National Institute Of Materials Physics - Romania

A new methodology to obtain magnetic information on magnetic nanoparticle (MNP) systems via electron tomography techniques is reported in this work. The new methodology is implemented in an under-development software package called Magn3t, written in Python and C++. A novel image-filtering technique that reduces the highly undesired diffraction effects in the tomography tiltseries has been also developed in order to increase the reliability of the correlations between morphology and magnetism. Using the Magn3t software, the magnetic shape anisotropy magnitude and direction of magnetite nanoparticles has been extracted for the first time directly from transmission electron tomography.

The ability of TiO2 to generate reactive oxygen species under UV radiation makes it an efficient candidate in antimicrobial studies. In this context, the preparation of TiO2 microparticles coated with Ca- and Cu-based composite layers over which Cu(II), Cu(I), and Cu(0) species were identified is presented here. The obtained materials were characterized by a wide range of analytical methods, such as X-ray diffraction, electron microscopy (TEM, SEM), X-ray photoelectron (XPS), and UV-VIS spectroscopy. The antimicrobial efficiency was evaluated using qualitative and quantitative standard methods and standard clinical microbial strains. A significant aspect of this composite is that the antimicrobial properties were evidenced both in the presence and absence of the light, as result of competition between photo and electrical effects. However, the antibacterial effect was similar in darkness and light for all samples. Because no photocatalytic properties were found in the absence of copper, the results sustain the antibacterial effect of the electric field (generated by the electrostatic potential of the composite layer) both under the dark and in light conditions. In this way, the composite layers supported on the TiO2 microparticles' surface can offer continuous antibacterial protection and do not require the presence of a permanent light source for activation. However, the antimicrobial effect in the dark is more significant and is considered to be the result of the electric field effect generated on the composite layer.

The hematite-based nanomaterials are involved in several catalytic organic and inorganic processes, including water decontamination from organic pollutants. In order to develop such species, a series of bimetallic hematite-based nanocomposites were obtained by some goethite composites-controlled calcination. Their composition consists of various phases such as alpha-FeOOH, alpha-Fe2O3 or gamma-Fe2O3 combined with amorphous (Mn2O3, Co3O4, NiO, ZnO) or crystalline (CuO) oxides of the second transition ion from the structure. The component dimensions, either in the 10-30 or in the 100-200 nm range, together with the quasi-spherical or nanorod-like shapes, were provided by Mossbauer spectroscopy and powder X-ray diffraction as well as transmission electron microscopy data. The textural characterization showed a decrease in the specific area of the hematite-based nanocomposites compared with corresponding goethites, with the pore volume ranging between 0.219 and 0.278 cm(3)g(-1). The best catalytic activity concerning indigo carmine removal from water in hydrogen peroxide presence was exhibited by a copper-containing hematite-based nanocomposite sample that reached a dye removal extent of over 99%, which correlates with both the base/acid site ratio and pore size. Moreover, Cu-hbnc preserves its catalytic activity even after four recyclings, when it still reached a dye removal extent higher than 90%.

In this study, three novel magnetic nanocomposites based on carboxyl-functionalized SBA-15 silica and magnetite nanoparticles were prepared through an effective and simple procedure and applied for methylene blue (MB) and malachite green G (MG) adsorption from single and binary solutions. Structure, composition, morphology, magnetic, and textural properties of the composites were thoroughly investigated. The influence of the amount of carboxyl functional groups on the physicochemical and adsorptive properties of the final materials was investigated. The capacity of the synthesized composites to adsorb MB and MG from single and binary solutions and the factors affecting the adsorption process, such as contact time, solution pH, and dye concentration, were assessed. Kinetic modelling showed that the dye adsorption mechanism followed the pseudo-second-order kinetic model, indicating that adsorption was a chemically controlled multilayer process. The adsorption rate was simultaneously controlled by external film diffusion and intraparticle diffusion. It was evidenced that the molecular geometry of the dye molecule plays a major role in the adsorption process, with the planar geometry of the MB molecule favoring adsorption. The analysis of equilibrium data revealed the best description of MB adsorption behavior by the Langmuir isotherm model, whereas the Freundlich model described better the MG adsorption.

Polycrystalline La(0.8)K(0.2-x)Pb(x)MnO3 (x = 0.05, 0.10, 0.15, 0.20) ceramics were successfully prepared by flash combustion route and their structural, morphological, magnetic and magnetocaloric properties were investi-gated. Structural analyses using X-ray diffraction reveal that all samples are crystallized in the rhombohedral structure and belong to R <(3) over bar > c space group. The increase of Pb doping does not modify the crystalline structure but changes the grain size and lattice parameters. X-ray photoelectron spectroscopy (XPS) fitting results of Mn 2p peaks confirmed the coexistence of Mn3+ and Mn4+ ions which contribute to the double exchange interactions improving the ferromagnetic order in the samples. The magnetization's temperature and magnetic field de-pendences indicate a second-order ferromagnetic-paramagnetic transition of the ceramics. A significant mag-netic entropy change near room temperature was observed for La0.8K0.1Pb0.1MnO3, showing considerable magnetocaloric properties. Furthermore, electron paramagnetic resonance spectroscopy (EPR) was also used to examine the ferromagnetic-paramagnetic transition.

This study presents the functionalization and characterization of graphene and electromagnetic interference (EMI) attenuation capacity in epoxy-nanocomposites. The modification of graphene involved both small molecules and polymers for compatibilization with epoxy resin components to provide EMI shielding. The TGA and RAMAN analyses confirmed the synthesis of graphene with a different layer thickness of the graphene sheets. Graphene samples with different layer thicknesses (monolayer, few layers, and multilayer) were selected and further employed for epoxy coating formulation. The obtained nanocomposites were characterized in terms of EMI shielding effectiveness, SEM, micro-CT, magnetic properties, and stress-strain resistance. The EMI shielding effectiveness results indicated that the unmodified graphene and hexamethylene diamine (HMDA) modified graphene displayed the best EMI shielding properties at 11 GHz. However, the epoxy nanocomposites based on HMDA modified graphene displayed better flexibility with an identical EMI shielding effectiveness compared to the unmodified graphene despite the formation of aggregates. The improved flexibility of the epoxy nanocomposites and EMI shielding characteristics of HMDA functionalized graphene offers a practical solution for textile coatings with microwave absorbing (MA) capacity.

The aim of this experimental work was to investigate the influence of the ion beam charge state on damage production in nanomaterials. To achieve this, we employed Raman spectroscopy, atomic force microscopy, and transmission electron microscopy to investigate nanomaterials irradiated by a 23 MeV I beam. We found a significant influence of the ion charge state on damage production in monolayer graphene, but found no evidence of this effect in bilayer and trilayer graphene, nor in graphite. Furthermore, we found no evidence of this effect in CaF2 and SiO2 nanocrystals irradiated with the same ion beam.

Cu2ZnSnS4 (CZTS) is regarded as one of the emerging materials for next-generation thin film solar cells. However, its synthesis is complex, and obtaining a single-phase CZTS thin film is difficult. This work reports the elaboration of Cu2ZnSnS4 thin films by a sequential magnetron sputtering deposition of Cu2SnS3 (CTS) and ZnS as stacked films. Initially, the CTS films were prepared on a soda lime glass substrate by annealing Cu and SnS2 stacked layers. Second, ZnS was deposited by magnetron sputtering on the CTS films. The CTS\ZnS stacks were then annealed in Sn + S or S atmospheres. The tetragonal CZTS structure was obtained and confirmed by grazing incidence X-ray diffraction and Raman spectroscopy. The morphological and compositional characteristics, measured by scanning electron microscopy and energy-dispersive spectroscopy, revealed large grains and dense surfaces with the elemental composition close to the intended stoichiometry. Additional X-ray photoemission spectroscopy measurements were performed to determine the surface chemistry and particularities of the obtained films. The optical properties, determined using conventional spectroscopy, showed optimal absorber layer band gap values ranging between 1.38 and 1.50 eV. The electrical measurements showed that all the films are p-type with high carrier concentrations in the range of 10(15) to 10(20) cm(-3). This new synthesis route for CZTS opens the way to obtain high-quality films by an industry-compatible method.

Cu2ZnSnS4 (CZTS) is regarded as one of the emerging materials for next-generation thin film solar cells. However, its synthesis is complex, and obtaining a single-phase CZTS thin film is difficult. This work reports the elaboration of Cu2ZnSnS4 thin films by a sequential magnetron sputtering deposition of Cu2SnS3 (CTS) and ZnS as stacked films. Initially, the CTS films were prepared on a soda lime glass substrate by annealing Cu and SnS2 stacked layers. Second, ZnS was deposited by magnetron sputtering on the CTS films. The CTS\ZnS stacks were then annealed in Sn + S or S atmospheres. The tetragonal CZTS structure was obtained and confirmed by grazing incidence X-ray diffraction and Raman spectroscopy. The morphological and compositional characteristics, measured by scanning electron microscopy and energy-dispersive spectroscopy, revealed large grains and dense surfaces with the elemental composition close to the intended stoichiometry. Additional X-ray photoemission spectroscopy measurements were performed to determine the surface chemistry and particularities of the obtained films. The optical properties, determined using conventional spectroscopy, showed optimal absorber layer band gap values ranging between 1.38 and 1.50 eV. The electrical measurements showed that all the films are p-type with high carrier concentrations in the range of 10(15) to 10(20) cm(-3). This new synthesis route for CZTS opens the way to obtain high-quality films by an industry-compatible method.

In this study curcumin was immobilized in a silica matrix to overcome its poor aqueous solubility and rapid degradation profile. Two kinds of sol-gel powders based on colloidal silica were synthesized and characterized, one prepared with an ethanolic solution of curcumin and the other using cethyltrimethylammonium bromide (CTAB) to solubilize the dye. The successful integration of curcumin in the matrix as well as the interaction with the components of the composite powders was validated by different analysis methods (DSC, FTIR). The samples morphology was evaluated by SEM. UV-Vis and fluorescence studies showed that curcumin was stable, in its enol configuration in both matrices. The sensitivity to ammonia was proved by exposing the powders to NH3 vapors in a sealed vessel. Color changes were measured with a colorimeter. UV-Vis spectra showed that the enol form of the dye in EtOH/CTAB based SiO2 matrices was energetically stable under NH3 atmosphere, even after being kept a few days at low temperature. A fluorescence quenching of both samples was noticed due to interaction curcumin-ammonia. Both samples have antimicrobial properties, the CTAB containing one being more efficient. The EtOH/CTAB based SiO2 powders may represent a novel signaling and antimicrobial system, useful for food or pharmaceutical applications. [GRAPHICS] .