National Institute Of Materials Physics - Romania

A novel and efficient one-pot system for green production of artificial lignin bio-composites has been developed. Monolignols such as sinapyl (SA) and coniferyl (CA) alcohols were linked together with caffeic acid (CafAc) affording a polymeric network similar with natural lignin. The interaction of the dissolved SA/CA with CafAc already bound on a solid support (S-C2/S-C6 CafAc) allowed the attachment of the polymeric product direct on the support surface (S-C2/S-C6-CafAc-L-1 and S-C2/S-C6-CafAc-L-2, from CA and SA, respectively). Accordingly, this procedure offers the advantage of a simultaneous polymer production and deposition. Chemically, oxi-copolymerization of phenolic derivatives (SA/CA and CAfAc) was performed with H2O2 as oxidation reagent using peroxidase enzyme (2-1B mutant of versatile peroxidase from Pleurotus eryngii) as catalyst. The system performance reached a maximum of conversion for SA and CA of 71.1 and 49.8%, respectively. The conversion is affected by the system polarity as resulted from the addition of a co-solvent (e.g., MeOH, EtOH, or THF). The chemical structure, morphology, and properties of the bio-composites surface were investigated using different techniques, e.g., FTIR, TPD-NH3, TGA, contact angle, and SEM. Thus, it was demonstrated that the SA monolignol favored bio-composites with a dense polymeric surface, high acidity, and low hydrophobicity, while CA allowed the production of thinner polymeric layers with high hydrophobicity.

In this work, we report on the variability of the Schottky effect in solution processed Ba1-xSrxTiO3 films (BST, x = 0, 0.5) grown on 0.5% Nb doped SrTiO3 substrates with top Pt electrodes (NSTO/BST/Pt). The films display leakage currents accompanied by varying degrees of hystereses in the current-voltage measurements. The magnitude of the leakage and hystereses depend on the Sr content. We focus on the current-voltage (I-V) behavior of our samples in the light of thermodynamic theory of ferroelectrics coupled with equations of semiconductors. Our calculations allowed us to unambigously determine the electronic character of the defects and related band bending effects in our samples. The extent of asymmetry and the hystereses in the I-V curves for x = 0 and 0.5 are shown to be controlled by the polarization in qualitative agreement with our calculations. Amplitude of the ferroelectric polarization, which is a function of composition here, has a strong impact on leakage currents in forward bias while this effect is much weaker under negative bias. The latter occurs as polarization pointing away from the NSTO semiconducting substrate causes depletion of carriers at the NSTO side of the NSTO/BST interface, increasing resistance to current flow through the stack. Such an occurence also increases the energy gap between the Fermi level and the conduction bands of the films, thereby reducing the bulk conduction through the film as well. The dependence of leakage currents on polarization direction points out to the possibility of a non-destructive read-out route in ferroelectric films much thicker than tunnel junctions. (c) 2018 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

New magneto-optical vitreous materials were obtained by melting-quenching technique comprising wet route raw materials preparation. The glass has the following composition in oxide mol. % 10 Li2O, 9 Al2O3, 5 ZnO, (35; 20; 50) B2O3,,(35; 50; 20) P2O5, 3 Bi2O3, 3 PbO, phosphorus and boron oxide being the vitreous network formers. It was also prepared a similar reference glass composition but without Bi2O3 and PbO. Optical and structural characterization by ultraviolet-visible (UV-Vis), Fourier Transform Infrared (FTIR) and Raman Spectroscopy of the bulk glasses showed a transmission over 90%, metaphosphate structure of glass together with Q(2) boron oxide units and P-O-B bonds. The mechanical parameters, hardness (H), Youngs modulus (E) and fracture toughness (KO of boron phosphate glasses, evaluated by micro- and nanoindentation techniques, demonstrated mostly higher values in comparison with those for alumino-phosphate glasses due to mixed borophosphate network. Thermal behavior was investigated by Differential Scanning Calorimetry (DSC) putting in evidence the vitreous transition temperature which decreases with about 45 degrees C when Bi and Pb oxides were added and two crystallization effects. The diamagnetic character of a highly transparent Bi and Pb oxide co doped boron phosphate glass was confirmed by ellipsometry, and the glass presented high magneto-optical properties at the top of the commercial bulk products.

The present study is focused on the wet chemical synthesis and the characterization of ZnO-CdS composites. The X-ray diffraction shows that the composites contain ZnO in hexagonal wurtzite structure and CdS in cubic phase. The scanning/transmission electron microscopy images reveal flower-like structures with different sizes depending on the CdS content. The optical investigations on composites reveal that the reflectance spectra disclose two thresholds of similar to 370 nm and similar to 460 nm associated with the ZnO and CdS, respectively. The photocatalytic activity measurements evidenced that the degradation efficiency of RhB in the presence of composites is higher comparatively with pristine ZnO, depending on the catalyst morphology, which varies with CdS content and the pH value of RhB solution. The electron paramagnetic resonance revealed the presence of the paramagnetic point defects in the samples. Thus, the wet chemical approaches are suitable for a large scale production of such ZnO-CdS composites having enhanced photocatalytic activity.

By platinum deposition on a 150 nm thick film of lead zirco-titanate oriented PZT(001), grown on strontium titanate (001) single crystals with a strontium ruthenate buffer layer, which did not show initial preferential out-of-plane orientation of its ferroelectric polarization, a band bending near the interface towards lower energies is observed using photoelectron spectroscopy, by following all core levels from the substrate (Pb 4f, Zr 3d, Ti 2p, O 1s). This is unexpected given the fact that platinum has a larger work function than PZT and a rectifying contact for electrons is expected to be built at the interface. This observation may have two explanations: (i) platinum forms an alloy with elements from PZT yielding a metal with considerable lower work function; (ii) platinum provides electrons to the substrate which are able to compensate the depolarization field generated by the outwards polarization state. Several arguments are brought in favor of the second hypothesis, especially the attenuation of core levels from the substrate which is well described by exponential functions with reasonable values of the photoelectron inelastic mean free path, suggesting the formation of a sharp interface. High resolution transmission electron microscopy confirmed the sharpness of the interface. (C) 2017 Elsevier B.V. All rights reserved.

Samples of MgB2 with relative density above 95% were obtained by spark plasma sintering (SPS) at 1150 A degrees C for a heating time of 100 A degrees C/min and a maximum pressure of 95 MPa. Dwell time was of 1, 4, 7, 10, and 20 min. Samples show that dwell time has a low influence on superconducting characteristics. However, small differences were observed and they are discussed from the viewpoint of density, structural, microstructural, critical current density, irreversibility field, and pinning type. The dominant contribution for all investigated samples is given by point and delta T (c) pinning.

Un-doped ZnO (UDZO) and Li-doped ZnO (LZO) polycrystalline thin films were grown on platinized silicon by pulsed laser deposition (PLD). The electrical properties were investigated on as-grown and annealed UDZO and LZO films with capacitor configuration, using top and bottom platinum electrodes. In the case of the as-grown films it was found that the introduction of Li increases the resistivity of ZnO and induces butterfly shape in the C-V characteristic, suggesting ferroelectric-like behavior in LZO films. The properties of LZO samples does not significantly changes after thermal annealing while the properties of UDZO samples show significant changes upon annealing, manifested in a butterfly shape of the C-V characteristic and resistive-like switching. However, the butterfly shape disappears if long delay time is used in the C-V measurement, the characteristic remaining non-linear. Pyroelectric signal could be measured only on annealed films. Comparing the UDZO results with those obtained in the case of Li: ZnO, it was found that the pyroelectric properties are considerably enhanced by Li doping, leading to pyroelectric signal with about one order of magnitude larger at low modulation frequencies than for un-doped samples. Although the results of this study hint towards a ferroelectric-like behavior of Li doped ZnO, the presence of real ferroelectricity in this material remains controversial. (C) 2017 Elsevier B.V. All rights reserved.

Hydroxyapatite-starch composites solidify rapidly via jellification, making them suitable candidates for robocasting. However, many aspects related to hydroxyapatite powder characteristics, hydroxyapatite-starch interaction, and composites composition and properties need to be aligned with robocasting requirements to achieve a notable improvement in the functionality of printed scaffolds intended for bone regeneration. This article presents a preliminary evaluation of hydroxyapatite-starch microcomposites. Thermal analysis of the starting powders was performed for predicting composites' behavior during heat-induced densification. Also, morphology, mechanical properties, and hydroxyapatite-starch interaction were evaluated for the jellified composites and the porous bodies obtained after conventional sintering, for different starch additions, and for ceramic particle size distributions. The results indicate that starch could be used for hydroxyapatite consolidation in limited quantities, whereas the composites shall be processed under controlled temperature. Due to a different mechanical behavior induced by particle size and geometry, a wide particle size distribution of hydroxyapatite powder is recommended for further robocasting ink development.

We investigate the dynamic behavior of perovskite solar cells by focusing on the relaxation time tau, which corresponds to the slow de-polarization process from an initial bias pre-poled state. The dynamic electrical model (DEM) is employed for simulating the J-V characteristics for different bias scan rates and pre-poling conditions. Depending on the sign of the initial polarization normal or inverted hysteresis may be induced. For fixed pre-poling conditions, the relaxation time, in relation to the bias scan rate, governs the magnitude of the dynamic hysteresis. In the limit of large tau the hysteretic effects are vanishing for the typical range of bias scan rates considered, while for very small tau the hysteresis is significant only when it is comparable with the measurement time interval.

Low-loss dielectrics with various microstructure and, consequently, different extrinsic losses were investigated by using terahertz time-domain spectroscopy. The losses have been extrapolated and compared with those measured at microwave frequencies. The results showed that extrinsic factors have a considerably contribution in microwave domain. The intrinsic limit of dielectric loss of low absorption polycrystalline materials have been estimated by terahertz spectroscopy.