National Institute Of Materials Physics - Romania

Six compounds of the types [M(dmbg)(2)]center dot nH(2)O ((1) M: Ni, n = 0; (4) M: Cu, n = 1; Hdmbg: N,N '-dimethylbiguanide) and, respectively, [ML]center dot nH(2)O (where (2) M: Ni, L: L-1, n = 0; (3) M: Ni, L: L-2, n = 0; (5) M: Cu, L: L-1, n = 0 and (6) M: Cu, L: L-2, n = 3, H2L1: ligand resulted from the condensation of (1) with ammonia and formaldehyde and H2L2: ligand resulted from the condensation of (4) with hydrazine and formaldehyde) were characterized as mononuclear species through information provided by NMR, electronic paramagnetic resonance (EPR) and UV-Vis spectroscopy as well as cyclic voltammetry. All data are consistent with macrocyclic formation by condensation. The complexes adopt a distorted square planar geometry resulting from the chelating behaviour of the corresponding ligands. The EPR spectra recorded after the addition of Cu(II) complexes into the corresponding Ni(II) complexes show a well resolved hyperfine structure with the superhyperfine pattern corresponding to four nitrogen atom donors. The cathodically shift of E-pc2 for both series can be correlated with the increased stability of the M(I) species through macrocyclic ligands. Geometry optimization studies for complexes (2), (3), (5) and (6) have further confirmed the experimental data. The pharmacokinetic computational results indicate that the complexes exhibit medium to low intestinal absorption and slow blood-brain barrier permeability but low toxicity. Their predictive pharmacodynamic profiles show that the compounds present the ability to inhibit protease activity. By corroborating the results of the in silico analysis with the experimental ones, the most promising complexes for antimicrobial applications are (1) and (2) and, respectively, (4) and (6) for the development of novel antitumour strategies.

Pottery vessels made of kaolin clay from the Roman Period (2nd, 3rd centuries CE) found in Romula (Re?ca village, Olt County, Romania) from Dacia Inferior (Malvensis) were investigated by petrographic, X-ray diffraction, X-ray fluorescence, thermal analysis, electron microscopy, and mechanical tests. Our results are compared with available data on kaolin clays and pottery vessels from other sites located along the lower course of Danube river and near the Black Sea, namely in Moesia Superior, Moesia Inferior, and Thracia. Archeological and geographical contexts are addressed. Results of our analysis suggest a local production of ceramics in Romula, by using raw materials from the north of Lower Danube, in opposition to the idea that kaolin ware was imported from the provinces south of the Danube.

In this paper, we report studies on Al2O3/Ge/Al2O3 trilayer memory structures deposited by magnetron sputtering at room temperature on p-Si substrates coated with 3 nm SiO2. The changes of the structure, morphology and memory properties induced by rapid thermal annealing (RTA) in a broad temperature range 550-900 degrees C have been carefully investigated. High resolution transmission electron microscopy (HRTEM) revealed the existence of distinct RTA effects for different temperature ranges, in correlation with memory properties measured on Al/Al2O3/Ge/Al2O3/SiO2/p-Si/Al devices. Thus, at temperatures smaller than 650 degrees C, Ge diffuses into adjacent Al2O3, the layers remaining amorphous. The memory window increases from as-deposited samples to those annealed at 600 degrees C reaching the maximum of 5.4 V. After RTA at 700 degrees C, Ge nanocrystals (NCs) in intermediate Ge layer and Ge-rich amorphous nanoparticles in Al2O3 tunnel oxide are formed. Increasing RTA temperature to 800 and 900 degrees C, Ge NCs are no longer formed due to Ge strong diffusion. Instead, Ge-rich mixed GeAl oxide NCs of unknown crystalline structure are evidenced by HRTEM. The memory window continuously decreases with annealing temperature in the range 650-900 degrees C. The ON (OFF) charge loss of only 11% (9.8%) was found by extrapolation to 10 years.

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.

The discovery of ferroelectricity in doped HfO2 represents an excellent opportunity to overcome the obstacles in manufacturing reliable ferroelectric field effect transistors (FeFET) for nonvolatile memory applications, considering that HfO2 is compatible with Si and Ge and it is already used in semiconductor industry. The presence of interface defects may have detrimental effects on the operation of FeFETs, so their role is systematically investigated in this study in correlation with the substrate doping. Metal-ferroelectric-semiconductor (MFS) structures are fabricated by depositing Hf0.5Zr0.5O2 (HZO) layers on n-type Ge substrate. Their electric properties are compared with those of MFS structures obtained by depositing HZO on p-type Ge, to study the influence of the doping. It is found that, although the ferroelectric properties of HZO are similar, the capacitance and impedance of the MFS structures behave differently. For n-Ge, the occupation probability of a large number of low-lying interface defect acceptor states, charges the interface negatively which adversely affects the C-V response of the MFS, albeit without harming the ferroelectric (P-V) hysteresis. Although the interface defects do not harm ferroelectricity, they could inhibit inversion in p-type Ge or accumulation in n-type Ge so they should be taken into account when designing Ge FeFET devices.

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.

Partially-oriented MgB2 bulk discs (13 and 9 %) with the starting compositions of (MgB2)(0.99)(B4C)(0.01) and (MgB2)(0.99)(c-BN)om were fabricated by slip casting under an H-0 = 12 T magnetic field (perpendicular to the disc surface) and subsequent spark plasma sintering. The maximum critical current density and irreversibility field are for H//H-0 (H=applied field). These values are higher or similar to the randomly-oriented samples with the same composition. The maximum volume pinning force (F-p) is lower in the partially-oriented ones than in the randomly-oriented samples. The pinning-force-related parameters depend on the additive and orientation. Assessment of the major pinning mechanism within the scaling and percolation models considering these parameters shows significant limitations. A method to scale F-p is proposed; for the randomly and partially-oriented samples (that show an extra peak in F-p), the single and double Gaussian functions fit well. The results suggest an anisotropic influence of carbon substituting for boron in the MgB2.

Doping SnO2 with trivalent lanthanide (Ln) metals aiming at optical applications faces several challenges. The elastic and electrostatic misfit between bulkier Ln activators and Sn host cation induces strain in the lattice as well as defects as a result of charge-compensation. These effects can be partially healed by thermal annealing. However, dopant segregation which occurs above a certain temperature drives quenching of Ln emission. In this work, we explore Li co-doping as a vehicle to improve the luminescence of lanthanide (Eu, Sm, Er, Dy and, Tb) doped SnO2 nanoparticles. In case of substitutional Ln dopants (Eu, Sm and Er), Li enhances significantly the Ln luminescence up to 40-46 times. The luminescence enhancement induced by Li co-doping is explained by an interplay of removal of nearby oxygen vacancies (Eu, Sm), improved Ln doping homogeneity (Er) and, improved crystallinity (Eu, Sm, Er). The improved crystallinity caused by Li co-doping accounts for less than 30% of the total enhancement. In the case of surface Ln dopants (Dy and Tb), Li co-doping does not alter the Ln emission, either in shape or intensity. Only a few Dy dopants succeed to substitute for Sn in the rutile lattice as shown by single-photon counting investigations. Collectively, our results show that the extent of luminescence enhancement induced by Li co-doping depend strongly on the Ln type. In SnO2, the common mechanisms that explain the Li induced enhancement of Ln luminescence in various hosts, either contribute partially (improved crystallization) or do not contribute at all (local structure distortion).

Two core-double-shell pH-sensitive nanocarriers were fabricated using Fe3O4 as magnetic core, poly(glycidyl methacrylate-PEG) and salep dialdehyde as the first and the second shell, and doxorubicin as the hydrophobic anticancer drug. Two nanocarriers were different in the drug loading steps. The interaction between the first and the second shell assumed to be pH-sensitive via acetal cross linkages. The structure of nanocarriers, organic shell loading, magnetic responsibility, morphology, size, dispersibility, and drug loading content were investigated by IR, NMR, TG, VSM, XRD, DLS, HRTEM and UV-Vis analyses. The long-term drug release profiles of both nanocarriers showed that the drug loading before cross-linking between the first and second shell led to a more pH-sensitive nanocarrier exhibiting higher control on DOX release. Cellular toxicity assay (MTT) showed that DOX-free nanocarrier is biocompatible having cell viability greater than 80% for HEK-293 and MCF-7 cell lines. Besides, high cytotoxic effect observed for drug-loaded nanocarrier on MCF-7 cancer cells. Cellular uptake analysis showed that the nanocarrier is able to transport DOX into the cytoplasm and perinuclear regions of MCF-7 cells. In vitro hemolysis and coagulation assays demonstrated high blood compatibility of nanocarrier. The results also suggested that low concentration of nanocarrier have a great potential as a contrast agent in magnetic resonance imaging (MRI).

The paper presents the possibility of detecting low H2S concentrations using CuWO4. The applicative challenge was to obtain sensitivity, selectivity, short response time, and full recovery at a low operating temperature under in-field atmosphere, which means variable relative humidity (%RH). Three different chemical synthesis routes were used for obtaining the samples labeled as: CuW1, CuW2, and CuW3. The materials have been fully characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), Raman spectroscopy, and X-ray photoelectron spectroscopy (XPS). While CuWO4 is the common main phase with triclinic symmetry, different native layers of CuO and Cu(OH)(2) have been identified on top of the surfaces. The differences induced into their structural, morphological, and surface chemistry revealed different degrees of surface hydroxylation. Knowing the poisonous effect of H2S, the sensing properties evaluation allowed the CuW2 selection based on its specific surface recovery upon gas exposure. Simultaneous electrical resistance and work function measurements confirmed the weak influence of moisture over the sensing properties of CuW2, due to the pronounced Cu(OH)(2) native surface layer, as shown by XPS investigations. Moreover, the experimental results obtained at 150 degrees C highlight the linear sensor signal for CuW2 in the range of 1 to 10 ppm H2S concentrations and a pronounced selectivity towards CO, CH4, NH3, SO2, and NO2. Therefore, the applicative potential deserves to be noted. The study has been completed by a theoretical approach aiming to link the experimental findings with the CuW2 intrinsic properties.