National Institute Of Materials Physics - Romania

Europium doped (0.1% and 1%) chlomborate BaO-B2O3-BaCl2 glass and glass-ceramic with embedded BaCl2 nanocrystals have been synthesised, investigated, and compared with the corresponding nanocrystalline powder. The structural analysis of the glass evidenced ionic bonds characteristic to the glass host structure and compositional changes during the melting. X-ray diffraction and transmission electron microscopy revealed the formation of orthorhombic BaCl2 nanocrystals of about tens on nm in size and a smaller amount of BaB2O4 nanocrystals. Structural analysis of the Eu2+-doped BaCl2 nanocrystals has shown a distortion of the crystalline cell assigned to the growth process, affected by defects and ionic impurities. Photoluminescence spectra of the glass-ceramic revealed Eu3+ and Eu2+ luminescent ion species, but only Eu2+ is incorporated within the BaCl2 nanocrystalline phase. Electron paramagnetic resonance measurements in X-band sustain the presence of Eu2+ ions. The EPR parameters (g values and hyperfine constants) resulting from the Q-band EPR spectra simulations recorded on glass-ceramic are similar to those in Eu2+-doped BaCl2 and confirmed the partial incorporation of Eu2+ ions within the BaCl2:Eu2+ nanocrystals in the glass-ceramics.

The local crystal/magnetic structures of the SrFe12-xInxO19 solid solutions (x = 0.1; 0.3; 0.6 and 1.2) were investigated using neutron powder diffraction. The measurements of the electric polarization for all investigated samples were carried out as a function of the external electric field. The presence of the ferroelectric and ferromagnetic ordering (dual ferroic ordering) in the SrFe12-xInxO19 hexaferrites at 300 K was found. This appearance contradicts to the conventional opinion describing their crystal structure (centrosymmetric space group P6(3)/mmc (No. 194)). The reason for the existence of a spontaneous polarization (nonzero dipole moment) in the SrFe12-xInxO19 hexaferrites continues controversial. The crystal structure of the hexaferrites was considered both the centrosymmetric P6(3)/mmc and non-centrosymmetric P6(3)mc space groups. This fact made it possible to find a connection between the emerging dipole moment and not equal distortions of the neighbor oxygen polyhedral. The nature description of the nonzero dipole moment formation in a quasi-centrosymmetrical system of the In-substituted SrFe12-xInxO19 hexaferrites was presented based on the neutron diffraction data. (C) 2021 Elsevier B.V. All rights reserved.

Piezoelectric hard/soft effects of multivalence co-dopants (Sb and Mn) in correlation with their location in the lattice, were investigated in PZT ceramics, prepared by conventional ceramic technology, with the following compositions: Pb0.98Sr0.02 ((Ti0.49Zr0.51)(1-0.015-x)Mn0.015Sbx)O-3 with x = 0, 0.005, 0.01, 0.02, 0.03, where antimony was initially assumed to substitute for Ti/Zr ions. The antimony valence state was found to be +3 in all samples by X-ray Photoelectron Spectroscopy investigations. The Electron Paramagnetic Resonance spectra evidenced a steep enhancement of the Mn2+ concentration upon increasing antimony doping level, explained by a charge compensation mechanism, between the Sb3+ ions substituting Pb2+ at the A-sites and the Mn2+ ions, localized at the B-sites. The incorporation of Sb3+ at the A-site of the PZT lattice is also supported by the variation of the lattice parameters, determined by X-ray Diffraction, with the increasing Sb concentration. The investigation of the dielectric, electromechanical and ferroelectric properties evidenced a hard piezoelectric behavior, mainly attributed to the presence of large sized Mn2+ ions, localized at B-sites. Our results prove that the piezoelectric hard/soft response is decisively influenced by the interplay between multiple valence states and locations of the co-dopants, on one hand, and the charge compensation mechanisms, on the other hand. This provides indirect information about the location of some co-dopants which can substitute for both cationic sites in the PZT based ceramics.

Many magnetotactic bacteria (MTB) biomineralize magnetite crystals that nucleate and grow inside intracellular membranous vesicles originating from invaginations of the cytoplasmic membrane. The crystals together with their surrounding membranes are referred to as magnetosomes. Magnetosome magnetite crystals nucleate and grow using iron transported inside the vesicle by specific proteins. Here, we tackle the question of the organization of magnetosomes, which are always described as constituted by linear chains of nanocrystals. In addition, it is commonly accepted that the iron oxide nanocrystals are in the magnetite-based phase. We show, in the case of a wild species of coccus-type bacterium, that there is a double organization of the magnetosomes, relatively perpendicular to each other, and that the nanocrystals are in fact maghemite. These findings were obtained, respectively, by using electron tomography of whole mounts of cells directly from the environment and high-resolution transmission electron microscopy and diffraction. Structure simulations were performed with the MacTempas software. This study opens new perspectives on the diversity of phenotypes within MTBs and allows to envisage other mechanisms of nucleation and formation of biogenic iron oxide crystals.

Fe-Gd amorphous thin films of different compositions and thicknesses were analyzed with respect to their magnetic and magneto-optical behavior. By preparing samples with the same Fe/Gd elemental ratio at different thicknesses, and of various Fe/Gd ratios at constant thickness, respectively, we were able to show the influences of these two parameters on the interconnected behavior of the two magnetic sub-lattices, one of Fe and the other of Gd, which are antiferromagnetically coupled. Magneto-Optical Kerr Effect (MOKE) measurements revealed reversed hysteresis loops for sample compositions crossing the magnetic compensation point. Temperature dependent magnetization curves highlighted the variation of the overall net contribution of the two magnetic sub-lattices by changing either the Fe/Gd elemental ratio or the film thickness. Fe-57 Conversion Electron Mossbauer (CEM) spectra give additional support to the specific magnetic behavior evidenced by temperature and field dependent Superconducting Quantum Interference Device (SQUID) magnetometry.

The issue of heavy metal and radionuclide contamination is still causing a great deal of concern worldwide for environmental protection and industrial sites remediation. Various techniques have been developed for surface decontamination aiming for high decontamination factors (DF) and minimal environmental impact, but strippable polymeric nanocomposite coatings are some of the best candidates in this area. In this study, novel strippable coatings for heavy metal and radionuclides decontamination were developed based on the film-forming ability of polyvinyl alcohol, with the remarkable metal retention capacity of bentonite nanoclay, together with the chelating ability of sodium alginate and with "new-generation" "green" complexing agents: iminodisuccinic acid (IDS) and 2-phosphonobutane-1,2,4-tricarboxylic acid (PBTC). These environmentally friendly water-based decontamination solutions are capable of generating strippable polymeric films with optimized mechanical and thermal properties while exhibiting high decontamination efficiency (DF approximate to 95-98% for heavy metals tested on glass surface and DF approximate to 91-97% for radionuclides Am-241, Sr-90-Y and Cs-137 on metal, painted metal, plastic, and glass surfaces).

In this study, we develop chitosan-hydroxyapatite (CS-HAp) composite layers that were deposited on Si substrates in radio frequency (RF) magnetron sputtering discharge in argon gas. The composition and structure of CS-HAp composite layers were investigated by analytical techniques, such as Fourier transform infrared spectroscopy (FT-IR), scanning electron microscopy (SEM), metallographic microscopy (MM), and atomic force microscopy (AFM). On the other hand, in the present study the second order derivative of FT-IR-ATR spectra, for compositional analyses of CS-HAp, were used. The SEM, MM, and AFM data have shown the formation of CS-HAp composite layers. The surface of CS-HAp composite layers showed uniform growth (at an Ar gas working pressure of p = 2 x 10(-3) mbar). The surface of the CS-HAp composites coatings became more nanostructured, becoming granular as the gas pressure increased from 5 x 10(-3) to 1.2 x 10(-2) mbar. However, our studies revealed that the surface morphology of the CS-HAp composite layers varies with the Ar gas working pressure. At the same time, optical properties are slightly influenced by Ar pressure. Their unique physicochemical properties make them suitable for various applications in the biomedical field, if we consider the already proven antimicrobial properties of chitosan. The antifungal properties and the capacity of the CS-HAp composite layers to inhibit the development of fungal biofilms were also demonstrated using the Candida albicans ATCC 10231 (C. albicans) fungal strain.

Hydroxyapatite (Ca-10(PO4)(6)(OH)(2), HAp), due to its high biocompatibility, is widely used as biomaterial. Doping with various ions of hydroxyapatite is performed to acquire properties as close as possible to the biological apatite present in bones and teeth. In this research the results of a study performed on thin films of hydroxyapatite co-doped with nitrogen and bromine (NBrHAp) are presented for the first time. The NBrHAp suspension was obtained by performing the adapted co-precipitation method using cetyltrimethylammonium bromide (CTAB). The thin layers of NBrHAp were obtained by spin-coating. The stability of the NBrHAp suspension was examined by ultrasound measurements. The thin layers obtained by the spin-coating method were examined by scanning electron microscopy (SEM), optical microscopy (OM), and metallographic microscopy (MM). The presence of nitrogen and bromine were highlighted by energy-dispersive X-ray spectroscopy (EDS) and X-ray photoelectron spectroscopy (XPS) studies. Fourier transform infrared spectroscopy (FTIR) was used to highlight the chemical status of nitrogen and bromine. In addition, the powder obtained from the NBrHAp suspension was analyzed by XRD. Moreover, the in vitro antimicrobial activity of the NBrHAp suspensions and coatings was investigated using the reference microbial strains Staphylococcus aureus ATCC 25923, Escherichia coli ATCC 25922, and Candida albicans ATCC 10231. The results highlighted the successful obtainment of N and Br co-doped hydroxyapatite suspension for the first time by an adapted co-precipitation method. The obtained suspension was used to produce pure NBrHAp composite thin films with superior morphological properties. The NBrHAp suspensions and coatings exhibited in vitro antimicrobial activity against bacterial and fungal strains and revealed their good antimicrobial activity.

Nanoscale thermometers with high sensitivity are needed in domains which study quantum and classical effects at cryogenic temperatures. Here, we present a micrometer sized and nanometer thick chromium selenide cryogenic temperature sensor capable of measuring a large domain of cryogenic temperatures down to tenths of K. Hexagonal Cr-Se flakes were obtained by a simple physical vapor transport method and investigated using scanning electron microscopy, energy dispersive X-ray spectrometry and X-ray photoelectron spectroscopy measurements. The flakes were transferred onto Au contacts using a dry transfer method and resistivity measurements were performed in a temperature range from 7 K to 300 K. The collected data have been fitted by exponential functions. The excellent fit quality allowed for the further extrapolation of resistivity values down to tenths of K. It has been shown that the logarithmic sensitivity of the sensor computed over a large domain of cryogenic temperature is higher than the sensitivity of thermometers commonly used in industry and research. This study opens the way to produce Cr-Se sensors for classical and quantum cryogenic measurements.