National Institute Of Materials Physics - Romania

This paper outlines a method of extraction of iron from water in the form of iron oxyhydroxide natural nanoclusters at comparatively low concentrations and varied ranges of pH using zinc acetate salt. The zinc acetate salt dissociates into Zn(2+)and acetate ions in water where Zn(2+)interacts with iron clusters present in a solution of a given iron concentration and pH, while the acetate ion helps in charge-neutralization based coagulation and consequent precipitation of such nanoclusters. The Zn(2+)ions may also lead to the growth of layered zinc hydroxide (LZH) nanosurfaces at pH >= 6 at sufficient loading. The advantage of this method is the active chemical interaction of Zn(2+)with Fe clusters, followed by growth, which ensures that only some added Zn ions remain in the water while the rest precipitate out along with the residual iron oxyhydroxide, especially at higher pH. The solid that precipitated under various different conditions was successfully evaluated by XRD (formation of ferrihydrite-like nanoclusters (n-Fh)), FTIR (the presence of acetate in the solid n-Fh), TEM (the presence of zinc at higher pH), and EXAFS (local structural characterization). ICP analysis of the obtained solid and the corresponding filtrate revealed the removal efficiency of iron and zinc from the solution at various initial concentrations and pH values. This method of extracting soluble Fh-like nanoclusters by charge neutralization appears to be a suitable promising tool for water purification, because ferrihydrite is capable of isolating other adsorbed contaminants from water, along with itself.

Graphene-based photocatalytic layers were prepared by reactive matrix assisted pulsed laser evaporation technique. Binary, nitrogen doped reduced graphene oxide (RGO)/TiO2 and ternary RGO/TiO2/graphitic carbon nitride (g-C3N4) compounds were synthesized and simultaneously deposited onto solid substrates. Aqueous dispersions of commercial graphene oxide platelets and TiO2 nanoparticles were prepared. NH3 or melamine powder was added to the dispersions to achieve enhanced nitrogen doping and synthesis of g-C3N4 during laser irradiation. The photocatalytic efficiency of the layers towards degradation of antibiotic, chloramphenicol and organic dye molecules was systematically investigated and correlated with structural, compositional, and morphological features. This study provides new insights into the importance of TiO2 crystal facets and the synergistic effects between TiO2 nanocrystals and the other constituents, nitrogen doped RGO and g-C3N4 of the hybrid layers. As a result of combined effect of constituent materials, TiO2, RGO, and g-C3N4 as well as N doping of RGO, through the generation of quaternary and pyrrolic N functionalities, the composite layers showed high photocatalytic efficiency for degradation of organic molecules. Stability and reusability experiments indicated that the composite layers maintain their high photodegradation efficiency towards organic molecules during consecutive degradation cycles. Active radical scavenging experiments were also carried out in order to determine the role of the main active species involved in the photocatalytic degradation process.

Iron oxides such as magnetite and maghemite coated with cetyltrimethylammonium bromide (CTAB) are very promising materials for wastewater treatment because iron oxide can be easily separated from solutions using the magnetic separation procedure Iron oxide (IO) coated CTAB was synthesized by an adapted co-precipitation method. In the present study, the IO-CTAB was used for removing arsenic from water for the first time. In the present study, the performance of iron oxide coated CTAB biocomposites as an adsorbent for arsenic removal from aqueous solutions was examined. X-ray diffraction (XRD) analysis and the results revealed a cubic phase Fd-3 m of Fe(3)O(4)with lattice a = 8.40 angstrom and average crystal size equal to 17.26 +/- 3 nm. The mean particle size calculated from transmission electron microscopy (TEM) was 19.86 +/- 1.7 nm. The results of the adsorption batch experiments and the data determined using the Langmuir and Freundlich models emphasized that IO-CTAB nanoparticles were favorable for the adsorption of As(III) ions from aqueous solutions. Ultrasound measurements have shown that IO-CTAB is a cost-effective biocomposite for removing arsenic from contaminated solutions. Moreover, x-ray photoelectron spectroscopy (XPS) has shown that during the process of arsenic absorption, there is oxidation from As(III) to As(V), which leads to a decrease in toxicity during this process. The results of the cytotoxic assays confirmed that the IO-CTAB nanoparticles did not induce any morphological changes in the HeLa cells and did not affect their proliferation after 24 h of incubation.

Polymer-based nanocomposites have recently received considerable attention due to their unique properties, which makes them feasible for applications in optics, sensors, energy, life sciences, etc. The present work focuses on the synthesis of nanocomposites consisting of a polytetrafluorethylene-like matrix in which metallic nano-silver are embedded, by using multiple magnetron plasmas. By successively exposing the substrate to separate RF magnetrons using as combination of target materials polytetrafluorethylene (PTFE) and silver, individual control of each deposition process is insured, allowing obtaining of structures in which silver nanoparticles are entrapped in-between two PTFE layers with given thicknesses. The topographical and morphological characteristics investigated by means of Scanning Electron Microscopy and Atomic Force Microscopy techniques evidenced the very presence of Ag nanoparticles with typical dimension 7 nm. The chemical composition at various depositing steps was evaluated through X-ray Photoelectron Spectroscopy. We show that the presence of the top PTFE layer prevents silver oxidation, while its thickness allows the tailoring of optical properties, as evidenced by spectroellipsometry. The appearance of chemical bonds between silver atoms and PTFE atoms at interfaces is observed, pointing out that despite of pure physical deposition processes, a chemical interaction between the polymeric matrix and metal is promoted by plasma.

Covalent immobilization of antibodies to protein G beads is a basic molecular biology method, although the beads present poor recovery results. Our aim was to reuse the immobilized antibody-protein G complex on a very small scale, therefore we optimized the crosslinking procedure to be used on the wells of a standard 96-well microplate. The method used involves the affinity binding of the antibody to the protein G surface, followed by the immobilization step using different crosslinking reagents, DMP and BS3, quenching the crosslinking reaction, and binding the antibody-specific antigen. By scaling down the procedure, we were able to reuse the anti-EGFR crosslinked wells more than 20 times. This method can be used to perform assays on a wide range of solid supports containing the protein G in an immobilized form, including functionalized nanosensors, for immunoprecipitation, protein and cell lysate purification, target protein enrichment.

With the aim of demonstrating phase coexistence of two magnetic phases in an intermediate annealing regime and obtaining highly coercive FePt nanocomposite magnets, two alloys of slightly off-equiatomic composition of a binary Fe-Pt system were prepared by dynamic rotation switching and ball milling. The alloys, with a composition Fe(53)Pt(47)and Fe55Pt45, were subsequently annealed at 400 degrees C and 550 degrees C and structurally and magnetically characterized by means of X-ray diffraction,Fe-57 Mossbauer spectrometry and Superconducting Quantum Interference Device (SQUID) magnetometry measurements. Gradual disorder-order phase transformation and temperature-dependent evolution of the phase structure were monitored using X-ray diffraction of synchrotron radiation. It was shown that for annealing temperatures as low as 400 degrees C, a predominant, highly ordered L1(0)phase is formed in both alloys, coexisting with a cubic L1(2)soft magnetic FePt phase. The coexistence of the two phases is evidenced through all the investigating techniques that we employed. SQUID magnetometry hysteresis loops of samples annealed at 400 degrees C exhibit inflection points that witness the coexistence of the soft and hard magnetic phases and high values of coercivity and remanence are obtained. For the samples annealed at 500 degrees C, the hysteresis loops are continuous, without inflection points, witnessing complete exchange coupling of the hard and soft magnetic phases and further enhancement of the coercive field. Maximum energy products comparable with values of current permanent magnets are found for both samples for annealing temperatures as low as 500 degrees C. These findings demonstrate an interesting method to obtain rare earth-free permanent nanocomposite magnets with hard-soft exchange-coupled magnetic phases.

In this work, the effects of graphene oxide (GO) concentrations (1.5 wt.%, 2.5 wt.%, and 5 wt.%) on the structural, morphological, optical, and luminescence properties of zinc oxide nanorods (ZnO NRs)/GO nanocomposites, synthesized by a facile hydrothermal process, were investigated. X-ray diffraction (XRD) patterns of NRs revealed the hexagonal wurtzite structure for all composites with an average coherence length of about 40-60 nm. A scanning electron microscopy (SEM) study confirmed the presence of transparent and wrinkled, dense GO nanosheets among flower-like ZnO nanorods, depending on the GO amounts used in preparation. Raman spectroscopy, Fourier transform infrared spectroscopy (FTIR), ultraviolet-visible (UV-Vis) absorption spectroscopy, and photoluminescence (PL) measurements revealed the impact of GO concentration on the optical and luminescence properties of ZnO NRs/GO nanocomposites. The energy band gap of the ZnO nanorods was independent of GO concentration. Photoluminescence spectra of nanocomposites showed a significant decrease in the intensities in the visible light range and red shifted suggesting a charge transfer process. The nanocomposites' chromaticity coordinates for CIE 1931 color space were estimated to be (0.33, 0.34), close to pure white ones. The obtained results highlight the possibility of using these nanocomposites to achieve good performance and suitability for optoelectronic applications.

GeSn alloys have the potential of extending the Si photonics functionality in shortwave infrared (SWIR) light emission and detection. Epitaxial GeSn layers were deposited on a relaxed Ge buffer on Si(100) wafer by using high power impulse magnetron sputtering (HiPI-MS). Detailed X-ray reciprocal space mapping and HRTEM investigations indicate higher crystalline quality of GeSn epitaxial layers deposited by Ge HiPI-MS compared to commonly used radio frequency magnetron sputtering (RF-MS). To obtain a rectifying heterostructure for SWIR light detection, a layer of GeSn nanocrystals (NCs) embedded in oxide was deposited on the epitaxial GeSn one. Embedded GeSn NCs are obtained by cosputtering deposition of (Ge1-xSnx)(1-y)(SiO2)(y) layers and subsequent rapid thermal annealing at a low temperature of 400 degrees C. Intrinsic GeSn structural defects give p-type behavior, while the presence of oxygen leads to the n-character of the embedded GeSn NCs. Such an embedded NCs/epitaxial GeSn p-n heterostructure shows superior photoelectrical response up to 3 orders of magnitude increase in the 1.2-2.5 mu m range, as compared to performances of diode based only on embedded NCs.

The present work reports for the first time, the employment of ferroelectric ZrO(2)films as energy storage capacitors utilized in pulsed power systems. Furthermore, the effect of insertion of a low permittivity dielectric HfO2:Al2O3(HAO) layer, with a thickness ranging from 2 to 8 nm, on the tunability of ferroelectric and energy storage characteristics of ZrO(2)films is assessed. The increase in thickness of the HAO layer gave rise to distorted ferroelectric loops with decreased polarization, coercive field, and hysteresis loss of the films. These results are correlated with the depolarization field induced by the insertion of the dielectric HAO layer. An optimum combination of high energy density of 54.3 J cm(-3)and good storage efficiency of 51.3% are obtained for the ZrO(2)film capacitors with 2 nm-thick HAO insert layer. These values correspond to an increase of similar to 55% and similar to 92%, from the respective values of pure ZrO(2)film capacitors. In addition, the HAO/ZrO(2)films showed a good fatigue endurance of energy storage performance over 10(9)electric field cycles. The energy storage density obtained from HAO(2 nm)/ZrO(2)film capacitor is found to be higher than that reported for several Pb-based as well as Pb-free ferroelectric ceramic films with complex compositions. The present study demonstrates that simple binary oxides such as ZrO(2)with ferroelectric behavior could be potential candidates for developing high performance energy storage capacitors.

The negative-capacitance effect in devices based on combined ferroelectric-dielectric gate oxides is thought to be a potential solution to break free from the so-called Boltzmann tyranny. To lower the power consumption in field-effect transistors, the subthreshold swing factor S should be reduced below the ther-modynamic limit of 60 mV per decade. Yet, despite numerous studies dedicated to this effect in the past decade, its origin in ferroelectric capacitors or ferroelectric-based superlattices remains unclear, being considered either a transitory product of polarization switching or an intrinsic phenomenon related to the presence of ferroelectric polarization. In this study it is shown, starting from simple electrostatic con-siderations, that negative capacitance is present during polarization switching and is accompanied by a significant increase of the current flowing through the ferroelectric capacitor. Coupled with piezo-force microscopy results, it is shown that the polarization orientation suddenly changes at the coercive voltage, accompanied by a complete reconfiguration of the potential barriers at the Schottky-like contacts present at the electrode-ferroelectric interfaces. A method to estimate the polarization-switching time, as the time associated with the presence of the negative-capacitance effect, is proposed. Values in the range from 100 to 1000 ns are obtained for epitaxial PbZr0.2Ti0.8O3 films. These findings suggest that negative capacitance may be an intrinsic effect in ferroelectrics but that it is a transitory effect, present only when ferroelectric polarization passes through zero (switching).