped titanium dioxide (TiO2:N) and carbon nanotubes (CNTs) as possible catalyst candidates for the rhodamine B (RhB) UV photodegradation are reported. The RhB photodegradation was evaluated by UV-VIS absorption spectroscopy using samples of TiO2:N and CNTs of the type of single-walled carbon nanotubes (SWNTs), double-wall carbon nanotubes (DWNTs), multi-wall carbon nanotubes (MWNTs), and single-walled carbon nanotubes functionalized with carboxyl groups (SWNT-COOH) having various concentrations of CNTs. The best photocatalytic performance was obtained for sample containing TiO2:N and 2.5 wt.% SWNTs-COOH, when approx. 85% of dye removal was achieved after 300 min. of UV irradiation. The reaction kinetics of RhB aqueous solutions containing TiO2:N/CNT mixtures followed a complex first-order kinetic model. The TiO2:N/CNTs catalyst induced higher photodegradation efficiency of RhB than TiO2:N due to the presence of CNTs, which act as adsorbent and dispersing agent and capture the photogenerated electrons of TiO2:N hindering the electron-hole recombination.

Polycrystalline NiO thick film-based gas sensors have been exposed to different test gas atmospheres at 250 degrees C and measured via simultaneous electrical resistance and work function investigations. Accordingly, we decoupled different features manifested toward the potential changes, i.e., work function, band-bending, and electron affinity. The experimental results have shown that the presence of moisture induces an unusual behavior toward carbon monoxide (CO) detection by considering different surface adsorption sites. On this basis, we derived an appropriate detection mechanism capable of explaining the lack of moisture influence over the CO detection with NiO-sensitive materials. As such, CO might have both chemical and dipolar interactions with pre-adsorbed or lattice oxygen species, thus canceling out the effect of moisture. Additionally, morphology, structure, and surface chemistry were addressed, and the results have been linked to the sensing properties envisaging the role played by the porous quasispherical-hollow structures and surface hydration.

The equimolar oxide mixture beta-Ga2O3-alpha-Fe2O3 was subjected to high-energy ball milling (HEBM) with the aim to obtain the nanoscaled GaFeO3 ortho-ferrite. X-ray diffraction, Fe-57 Mossbauer spectroscopy, and transmission electron microscopy were used to evidence the phase structure and evolution of the equimolar nano-system beta-Ga2O3-alpha-Fe2O3 under mechanochemical activation, either as-prepared or followed by subsequent calcination. The mechanical activation was performed for 2 h to 12 h in normal atmosphere. After 12 h of HEBM, only nanoscaled (similar to 20 nm) gallium-doped alpha-Fe2O3 was obtained. The GaFeO3 structure was obtained as single phase, merely after calcination at 950 degrees C for a couple of hours, of the sample being subjected to HEBM for 12 h. This temperature is 450 degrees C lower than used in the conventional solid phase reaction to obtain gallium orthoferrite. The optical and magnetic properties of representative nanoscaled samples, revealing their multifunctional character, were presented.

In this work, new films containing composite materials based on blends of thermoplastic polymers of the polyurethane (TPU) and polyolefin (TPO) type, in the absence and presence of BaTiO3 nanoparticles (NPs) with the size smaller 100 nm, were prepared. The vibrational properties of the free films depending on the weight ratio of the two thermoplastic polymers were studied. Our results demonstrate that these films are optically active, with strong, broad, and adjustable photoluminescence by varying the amount of TPU. The crystalline structure of BaTiO3 and the influence of thermoplastic polymers on the crystallization process of these inorganic NPs were determined by X-ray diffraction (XRD) studies. The vibrational changes induced in the thermoplastic polymer's matrix of the BaTiO3 NPs were showcased by Raman scattering and FTIR spectroscopy. The incorporation of BaTiO3 NPs in the matrix of thermoplastic elastomers revealed the shift dependence of the photoluminescence (PL) band depending on the BaTiO3 NP concentration, which was capable of covering a wide visible spectral range. The dependencies of the dielectric relaxation phenomena with the weight of BaTiO3 NPs in thermoplastic polymers blends were also demonstrated.

A one-step method assisted by hydrothermal treatment was approached to obtain nanocrystalline 1 and 10 mol. % In doped 2 mol.% Pd-SnO2 powders using a non-ionic surfactant Brij52 and Polyethylene glycol 6000 (PEG) as templates. Depending on In content, the samples were labeled as Pd1InSn and Pd10InSn. The obtained materials consist of nanosized crystallites packed into micrometric grains with a high porosity, as revealed by the morphological and structural investigations (SEM, TEM). A dependence of the grain size with respect to the In content has been revealed i.e. the sample Pd1InSn was showing an average grain size of around 10 nm, whilst for the sample Pd10InSn the average grain size was found to be around 5 nm. The XPS investigations highlighted the differences occurred in the surface chemistry in terms of surface hydroxylation as well as the chemical states of Pd. The sensing properties towards different CO concentrations have been examined under infield background conditions, at low operating temperature of 50 degrees C. The sensing mechanism model for CO was discussed in detail according to the possible interplay between oxygen and water related species based on the experimentally results acquired through simultaneous electrical resistance and work function measurements.

ZnO nanostructures with intrinsic and extended defects were prepared by rapid decomposition of zinc-propio-nate and annealing at 400 degrees C-970 degrees C. The correlation between the structure/morphology, type of native defects (photoluminescence (PL), EPR) and ferromagnetism was investigated, together with ammonia adsorption capacity. All the samples show room temperature ferromagnetism (RTFM). Crystallite size increases while the unit cell volume, c-axis constant, microstrain and saturation magnetization relax with increasing temperature; morphology varies from aggregated nanoparticles to frameworks of well-welded crystals. 400 degrees C-800 degrees C annealed samples show a broad visible and/or a prominent violet-blue PL emission and, two narrow g = 2.0065 and g = 1.9632 EPR signals. 800 degrees C-970 degrees C annealed samples exhibit very intense green-yellow photoluminescence. The intrinsic defects in conjunction with a deformed lattice and/or pinned by grain-boundaries appear responsible for RTFM and Curie temperature exceeding 700 degrees C. Tuning the morphology, PL intensity and ferromagnetic signal by choice of annealing temperature can find applications in (gas) sensing, photonic/optoelectronic and spintronic devices.

The influence of Ag and Au nanoparticles and reduced graphene oxide (RGO) sheets on the photodegradation of alpha-lipoic acid (ALA) was determined by UV-VIS spectroscopy. The ALA photodegradation was explained by considering the affinity of thiol groups for the metallic nanoparticles synthesized in the presence of trisodium citrate. The presence of excipients did not induce further changes when ALA interacts with Ag and Au nanoparticles with sizes of 5 and 10 nm by exposure to UV light. Compared to the Raman spectrum of ALA powder, changes in Raman lines' position and relative intensities when ALA has interacted with films obtained from Au nanoparticles with sizes between 5 and 50 nm were significant. These changes were explained by considering the chemical mechanism of surface-enhanced Raman scattering (SERS) spectroscopy. The photodegradation of ALA that had interacted with metallic nanoparticles was inhibited in the presence of RGO sheets.

Oxide dispersion-strengthened ferritic steels (ODSFSs) are promising structural materials for applications in fusion and fission power reactors, but further improvement in their (high-temperature) mechanical properties and ferrite phase stability is required. This work demonstrates that an approach to produce Fe14Cr ODSFSs with a stable ferrite phase and improved strength could involve grain size strengthening by long-term milling with a tiny amount of nitrogen. Fe-14Cr-3W-0.4Ti-0.25Y(2)O(3) powders were ball-milled up to 170 hours under an argon atmosphere. In addition to X-ray diffraction, the change in product quality during milling and upon heating was thoroughly investigated by more sensitive magnetic and thermal analysis by measuring the saturation magnetization sigma(s), coercivity H-c, Curie temperature T-c, and temperature of ferrite-austenite (alpha ->gamma) transition T-alpha ->gamma. A pronounced modification of magnetic and microstructure parameters was observed when milling over 70 hours and upon heating above 800 degrees C and was found to be generated by long-term milling with a tiny amount of nitrogen. Upon heating, the nitrogen, incorporated during milling, developed a transition region, with the decomposition of nitrides precipitated at the earlier stage of heating followed by austenite decomposition, nitrogen degassing, and microstructure refinement to a grain size of a few tenths of a nm (e.g., 28 nm by heating at 910 degrees C of 100-hour milled powder). The resulting ferrite phase with refined grains is highly stable to (further) heating. The powders milled for 70 and 100 hours containing 0.175 and 0.500 wt pct nitrogen, respectively, were consolidated at 1100 degrees C with subsequent annealing at 1050 degrees C and subjected to Vickers hardness and 3-point bending tests. The steel produced from the powder milled for 70 hours shows lower hardness, higher density (close to the theoretical value of 7.8 g/cm(3)), and fracture strain. The ductility of this ODS alloy (0.075 fracture strain) is comparable with Eurofer97 (0.075 fracture strain), whereas its strength (2070 MPa ultimate stress) is significantly higher than that of Eurofer97 (1222 MPa ultimate stress). This improvement was attributed to grain size strengthening-the refined grains (promoted by milling with nitrogen) could be effectively pinned by Y-Ti-O dispersoids.

Fe-14Cr-0.4Ti-0.25Y(2)O(3) ferritic steels were produced by varying the amount of residual process control agent, PCA (ethanol), in the ball-milled powders and changing the spark-plasma-sintering, SPS, temperature. Near the-oretical density (99.3%), high Vickers hardness (501-920 HV, measured by applying a load of 100 g for 5 s) and fine grain size (26-36 nm), very stable against heating, can be achieved on ODS ferritic steels, consolidated from powders with a low amount of PCA and processing temperature in the range of 1000 degrees C-1100 degrees C. Additional grain refinement occurs near alpha -> gamma transition which is generated by the reaction of the traces of PCA with the ferritic matrix upon heating. High local temperatures and the evolved thermally activated processes, at the contact points between particles/at the particle surfaces during SPS-consolidation, were demonstrated to be the main factors responsible for improved densities and hardness. The role of PCA in the sintering, thermal and microstructure particularities and its impact on the quality of the final steel was thoroughly analysed throughout the work. (C) 2019 Elsevier B.V. All rights reserved.

Nanoclustered Pd (2 mol%) was used to decorate Zn doped SnO2 (10 mol% Zn) in order to increase its sensing performances. Zn doped SnO2 built from nanoparticles was prepared by a hydrothermal method using a nonionic surfactant -Brij52 and Tripropylamine (TPA) as co-templates. The presence of well-dispersed Zn2+ ions in the SnO2 matrix leads to a nonstoichiometric surface. Pd was deposited by subsequent wet impregnation using hydrazine as reducing agent. The as obtained powders were deposited as thick layers onto commercial substrates, in order to obtain the sensitive structures. The coexistence of a mixture of valence states (Pd-0, Pd2+ and Pd4+) was highlighted on the surface of the as prepared layers. Several aspects have been followed regarding the Zn and Pd dispersion into the SnO2 matrix: the large scale and low scale morphology (SEM and TEM/HRTEM) in relation with the synthesis route, the obtained crystallographic phases (XRD, SAED) and the way in which the Zn2+ ions are inserted into the SnO2 structure (XRD, XPS, EPR), the spatial distribution of the added chemical elements, Zn and Pd (SEM, STEM, EDS). All these morphological and structural aspects, as well as the Pd surface chemistry, have been correlated with the sensing properties of the nanostructured materials under controlled gas atmosphere. Through this study, we could harvest the specific role of the aforementioned loadings towards selective detection of low NO2 concentrations, between 350 ppb to 5 ppm, at low operating temperature of 100 degrees C, for infield conditions.

Among the rare-earth-free systems that are currently investigated in search for novel permanent magnet solutions for various applications, with special emphasis on the magnets required to operate in extreme conditions, the FePt binary system, where the tetragonal hard magnetic L1(0) phase can be formed by suitable microstructure processing via annealing, has been extensively studied. A variation of this system, the ternary FeMnPt system, has been also recently shown to exhibit good permanent magnet behavior due to the suitable formation of the L1(0) phase. In addition to be likely to form the L1(0) phase as its parent binary system, the ternary FeMnPt benefits from the reduced costs due to the reduced amount of Pt and may exhibit particular magnetic structure due to the influence of the antiferromagnetic Mn. In the present work, we have employed a mixed sputtering technique, based on the use of both elemental and compound target for developing L1(0) FeMnPt thin films with specific structural features that triggers better magnetic performances in terms of coercivity and maximum energy products. The as-obtained films have been thermally annealed and characterized by means of transmission electron microscopy, X-ray diffraction, Mossbauer spectroscopy, magneto-optic Kerr effect (MORE) and SQUID magnetometry. The aim is to correlate the Mn induced microstructural and lattice changes with the magnetic properties and to optimize the microstructure for an early formation of the ordered L1(0) phase and increased coercivity compared to the as-prepared, structurally disordered, face centred cubic initial state of the films.

The annealing of crystalline defects in Si single crystals created by ion implantation at room temperature was investigated. Silicon single crystals were firstly implanted at room temperature with 1.345 MeV Au1+ ions at fluences from 1 x 10(13) to 1 x 10(14) at/cm(2) to induce damage. A second implantation at room temperature was afterwards performed with 10 MeV Co3+ ions at a fluence of 3 x 10(14) at/cm(2). All samples were analyzed afterwards by Rutherford backscattering in random and channeling geometry to assess the crystalline damage present in the surface region. The results showed a significant reduction of the degree of damage or a reduction of the size of damaged region. The morphology and local atomic structure, studied using high -resolution electron microscopy, selected area electron diffraction and high resolution X-ray diffraction confirmed the reduction of damage degree and volume caused by Au implantation after Co implantation.

Five new copper(II) acrylate complexes (acr is the acrylate anion: C3H3O2) with imidazole derivatives (2-methylimidazole/2-MeIm, 5-methylimidazole/5-MeIm, 2-ethylimidazole/2-EtIm) of type: cis-[Cu(2-RIm)(2)(acr)(2)]xH(2)O ((1): R = -CH3, x = 2; (4): R = -CH2-CH3, x = 0), trans-[Cu(2-RIm)(2)(acr)(2)] ((2): R = -CH3; (5): R = -CH2-CH3) and trans-[Cu(5-RIm)(2)(acr)(2)] ((3): R = -CH3) have been prepared and characterized by elemental analysis, Fourier Transform Infrared spectrometry (FTIR), Electron Paramagnetic Resonance (EPR), electronic reflectance spectroscopy, scanning electron microscopy, and mass spectrometry. The single crystal X-ray diffraction study of complexes (2) and (5) reveals that the copper(II) ion is located on an inversion center and show elongated octahedral geometry completed by two coplanar bidentate acrylates and two unidentate imidazole derivatives displayed in trans positions. For complex (4) the single crystal X-ray diffraction shows that the copper(II) ion is in a distorted octahedral environment which can be easily confused with a trigonal prism completed by two bidentate acrylates and two unidentate imidazole derivatives displayed in cis positions. These results indicate the fact that complexes (4) and (5) are the geometric isomers of the same compound bis(acrylate)-bis(2-ethylimidazole)-copper(II). Complexes (1) and (2), as well as (4) and (5), were produced simultaneously in the reaction of the corresponding copper(II) acrylate with imidazole derivatives in methanol solution. Furthermore, in order to be able to formulate potential applications of the obtained compounds, our next goal was to investigate the in vitro antimicrobial activity of the synthesized complexes against Gram-positive and Gram-negative bacteria, as well as fungal strains, of both clinical and ecological importance (biodeterioration of historical buildings). The trans isomers (2) and (5), followed by (4) have shown the broadest range of antimicrobial activity. In case of (1) and (2) isomers, the trans isomer (2) was significantly more active than cis (1), while the cis isomer (4) proved to be more active than trans (5). Taken together, the biological evaluation results indicate that the trans (2) was the most active complex, demonstrating its potential for the development of novel antimicrobial agents, with potential applications in the biomedical and restoration of architectural monuments fields.

The influence of single-walled carbon nanotubes enriched in semiconductor (S-SWNTs) and metallic (M-SWNTs) tubes on the photoluminescence (PL) of polyaniline (PANI), electrosynthesized in the presence of the H2SO4 and HCl solutions, is reported. The emission bands peaked at 407-418 and 440-520 nm indicate that the electropolymerization of aniline (ANI) leads to the formation of short and longer macromolecular chains (MCs), respectively. We demonstrate that the reaction product consists of ANI tetramers (TT) and trimers (TR) as well as PANI-salt. Using Raman scattering and IR absorption spectroscopy, a covalent functionalization of SWNTs with shorter and longer MCs of PANI-salt is demonstrated. The presence of S-SWNTs and M-SWNTs induces a decrease in ANI TT weight in the reaction product mass consisting in S-SWNTs and M-SWNTs covalently functionalized with PANI-emeraldine salt (ES) and PANI-leucoemeraldine salt (LS), respectively. A PANI PL quenching is reported to be induced of the S-SWNTs and M-SWNTs. A de-excitation mechanism is proposed to explain PANI PL quenching.

Low carbon Fe-C steel surface has been studied before and after electrolytic galvanization. The corrosion products formed under atmospheric conditions on the Fe-C steel were identified and characterised by X-ray diffraction (XRD), transmission Mossbauer spectroscopy, conversion electron Mossbauer spectroscopy (CEMS), and conversion X-ray Mossbauer spectroscopy (CXMS). In decreasing order of abundance the found corrosion phases were magnetite, hematite, and goethite. After the surface preparation, an electrolytic galvanization process was applied. A magnetic anisotropy was evidenced after preparation, in the superficial layer of around 250 nm thickness. Scanning electron microscopy (SEM) analyses evidenced the formation of a uniform thin Zn film of 8 mu m at the surface of steel. No other Fe-Zn phases were identified at the steel-Zn interface.

A novel class of quaternary intermetallic alloys based on CoPt is investigated in view of their interesting magnetic properties induced by the presence of hard magnetic L1(0) phase. A Co48Pt28Ag6B18 alloy has been prepared by rapid solidification from the melt and subjected to various isothermal annealing procedures. The structure and magnetism of both as-cast and annealed samples as well as the phase evolution with temperature are investigated by means of thermal analysis, X-ray, and selected area electron diffraction, scanning and high-resolution electron microscopy, and magnetic measurements. The X-ray diffraction (XRD) analysis shows that both the as-cast alloy and the sample annealed at 400 degrees C (673 K) have a nanocrystalline structure where fcc CoPt phase predominates. Annealing at 473 degrees C promotes the formation of L1(0) phase triggered by the disorder-order phase transformation as documented in the differential scanning calorimetry results. The sample annealed at 670 degrees C (943 K) shows full formation of L1(0) CoPt as revealed by XRD. Magnetic measurements showed coercivity values ten times increased compared to the as-cast state. This confirms the full formation of L1(0) CoPt in the annealed samples. Moreover, detailed atomic resolution HREM images and SAED patterns show the occurrence of the rarely seen (003) superlattice peaks, which translated into a high ordering of the L1(0) CoPt superlattice. Such results spur more interest in finding novel classes of nanocomposite magnets based on L1(0) phase.

We have undertaken a temperature-dependent, investigation of the thermodynamics, structure, morphology and magnetism of two MnAl nanocomposite alloys (Mn60Al40 and Mn55Al45). Differential scanning calorimetry (DSC) studies allowed the determination of the exo-effects occurring in the structural phase transformation of MnAI, while by using temperature-dependent X-ray diffraction of synchrotron radiation we were able to monitor the phase transformation effects and the evolution with temperature of various structural phases occurring in the samples. We have shown that slight changes in stoichiometry (5 at.%) give rise to different phase structure in the as-cast state. While in Mn60Al40 only hcp epsilon phase can be found, in Mn55Al45 as-cast alloy, there is a quite complex phase structure with a mixture of gamma(2) (Al8Mn5) and epsilon as well as ferromagnetic MnAI T-phase. Activation energies of about 165 kJ/mol and 290 kJ/mol have been calculated from the Ozawa-Flynn-Wall analysis of DSC experimental data. These findings are in good agreement with the results obtained from XRD. For the Mn55Al45 as cast alloy, we have confirmed by temperature-dependent synchrotron XRD that the hcp e phase decomposes through the migration of interphase interfaces with the transformation rate controlled by boundary diffusion processes. High-resolution transmission electron microscopy have confirmed the phase structure obtained by XRD, while magnetic properties, obtained for the as-cast alloys are consistent with the multiphase character of the samples and in good agreement with previously reported results. The magnetization does not saturate for the maximum applied field of about 4 x 10(6) A/m and a marked coercivity of about 160 kA/m is obtained for the Mn55Al45 as-cast alloy.

Because of the unique properties of the ferroelectric perovskite particles with a well-defined anisotropic form like shape-and size dependent at low dimensions they have all the attention of the scientific world. Extensive morphostructural techniques will be used to characterize the piezoelectric material.

Refined structure of the ferritic phase induced by mechanical milling (under reducing atmosphere) and its thermal stability are required in various applications of nanostructured ferritic alloys. The impurification with nitrogen and oxygen uptaken from the air is very probable during ball-milling, especially at the long-time high-energy milling conditions. As a rule, these interstitial impurities in as-milled powders are in quantities under the sensibility limit of conventional measurement techniques, such as XRD and SEM/ EDS. To evidence the tendency for microstructure modification by impurities introduced during milling, the Fe-14Cr-3W-0.4Ti-0.25Y(2)O(3) (Fe14Cr) ferritic steel powders (re)loaded in air and milled up to 170 h with interruption of the milling process, and heated up to 1373 K were investigated by thermal analysis in correlation with X-ray diffraction and scanning electron microscopy. XRD failed to detect the impurities in powders milled up to 38 h in air although a consistent mass loss related to the degassing of N-2 was registered in thermogravimetric, TG, curves. (Fe,Cr)(4)N, fcc-c, (Fe, Cr)(2)O-3 impurity phases in powders milled over 38 h in air and (Fe,Cr)(2)O-4 formed upon heating were readily detected by XRD. The analysis of these results allowed to better understand the impurification process and to generalise it for any as-milled Fe-Cr-based alloy powder processed in any milling conditions irrespective of the milling atmosphere, duration and thus, of amounts of contaminants. The quality of three powders milled for 170 h in three different conditions was compared: in air, under an argon atmosphere with interruptions of the milling process and under an argon atmosphere without interruption of the milling process. The contamination of powder milled for 170 h under an argon atmosphere without interruption of the milling process is insignificant (corresponding to less than 0.5 mass% mass loss in TG) as compared to powders obtained in the other two milling conditions. New approaches for minimising the contamination from air are suggested.

Amorphous hematite synthesized by a simple and fast microwave route was used to obtain Fe16N2 fine particles by reducing in 5% H-2/Ar gas flow, followed by long time nitridation in ammonia gas flow at temperatures below 200 degrees C. Depending on nitridation temperature, various amounts of metallic iron were present along with the alpha" -Fe16N2 main phase. A small amount of iron oxide was observed by Mossbauer spectroscopy, but it was undetected by X-ray diffraction due to its high degree of amorphization. Increased amounts of Fe3N and Fe4N phases were observed at a nitridation temperature above 150 degrees C, which had a detrimental effect on the magnetic properties. Structural information and phase composition were extracted from Rietveld refinement of the XRD data. Values of the magnetization at saturation measured at 40 kOe and 25 degrees C of 222 emu/g for alpha"-Fe16N2 and 192 emu/g for metallic iron were obtained via magnetic measurements, Rietveld, and Mossbauer analysis.

Synthetic physiological fluids are currently used as a first in vitro bioactivity assessment for bone grafts. Our understanding about the interactions taking place at the fluid-implant interface has evolved remarkably during the last decade, and does not comply with the traditional International Organization for Standardization/final draft International Standard 23317 protocol in purely inorganic simulated body fluid. The advances in our knowledge point to the need of a true paradigm shift toward testing physiological fluids with enhanced biomimicry and a better understanding of the materials' structure-dissolution behavior. This will contribute to "upgrade" our vision of entire cascades of events taking place at the implant surfaces upon immersion in the testing media or after implantation. Starting from an osteoinductive bioglass composition with the ability to alleviate the oxidative stress, thin bioglass films with different degrees of polymerization were deposited onto titanium substrates. Their biomineralization activity in simulated body fluid and in a series of new inorganic-organic media with increasing biomimicry that more closely simulated the human intercellular environment was compared. A comprehensive range of advanced characterization tools (scanning electron microscopy; grazing-incidence X-ray diffraction; Fourier-transform infrared, micro-Raman, energy-dispersive, X-ray photoelectron, and surface-enhanced laser desorption/ionization time-of-flight mass spectroscopies; and cytocompatibility assays using mesenchymal stem cells) were used. The information gathered is very useful to biologists, biophysicists, clinicians, and material scientists with special interest in teaching and research. By combining all the analyses, we propose herein a step forward toward establishing an improved unified protocol for testing the bioactivity of implant materials.

TiO2-based photocatalysts were obtained during previous years in order to limit pollution and to ease human daily living conditions due to their special properties. However, obtaining biocompatible photocatalysts is still a key problem, and the mechanism of their toxicity recently received increased attention. Two types of TiO2 nanoparticles co-doped with 1% of iron and nitrogen (TiO2-1% Fe-N) atoms were synthesized in hydrothermal conditions at pH of 8.5 (HT1) and 5.5 (HT2), and their antimicrobial activity and cytotoxic effects exerted on human pulmonary and dermal fibroblasts were assessed. These particles exhibited significant microbicidal and anti-biofilm activity, suggesting their potential application for microbial decontamination of different environments. In addition, our results demonstrated the biocompatibility of TiO2-1% Fe-N nanoparticles at low doses on lung and dermal cells, which may initiate oxidative stress through dose accumulation. Although no significant changes were observed between the two tested photocatalysts, the biological response was cell type specific and time- and dose-dependent; the lung cells proved to be more sensitive to nanoparticle exposure. Taken together, these experimental data provide useful information for future photocatalytic applications in the industrial, food, pharmaceutical, and medical fields.

Compatibility of screen-printed piezoelectric 0.65Pb(Mg1/3Nb2/3) O-3-0.35PbTiO(3) thick films with metalized low-temperature co-fired (LTCC) ceramic substrates is examined. Such substrates are interesting for micro-electro mechanical systems, for example for piezoelectric sensors and actuators, where functional layers are usually Pb-based piezoelectrics. In this study the special attention is given to the influence of the Au, Ag and Ag/Pd electrode materials coated over the LTCC on the functional properties of the films. The best phase purity, dielectric and piezoelectric properties were obtained in the films on gilded substrates. No secondary phases were observed at the film/Au interface by scanning electron microscope. The piezoelectric coefficient d(33) of the films on gilded substrates is equal to 120 pC/N.

The exciton-phonon interaction, considered as a stimulated Raman scattering process, is studied in different semiconductor mixtures: PbI2/TiO2, PbI2/Si and CdS/Si. Raman spectra recorded at excitation wavelengths of 514.5 and 488 nm for PbI2 and CdS, respectively, reveal a strong enhancement of the Raman lines peaked at 97 and 305 cm(-1), evaluated by the ratio I-TK/I-300 (K) between the relative intensities of the spectra recorded in the temperature range of 88-300 K. It is found that PbI2 and CdS exhibit a decrease in the Raman intensity modes with decreasing temperature, while in TiO2 and Si an increase in the Raman lines intensities peaked at 138 and 520 cm(-1) is observed. This behavior can be explained by an energy transfer process from PbI2 or CdS towards TiO2 and Si. This explanation is supported by the schematic potential energy levels diagram obtained from the density of states, which is calculated using the density functional theory. According to this energy levels diagram, the electrons are expected to migrate directly from the conduction band (CB) energetic levels of the PbI2 and CdS towards the CB levels of TiO2 and Si.

In this contribution the design and fabrication of ceramic microsystems with integrated different microfluidic elements and sensors will be presented. Ceramic microsystems are based on unconventional application of low-temperature co-fired ceramic technology and materials. This unconventional application is related to three-dimensional ceramic structures, such as cantilevers, ledges, bridges, diaphragms, valleys, channels, holes and cavities, valves, mixers, diffusors, distributors, collectors, flow limiters, sensors, and actuators.

Fe16N2 fine particles were prepared by reduction in 5% H-2/Ar gas mixture flow, starting from goethite or hematite precursors, followed by nitridation in ammonia gas flow. Small amounts of metallic iron and iron oxide are present besides the main phase which is an ordered iron nitride having martensite structure (alpha''-Fe16N2) as revealed by Mossbauer spectroscopy measurements. However, X-ray diffraction data do not show any traces of oxides due to their high degree of amorphization. When nitridation is performed at about 150 C-0, Fe4N phase begins to form and its presence deteriorates the magnetic properties. The samples prepared by nitridation of goethite present better magnetic properties compared to those obtained by nitridation of hematite. Magnetic and Mossbauer measurements performed at ambient temperature were corroborated in order to extract the magnetization at saturation value for each phase which occurs in the obtained samples. The corresponding values are 226 emu/g for Fe16N2 and 198 emu/g for metallic iron contained in the prepared powders.

FePt system attracts currently a great deal of interest for applications as future RE free permanent magnets. Among the key issues to be solved one may count the decreasing of the ordering temperature and improvement of magnetic behavior. For that purpose we have studied the effect of a nitriding post-synthesis procedure on the FePtAgB melt spun ribbons, aimed at refining the microstructure and enhancing the magnetic performances. Deep structural characterization by transmission electron microscopy, electron diffraction, energy dispersive X-ray spectroscopy and X-ray diffraction allowed us to observe the morphology and to correctly assign and identify the nature of the main granular phases observed. Nitriding procedure is shown to strongly enhance the (001) texturing and the degree of ordering of the L1(0) FePt phase, as well as largely increase of coercivity, compared to the as-cast state. These changes are interpreted in terms of Ag segregation towards intergranular region associated to N diffusion and creation of vacancies that favor consistently the process of ordering the FePt grains into the L1(0) tetragonal phase. (C) 2015 Elsevier B.V. All rights reserved.

Spark Plasma Sintering (SPS) and High Pressure-High Temperature (HPHT) methods were chosen in order to study the behaviour of metastable cubic boron nitride (cBN) during sintering of Al2O3 + 30 vol.% cBN composites at low and high pressure. Relatively low sintering temperatures were used to avoid the undesired reverse transformation of cBN to hexagonal, graphite-like form. The microstructure, and phase composition as well as physical and mechanical properties of the resulting Al2O3-cBN composites were investigated. In the ball-on-disc tests, the coefficient of friction and the specific wear rate of the sintered samples were determined by rotating the sample against a stationary alumina ball. The best composites obtained by SPS (at 1300 degrees C/75 MPa) had slightly lower density, Young's modulus and hardness than those obtained by HPHT but their wear resistance was much better. Formation of hBN was suppressed up to 1300 degrees C during SPS consolidation at the pressure of 75 MPa. (C) 2016 Elsevier Ltd. All rights reserved.

Aluminum doped zinc oxide (AZO) thin films were obtained by pulsed laser deposition on (001) SrTiO3 (STO) on a range of substrate temperatures during ablation between 300 degrees C and 600 degrees C. A hexagonal system lying on a cubic one should be difficult to be obtained in epitaxial form. The geometrical selection of the AZO growth on (001) STO is not giving a unique preferential orientation. Two orientations, c-axis (along [001]) and 110, have been observed experimentally with different ratios at different substrate temperature. Discussions are made with respect to the temperature dependence of lattice mismatch between the two cases and the cubic surface of the substrate, and to the substrate surface morphology and terminating atomic layer composition. The 110 AZO is the main phase at deposition temperature of 550 degrees C, while for other substrate temperatures the 001 is the preferential orientation. The conductive character of 110 AZO thin film have been inferred from both ellipsometry spectra and current-voltage measurements. Excepting the samples deposited at 300 degrees C, the lowest resistivity is recorded for the samples with 110 AZO as the main phase. (C) 2015 Elsevier B.V. All rights reserved.

FePt-based alloys are currently under scrutiny for their possible use as materials for perpendicular magnetic recording. Another possible application is in the field of permanent magnets without rare-earths, magnets that may operate at higher temperatures than the classic Nd-Fe-B magnets. Within this study, FeCoPt alloys prepared by rapid solidification from the melt are structurally and magnetically characterized. In the as-cast FeCoPt ribbons, a three-phase structure comprising well-ordered CoFePt and CoPt L1(0) phases embedded in a disordered fcc FePt matrix was evidenced by XRD, HREM and SAED. Extended transmission electron microscopy analysis demonstrates the incipient formation of ordered L1(0) phases. X-ray diffraction was used to characterize the phase structure and to obtain the structural parameters of interest for L1(0) ordering. In the as-cast state, the co-existence of hard magnetic CoFePt and CoPt L1(0) tetragonal phases with the soft fcc FePt phase is obtained within a refined microstructure made of alternatively disposed grains (grain sizes from 1 to 7 nm). Following a thermal treatment of 1 h at 670 degrees C, the soft magnetic fcc matrix phase transforms to tetragonal L1(0) phases (disorder-order transition). The resulting CoPt and CoFePt L1(0) phases have grains of around 5-20 nm in size. In the as-cast state, magnetic measurements show a quite large remanence (0.75 T), close to the value of the parent L1(0) FePt phase. Coercive fields of about 200 kA/m at 5 K were obtained, comparable with those reported for some FePt-based bulk alloys. Upon annealing both remanence and coercivity are increased and values of up to 254 kA/m at 300 K are obtained. The polycrystalline structure of the annealed FeCoPt samples, as well as the formation of multiple c-axis domains in different CoPt and CoFePt regions (which leads to a reduction of the magneto-crystalline anisotropy) may account for the observed coercive fields that are lower than in the case of very thin FeCoPt films. A Curie temperature of about 820 K (close to 550 degrees C) is reported for the Fe35Co15Pt50 alloy which opens wide possibilities for the use of such magnets in high operating temperature industrial applications. The present results indicate that ternary FeCoPt alloys hold a great potential as a novel class of rare earth free exchange-spring coupled nanocomposite magnets. (C) 2015 Elsevier B.V. All rights reserved.

The development of innovative technologies to modify natural textiles holds an important impact for medical applications, including the prevention of contamination with microorganisms, particularly in the hospital environment. In our study, Fe and N co-doped TiO2 nanoparticles have been obtained via the hydrothermal route, at moderate temperature, followed by short thermal annealing at 400 degrees C. These particles were used to impregnate polyester (PES) materials which have been evaluated for their morphology, photocatalytic performance, antimicrobial activity against bacterial reference strains, and in vitro biocompatibility on human skin fibroblasts. Microscopic examination and quantitative assays have been used to evaluate the cellular morphology and viability, cell membrane integrity, and inflammatory response. All treated PES materials specifically inhibited the growth of Gram-negative bacilli strains after 15 min of contact, being particularly active against Pseudomonas aeruginosa. PES fabrics treated with photocatalysts did not affect cell membrane integrity nor induce inflammatory processes, proving good biocompatibility. These results demonstrate that the treatment of PES materials with TiO2-1% Fe-N particles could provide novel biocompatible fabrics with short term protection against microbial colonization, demonstrating their potential for the development of innovative textiles that could be used in biomedical applications for preventing patients' accidental contamination with microorganisms from the hospital environment.

In this work the screen-printed piezoelectric 0.65Pb(Mg1/3Nb2/3)O-3-0.35PbTiO(3) thick films were prepared on metalized low-temperature co-fired ceramic substrates. Such substrates are interesting for micro-electro mechanical systems, for example for piezoelectric sensors and actuators. The prepared thick films exhibit the piezoelectric coefficient d(33) equal to 120 pC/N.

Nano-composite magnets with L1(0) structure derived from binary FePt alloys and prepared as melt-spun ribbons are of current interest due to their higher operating temperature and the ability to be cast as a two-phase magnet with exchange spring magnetic properties, as both soft and hard magnetic phase may emerge from the same metastable precursor, i.e. the disordered cubic A1 phase. The present paper studies the effect of Mn addition on the thermal stability and phase structure, on the abundance of the hard magnetic phase and relative proportion of the soft ones, on the microstructure of the alloy as a function of temperature and on the overall magnetic properties. The interplay of the various magnetic sublattices in the ordering of the L1(0) phases as a consequence of introducing antiferromagnetically coupled Mn atoms in the alloy composition is discussed and interpreted in terms of microstructural changes induced by this addition as revealed by high resolution transmission electron microscopy and Xray diffraction. The temperature evolution of the phase composition and structural parameters is monitored using synchrotron radiation powder diffraction, while the compositional aspects are investigated using proton-induced X-ray emission and energy dispersive X-ray spectroscopy. Magnetic measurements reveal the magnetic parameters of interest (coercivity, remanence, Curie temperature, saturation magnetization), as well as the exchange-coupled two-phase nature of these magnets and provide information that hints at possible spin reorientation transitions in the Mn-containing planes of the L1(0) superlattice. (C) 2015 Elsevier Ltd. All rights reserved.

Rare-earth free (RE-free) exchange coupling nanocomposite magnets are intensively studied nowadays due to their potential use in applications demanding stable high-temperature operation and corrosion resistance. In this respect, the FePt alloy system is one of the most actively addressed potential permanent magnet solutions. In FePt alloys, promising magnetic features arise from the co-existence of hard magnetic L1(0) FePt and soft magnetic L1(2) Fe3Pt phases emerged from the same metastable precursor. The present work deals with an in-situ temperature-resolved synchrotron radiation study of the thermal stability, thermal expansion and microstructure evolution in exchange-coupled FePtAgB alloys. The as-cast microstructural state as well as the optimized magnetic behavior are given as reference and correlated to the observed microstructural evolution with temperature. The melt-spun Fe48Pt28Ag6B18 alloy ribbons were examined in situ by synchrotron X-ray powder diffraction from ambient temperature up to 600 degrees C. The FePt-Fe3Pt exchange-coupled microstructure achieved by rapid solidification is not significantly altered during the high temperature exposure. The thermal expansion of the FePt L1(0) unit cell has been found to be strongly anisotropic, being essentially an in-plane expansion which may be seen as an anisotropic invar effect. For the FePt L1(0) phase, a significant deviation from linear thermal expansion is observed at the Curie temperature T-C = 477 degrees C. This non-linear behavior above T-C is tentatively linked to a diffusion/segregation mechanism of Ag. The promising hard magnetic properties as well as the direct formation of the L1(0) phase from the as-cast state are directly related to the presence of Ag in the intergranular regions. (C) 2014 Elsevier B.V. All rights reserved.

In this paper electrical conductivity analysis of a new material, designed to be used as a solid electrolyte for intermediate temperature fuel cells (IT-SOFC) was performed. The material is based on a composite of scandia doped ceria (SDC) and yttria doped alumina (YA) which ensures higher mechanical stability. The initial powders were obtained by sol-gel method. The samples were prepared by cold pressing and sintering at 1500 degrees C. Materials with variation of the composition (SDC/YA = 95/5; 90/10, 85/15 mass %) were studied. The conductivity was determined by Electrochemical Impedance Spectroscopy. According of the electrochemical analysis the composites with 5 and 10 mass % YA exhibit better conductivity. The results are in correlation with morphological investigation, realized by SEM.

The FePt system has important perspectives as high-temperature corrosion-resistant magnets. In the form of rapidly solidified melt-spun ribbons, FePt-based magnets may exhibit in certain cases a two-phase hard-soft magnetic behaviour. The present paper deals with a microstructural and magnetic study of FePtAgB alloys with increasing Ag content. The aim is to identify and confirm the effect of Ag addition in decreasing the temperature of the FePt disorder-order structural phase transformation. A detailed high-resolution transmission electron microscopy study is employed, and the alternative disposal of hard and soft regions within the two-phase microstructure is observed and interpreted with respect to the X-ray diffraction results. In the as-cast Ag-containing samples, it is shown that there is an optimum of the Ag content for which best magnetic properties are obtained. Ag addition creates a nonlinear behaviour of the coercive field and the ordering parameter, similar to the RKKY interaction-induced interlayer exchange coupling (IEC) observed in magnetic layers separated by non-magnetic spacer layers. Direct formation of the L1(0) phase from the as-cast state in the FePtAgB alloys is reported with magnetic parameters compatible to other exchange spring permanent nanomagnets. These findings open novel perspectives into utilization of such alloys in applications requiring magnets operating in high-temperature industrial environments.

We report the synthesis of a room temperature ferromagnetic Mn-Ge system obtained by simple deposition of manganese on Ge(001), heated at relatively high temperature (starting with 250 degrees C). The samples were characterized by low energy electron diffraction (LEED), scanning tunneling microscopy (STM), high resolution transmission electron microscopy (HRTEM), X-ray photoelectron spectroscopy (XPS), superconducting quantum interference device (SQUID), and magneto-optical Kerr effect (MOKE). Samples deposited at relatively elevated temperature (350 degrees C) exhibited the formation of similar to 5-8 nm diameter Mn5Ge3 and Mn11Ge8 agglomerates by HRTEM, while XPS identified at least two Mn-containing phases: the agglomerates, together with a Ge-rich MnGe similar to 2.5 phase, or manganese diluted into the Ge(001) crystal. LEED revealed the persistence of long range order after a relatively high amount of Mn (100 nm) deposited on the single crystal substrate. STM probed the existence of dimer rows on the surface, slightly elongated as compared with Ge-Ge dimers on Ge(001). The films exhibited a clear ferromagnetism at room temperature, opening the possibility of forming a magnetic phase behind a nearly ideally terminated Ge surface, which could find applications in integration of magnetic functionalities on semiconductor bases. SQUID probed the co-existence of a superparamagnetic phase, with one phase which may be attributed to a diluted magnetic semiconductor. The hypothesis that the room temperature ferromagnetic phase might be the one with manganese diluted into the Ge crystal is formulated and discussed.

A comparative study of two different biocatalytic models, e.g. enzyme immobilized on magnetic particles (EIMP) and cross-linking enzyme aggregates onto magnetic particles (CLEMPA) was performed. The first model was designed as enzyme-immobilized on the magnetic particles surface (EIMP). The second model was constructed as a network structure with the enzyme aggregates and magnetic particles placed into the nodes and polyglutaraldehyde cross-linker as the network ledges. The design was called cross-linking enzyme aggregates onto magnetic particles (CLEMPA). The biocatalysts were prepared using lipase enzyme from Aspergillus niger for catalyzing the glycerol (Gly) conversion to glycerol carbonate (GlyC). The biocatalyst characteristics for both designs (EIMP and CLEMPA) were evaluated using scanning electron microscopy (SEM), laser light scattering (LLS) and UV-Vis techniques. The EIMP model was strongly influenced by the composition of the polymeric layer covering the particles surface, while the size of the magnetic particles affected mostly the CLEMPA design. Also, the biocatalytic capacity of the tested models was evaluated as maximum 52% Gly conversion with 90% GlyC selectivity for EIMP, and 73% Gly conversion with 77% GlyC selectivity for CLEMPA. Both biocatalytic models were successfully used to prepare GlyC from "crude" glycerol collected directly from the biodiesel process (e.g. 49% Gly conversion with 91% GlyC selectivity for EIMP and 70% Gly conversion with 80% GlyC selectivity for CLEMPA).

In this paper, we report on the structural, optical, and electrical properties of a wide compositional range of AlxIn1-xN thin layers deposited on glass and polyethylene terephthalate substrates. AlxIn1-xN layers of controlled composition were obtained by a simple reactive magnetron co-sputtering protocol, using a single aluminium target with indium insets, by varying the Al/In target surface area ratio, and the composition of the deposition atmosphere. The relevant physical properties were investigated and discussed. It is shown that the texture of the thin films is dependent on the cation ratio, while the bowing parameters of lattice constants and band gap values are larger than those of epitaxial layers. (C) 2014 AIP Publishing LLC.

Tetragonal Sr2FeMoO6 powders were prepared by the sol gel and solid-state reaction methods. The structure, microstructure and magnetic characteristics of the double perovskite Sr2FeMoO6 in the form of as-prepared powders and classical sintered ceramics were analyzed and compared. Moreover, the magnetic properties of Sr2FeMoO6 ceramics obtained by sol gel and solid state reaction methods and sintered by the classical method were compared with those of Sr2FeMoO6 ceramics obtained by the same two methods, but sintered by the spark plasma sintering technique. The morphology of the powders obtained from the gel precursor and oxides mixture was characterized by homogeneity, as well as the grains shape and size. The powder prepared by the sol gel method was finer (particle average size of 0.6 mu m) than those obtained from oxides mixture (particle average size of 0.9 mu m). Sintered ceramics with tetragonal Sr2FeMoO6 phase were prepared from the two mentioned powders by classical sintering at 1200 degrees C, 2 h in 5%H-2/Ar. The pellets obtained from the gel powder exhibited higher magnetic characteristics than those derived from the oxides mixture. The saturation magnetization and the total magnetic moment of the samples prepared by the sol-gel method were M-sat=41.18 emu/g and mu(exp)/f.u.=3.26, respectively, while for the samples derived from the oxides mixture were M-sat=40.77 emu/g and mu(exp)/f.u=3.10. Also, Sr2FeMoO6 pellets sintered by the conventional method showed higher saturation magnetization values than those sintered by spark plasma sintering technique. (C) 2014 Elsevier Ltd and Techna Group S.r.l. All rights reserved.

Double perovskite Sr2FeMoO6 was prepared by two ways consisting in sol gel technique and solid-state reaction method. The resulting powders from gel and mixed oxides precursors showed microstructures consisting of very fine grains (0.5-0.8 mu m) and a crystalline perovskite structure. The structural and microstructural properties of the double perovskite Sr2FeMoO6 powders as-prepared and ceramics were compared. Tetragonal Sr2FeMoO6 pellets were prepared from the two powders by spark plasma sintering at: 1000, 1100 and 1200 degrees C and then annealing at 1200 degrees C, 2 h in 5%H-2/Ar. The pellets presented different magnetic characteristics. The saturation magnetization of the samples prepared by sol-gel is close to those prepared by conventional synthesis method. (C) 2013 Elsevier Ltd. All rights reserved.

Postsynthetic modification of [Cu2(mand)2(hmt)] (mand=mandelic acid, hmt=hexamethylenetetramine) with a chiral, dimeric chromium(III)salen complex led to a robust structure. Characterization of this new material showed that it perfectly preserved the textural and structural properties of the parent metalorganic framework (MOF). Although epoxidation of trans-methyl cinnamate with hydrogen peroxide led to copper leaching of 23%, experiments performed with N-methylmorpholine-N-oxide indicated no leaching, even after 72h of exposure. The obtained chiral MOF is an effective catalyst for the enantioselective epoxidation of trans-methyl cinnamate and leads to (2R,3S)-phenylglycidate with a high enantiomeric excess at room temperature.

A new HA/Y2O3:alpha Al2O3 system was obtained by the deposition of a hydroxyapatite thin layer (similar to 150 nm), by magnetron sputtering, onto sintered substrates of low yttria (150 ppm) doped alumina. The yttria doped alumina was synthesized from very pure nanopowders, by mechanical homogenization, followed of pressing, sintering and different annealing regimes, in order to obtain bodies with various degree of nano-micro-structuration. TEM/HRTEM, SEM and EDS morpho-compositional analysis techniques were used to characterize the yttria doped alumina substrate and the hydroxyapatite superficial layer. The interfacial bonding strength between the sintered substrate and the hydroxyapatite thin film was analyzed by SEM. The evolution of the grains growth of the Y2O3:alpha Al2O3 substrate samples, with and without the hydroxyapatite covering layer is observed and discussed. A strong structural interdependence between the covering layer and the sintered substrate was emphasized. The grains' growth behaviour of the studied samples showed a linear evolution. A mathematical model for the grain growth process description was built, the grain size being interpreted as a random variable having a log-normal or Weibull probability density function.

We report on the synthesis of electrode layers by Pulsed Laser Deposition technique. We selected Nickel Oxide-8Yttria-Stabilized Zirconia as anode, La0.6Sr0.4Co0.2Fe0.8O3-delta perovskite material as cathode, and Yttria doped (Ceria-alpha Alumina) as electrolyte. We studied electrode structure (average grain size, porosity, and grain shape), the deposition uniformity and electrode-electrolyte interfaces. The electrodes were investigated in terms of morphology (Scanning Electron Microscopy) and composition (Energy Dispersive X-ray Spectroscopy). The initial powder and the synthesized cathodes have been investigated superficially and in bulk by Mossbauer spectroscopy, in order to detect and analyse local properties. We identified the conditions for electrode layer synthesis in respect with porosity, composition, and mean grain size.

The complementary investigation techniques, Mossbauer spectroscopy, transmission electron microscopy with selected area electron diffraction (TEM/SAED), X-ray diffraction (XRD) have been used to investigate the fate of the Valea lui Stan, Romania, gold-ore nanoscale-minerals during the long time of residence in the waste dumps. The preliminary investigations showed such waste dumps to contain significant amount of metals which cannot be identified by conventional methods. An intense research activity started up in order to evaluate the possibilities to recycle Valea lui Stan waste dumps and to recover metals by chemical or phytoextraction procedures. The waste dumps naturally show different mineral constituents with clay minerals as major phases, observed by XRD-technique. Although the waste dumps materials have whitish-yellowish colours, MOSSBAUER technique evidences the presence of the finely dispersed iron bearing minerals. The authors are focusing to inspect and analyze Fe-compounds in the samples collected from Valea lui Stan's waste dumps in order to identify the magnetic phases by Mossbauer technique.

In this paper the electrochemical analysis of new materials, designed to be used as solid electrolytes for intermediate temperature fuel cells (IT-SOFC) was made. The materials are two different composites based on ceria 10YDC + (10%) 150ppm YA and 10ScDC + (10%) 150ppm YA, obtained by sol-gel method and sintered at temperature of 1500 degrees C. The electrochemical investigation was performed by Electrochemical Impedance Spectroscopy technique. According of these analyses the composite 10YDC + (10%) 150ppm YA presents better conductivity than 10ScDC + (10%) 150ppm YA. These results were related with morphological investigation, realized by SEM.

The effects of the self-assembled 4,4'-thio-bis-benzenethiolate protected gold nanoclusters onto a p-GaAs (1 0 0) electrode were examined by AFM, XPS, SHG and EIS investigations. The AFM and XPS results revealed a well-ordered overlayer exhibiting a bi-modal highly correlated fractal behavior which, however, cannot fully protect the semiconducting surface against the oxidation in air. The EIS data pointed out the influence exerted by the gold-monolayer protected clusters (Au-MPCs) over the charging/discharging processes observed at p-GaAs (1 0 0) electrode. Although the applied potential is varied linearly, the potential drop within the semiconductor space charge region as well as that across the Au-MPCs layer undergoes stepped changes supposed to result in the discrete charging of the Au-MPCs. These effects point to an electronic equilibrium between the Au-MPCs and the semiconducting substrate. Fermi level pinning and enhancement of the SHG response in the potential range where the surface/interface states in the semiconductor band gap become electrically active bring further proof in this respect. (c) 2012 Elsevier Ltd. All rights reserved.

The hydrogen storage material lithium borohydride was infiltrated from solvent solution into the pores of the carbon replica of MSU-H mesoporous silica by the incipient wetness method. Different amounts of lithium borohydride up to 40 % from the weight of the high surface area carbonic material were used. By this method was achieved a good dispersion of the hydride into the carbonaceous support. The hydrogen desorption starts at temperatures as low as 150 degrees C for the sample with 8 wt% LiBH4 dispersed onto the MSU-H carbon replica while pure LiBH4 does not release hydrogen below 300 degrees C. After rehydrogenation, a lower amount of hydrogen is desorbed due to the fact that increasing temperature up to 400 degrees C a part of hydride segregates outside the pores of the carbonaceous support.

Replacing the graphite with carbides in the mixture with Fe powder may be an alternative technological process, by the fact that as carbides decompose when heated, the carbon is set free and diffuses into the Fe network ensuring chemical and structural homogeneity corresponding to sintered steels. Using cementite nanopowder mix with Fe powder is to ensure a better compaction by pressing, less time to decompose and C diffusion into the Fe network in a remarkably chemical homogeneity. The obtaining procedure for Fe3C consists in direct carburation of Fe powder in a special chamber.

The combined investigation techniques, electron probe microanalysis (EPMA), Mossbauer spectroscopy (NGR), transmission electron microscopy (TEM), selected area electron diffraction (SAED), X-ray diffraction (XRD),) evidenced the third level of the inclusions at nanosize scale for specific minerals of different Romanian metamorphic deposits. So, NGR technique reveals the contribution of the (Mn, Fe) oxides - small particles at standard (RT) and at very low temperature (LHeT) in the Fe-52 gamma - ray signal of manganoan-fayalites (Razoare deposit). The EM analysis techniques confirmed the presence of the nanometric Fe and Mn oxides inclusions in manganoan fayalites, as well as of pyroxferroite (Razoare deposit). On the other hand, an extensive investigation of the gold ores in the South Carpathians (Costesti, Valea lui Stan and Jidostita) has been performed by using a fruitful combination among the above mentioned complementary mineralogical and structural methods. The investigation of the representative sulfide samples by the structural techniques relieved new minerals in the gold ores, the presence of submicroscopic inclusions of uytenbogaardtite, cobaltite and loellingite as well as the "coral like" aggregates of nanometric gold.

The attractive properties of Yttria doped ceria, particularly the structural and material properties, have led to vast research efforts to investigate and develop such materials. One of the main applications of this ceramic is in the IT-SOFC. The aim of this paper is the preparation and characterization of Y doped Ceria and low doped alpha-Al2O3, a new composite for IT-SOFC (10 mol %) Y:CeO2 and (150 ppm) Y:alpha-Al2O3 composite were obtained by sol-gel or mechanical route for 10YDC and 150 Y:alpha-Al2O3. Shapes, size distributions and the mean of grains were determined by SEM, EDX and statistical investigations.

The attractive properties of ceria, particularly the conductivity and chemical stability, have led to vast research efforts to investigate, characterize and develop such materials. One of the main applications of this ceramic is in the solid oxides fuel cells for intermediate temperatures IT-SOFC. The aim of this work is the preparation and characterization of cubic ceria nanopowders doped with 10 mol % yttria or Scandia. A thermal treatment (calcinations) was applied on the obtained nanopowders, which were consequently investigated by X-ray diffraction (XRD), transmission electron microscopy (TEM) and selected aria electron diffraction (SAED).

The attractive properties of Yttria doped ceria, particularly the structural and material properties, have led to vast research efforts to investigate and develop such materials. One of the main applications of this ceramic is in the solid oxides fuel cells for intermediate temperatures IT-SOFC. The aim of this paper is the preparation and characterization of Y doped Ceria - low Y doped alpha-Al2O3, a new composite for IT-SOFC. (10 mol %) Y : CeO2 and (150 ppm) Y : alpha - Al2O3 - composite were obtained by sol-gel or mechanical route for 10YSC, mechanical route for 150 Y : alpha - Al2O3. Grain shapes, grain size distributions and the mean grain value were determined by SEM, EDX and statistical investigations.

Yttria doped ceria reinforced with yttria doped alumina compound for IT-SOFC applications has been prepared by sol-gel method and sintered at 1300 degrees C, 1400 degrees C, 1500 degrees C. XRD, and SEM show the presence of a needle-like cerium-magnetoplumbite (CeAl11O17) phase in the compound; the oxygen deficient phase grows from the alumina phase by using ceria from the surrounding matrix and releasing oxygen ions As the sintering temperature is increased, the alumina phase is gradually transformed into CeAl11O17. Compared to the yttria doped ceria without reinforcement, the obtained compounds with ceria-magnetoplumbite show only a slight decrease of the Young elasticity modulus. However, the samples become brittle after backing in oxygen atmosphere (1000 degrees C, and 1500 degrees C).

Nitrogen doped TiO2 aerogels were obtained by sol gel process followed by supercritical drying with liquid CO2. Urea and NH3 (25% aqueous solution) were used as nitrogen sources. The as-prepared aerogels were submitted to thermal treatments performed under different experimental conditions (temperature and heating time). Increasing the temperature from 450 degrees C to 550 degrees C a decrease about 32% and 15.4% of the particle size and surface OH groups' concentration, respectively and an increase about 21.4% of the incorporated nitrogen in TiO2 lattice were observed. The immersion of the TiO2 aerogels in NH3 solution induced a decreasing by 48.86% and by 80% of the S-BET and the aerogel porosity, respectively. The photocatalytic activity of the obtained N-doped TiO2 was found to depend mainly on the nitrogen incorporation in the TiO2 lattice. (C) 2009 Elsevier Inc. All rights reserved.

Despite many investigations already performed with respect to sintering stability and grain growth vs. annealing conditions in low yttrium doped alpha- Al2O3 (150 ppm) - some fundamental questions are still open. These questions concern mainly the influence of small level of impurities at grain boundary in the sintering behavior and grains growth of the materials, i.e. the microstructure function of the annealing time at annealing temperature of 1650 degrees C. The low yttrium doped alpha- Al2O3 (150 ppm) samples were sintered and annealed at high temperatures. Besides conventional micro structural studies, such as grain diameter and grain size functions of distribution of the annealing temperature were studied by electron microscopy investigations and statistical measurement. The implications of the different microstructures with respect to micro structural stability have discussed and compared to observations described in the literature.

The attractive properties of zirconia, particularly fracture toughness, wear resistance and chemical stability, have led to vast research efforts designed to investigate, characterize and develop such materials. Applications vary from structural, mechanical, biomedical to electrical, especially the fuel cells field. The current study is aiming at preparation and structural characterization Of 10% Y2O3 stabilized ZrO2 nanometric powders. The sol-gel method is known to be easy to use for producing various kinds of materials, structured at nanometric level, so was chosen for the elaboration of powders. Different thermal treatments were applied to the obtained materials, which were consequently investigated through thermal analysis, X-ray diffraction (XRD) scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The characteristics Of Y2O3 doped zirconia powders are influenced by the processing parameters and proved promising for further applications in, for example, the Solid Oxides Fuel Cell field.

Hydroxyapatite (HAP) thin films (0.2 pm, 0.3 pm and 1.2 mu m thickness) were grown by RF magnetron sputtering in argon atmosphere onto silicon substrates at high deposition rates (0.6 mu m/h). Crystalline HAP films were obtained using a low temperature (100 degrees C) followed by post-deposition annealing at 300 degrees C, 450 degrees C, 500 degrees C and 550 degrees C in environmental air for 1 hour. An important influence of the films thickness upon the crystallization degree was noticed at intermediate annealing temperatures, as obtained from XRD measurements. For low and high temperatures similar values were obtained with a better crystallization degree for the thinner films. FTIR absorption led to the same conclusion considering the shape of stretching and bending PO4 lines. This suggests that the crystallization process has a diffusion component besides usual thermal activation process.