National Institute Of Materials Physics - Romania

In the last decade orthorhombic hafnia and zirconia films have attracted tremendous attention arising from the discovery of ferroelectricity at the nanoscale. However, an initial wake-up pre-cycling is usually needed to achieve a ferroelectric behaviour in these films. Recently, different strategies, such as microstructure tailoring, defect, bulk and interface engineering, doping, NH3 plasma treatment and epitaxial growth, have been employed to obtain wake-up free orthorhombic ferroelectric hafnia and zirconia films. In this work we review recent developments in obtaining polar hafnia and zirconia-based thin films without the need of any wake-up cycling. In particular, we discuss the rhombohedral phase of hafnia/ zirconia, which under a constrained environment exhibits wake-up-free ferroelectric behaviour. This phase could have a strong impact on the current investigations of ferroelectric binary oxide materials and pave the way toward exploiting ferroelectric behaviour for next-generation memory and logic gate applications. Crown Copyright (c) 2022 Published by Elsevier Ltd. All rights reserved.

The role of Ag addition on the structural, dielectric, and mechanical harvesting response of 20%(xAg - (1 - x)BaTiO3) - 80%PVDF (x = 0, 2, 5, 7 and 27 vol.%) flexible composites is investigated. The inorganic fillers were realized by precipitating fine (similar to 3 nm) silver nanoparticles onto BaTiO3 nanoparticles (similar to 60 nm average size). The hybrid admixtures with a total filling factor of 20 vol.% were embedded into the PVDF matrix. The presence of filler enhances the amount of beta-PVDF polar phase and the BaTiO3 filler induces an increase of the permittivity from 11 to 18 (1 kHz) in the flexible composites. The addition of increasing amounts of Ag is further beneficial for permittivity increase; with the maximum amount (x = 27 vol.%), permittivity is three times larger than in pure PVDF (epsilon(r) similar to 33 at 1 kHz) with a similar level of tangent losses. This result is due to the local field enhancement in the regions close to the filler-PVDF interfaces which are additionally intensified by the presence of silver nanoparticles. The metallic addition is also beneficial for the mechanical harvesting ability of such composites: the amplitude of the maximum piezoelectric-triboelectric combined output collected in open circuit conditions increases from 0.2 V/cm(2) (PVDF) to 30 V/cm(2) for x = 27 vol.% Ag in a capacitive configuration. The role of ferroelectric and metallic nanoparticles on the increasing mechanical-electric conversion response is also been explained.

Luminescent nanocrystals embedded into silica microspheres were shown to be useful for silica labeling for biological applications, ensuring mechanical and chemical stability, nontoxicity, biocompatibility and optical properties. We used sol-gel technology to prepare silica nanospheres embedded with fluorescent and magnetic Eu3+(1 mol%)-doped CeO2 nanocrystals. The X-ray diffraction pattern analysis and transmission electron microscopy investigations showed CeO2:Eu3+(1 mol%) nanocrystals of about 9 nm size and Ce3+ ions substitution by the Eu3+ ions; the nanocrystals dispersed inside the nanosized silica spheres of about 400 nm diameters. The photoluminescence spectra recorded under UV-light excitation showed Eu3+ ions luminescence peaks (D-5(0)-F-7(J), J = 0-4) accompanied by a weaker 425 nm luminescence due to the silica matrix; the quantum yield was 0.14. The weak hysteresis loop and magnetization curves recorded up to 20,000 Oe showed dominantly paramagnetic behavior associated with the silica matrix; a slight opening of the hysteresis loop to a very small magnetic field (about 0.005 Oe) was due to the presence of the two rare earth ions. The photonic crystal properties of SiO2-CeO2:Eu3+(1 mol%) silica nanospheres deposited as films on quartz plates were revealed by the two weak attenuation peaks at 420 and 500 nm and were associated with the reflection from different planes. The SiO2-CeO2:Eu3+(1 mol%) nanospheres are attractive potential candidates for photonics-related applications or for multifunctional bio-labels by combining the luminescence and magnetic properties of the nanocrystals.

This contribution concerns the effect of the chemical composition of the brucite-type layer of bi-cationic LDH materials ZnxAl and MgxAl (x = 2-5) and tri-cationic LDH MgyZnzAl (y + z = 4, y = 1, 2, 3) on their catalytic activity for olefin epoxidation with H2O2 in the presence of acetonitrile. LDH materials were prepared by the standard method of co-precipitation at constant pH 10, using an aqueous solution of the corresponding metal nitrates and a basic solution containing NaOH and Na2CO3. The fresh LDHs were calcined to yield the corresponding mixed oxides and then the recovery of the LDH structure by hydration of the mixed oxides was performed. The resulting samples were characterized by AAS, XRD, DRIFT, DR-UV-Vis, BET and determination of basic sites. The results of the catalytic tests for olefin epoxidation were well correlated with the basicity of the samples, which was in turn related to the M2+/Al3+ ratio and the electronegativity of different bivalent metals in the brucite-type layer.

Fe (acceptor) and Nb (donor) doped epitaxial Pb(Zr0.2Ti0.8)O-3 (PZT) films were grown on single crystal SrTiO3 substrates and their electric properties were compared to those of un-doped PZT layers deposited in similar conditions. All the films were grown from targets produced from high purity precursor oxides and the doping was in the limit of 1% atomic in both cases. The remnant polarization, the coercive field and the potential barriers at electrode interfaces are different, with lowest values for Fe doping and highest values for Nb doping, with un-doped PZT in between. The dielectric constant is larger in the doped films, while the effective density of charge carriers is of the same order of magnitude. An interesting result was obtained from piezoelectric force microscopy (PFM) investigations. It was found that the as-grown Nb-doped PZT has polarization orientated upward, while the Fe-doped PZT has polarization oriented mostly downward. This difference is explained by the change in the conduction type, thus in the sign of the carriers involved in the compensation of the depolarization field during the growth. In the Nb-doped film the majority carriers are electrons, which tend to accumulate to the growing surface, leaving positively charged ions at the interface with the bottom SrRuO3 electrode, thus favouring an upward orientation of polarization. For Fe-doped film the dominant carriers are holes, thus the sign of charges is opposite at the growing surface and the bottom electrode interface, favouring downward orientation of polarization. These findings open the way to obtain p-n ferroelectric homojunctions and suggest that PFM can be used to identify the type of conduction in PZT upon the dominant direction of polarization in the as-grown films.

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] .

We present an array of 225 field-effect transistors (FETs), where each of them has a graphene monolayer channel grown on a 3-layer deposited stack of 22 nm control HfO2/5 nm Ge-HfO2 intermediate layer/8 nm tunnel HfO2/p-Si substrate. The intermediate layer is ferroelectric and acts as a floating gate. All transistors have two top gates, while the p-Si substrate is acting as a back gate. We show that these FETs are acting memtransistors, working as two-input reconfigurable logic gates with memory, the type of the logic gate depending only on the values of the applied gate voltages and the choice of a threshold current.

Bulk high density MgB2 and a composite material made of a PLA matrix and MgB2 powder inclusions were in vivo tested as candidates for biodegradable materials for orthopedic implants. A rat model was used. Implants were introduced into femoral bone, in transversal and longitudinal directions. Assessment of the implant-tissue interaction was performed by X-ray imaging, X-ray computer tomography, electron microscopy, cytology, and histopathology on samples at 40 and 90 days after surgery. Both materials are biocompatible, bone and adjacent soft tissue showing good tolerance of implants. Biodegradation of MgB2 is faster than for PLA-MgB2 composite, but in both cases, it is accompanied by bone regeneration. Results suggest that use of MgB2-containing composites can promote space and time control of degradation and promotes MgB2 as a promising material for fracture repair. (c) 2022 The Authors. Published by Elsevier B.V. This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).

Nano-nitride reinforcement of Fe-Cr alloys are under intense investigations, e.g., along with oxide-strengthened, nitride-strengthened reduced activation steels with superior high temperature mechanical properties are developed as materials for nuclear energy applications. Fe14Cr alloy powders were produced by mechanical milling for up to 170 h under a nitrogen atmosphere followed by heating under an Ar5%H-2 atmosphere to 600 degrees C-1120 degrees C. The samples were investigated by means of X-ray diffraction, DTA/TG and magnetic measurements. CrN, detected after milling for 58 h, reached 39 wt % (5.3 wt.% total N) at 170 h milling. The ferrite supersaturated with nitrogen shows a strong decrease in grain size and saturation magnetization, an increase in lattice constant, microstrain and coercivity, H-c. Upon heating, the metastable ultrafine alpha-ferrite and CrN in the as-milled samples undergo transformations and recrystallization into ferrite grains free of super-saturation, whose microstructure follows a continuous relaxation. The supersaturation with nitrogen was retained upon heating in the relatively stable ferrite crystalized at the milling stage. This microstructure undergoes a discontinuous relaxation in the 800 degrees C-1120 degrees C region: a pronounced decrease of grain size (down to similar to 25 nm), an increase of lattice constant, microstrain and H-c. These improvements were associated with features of discontinuous precipitation reaction of coherent nitride precipitates (involving a new alpha ''-phase with expanded lattice), in connection with the heating in the austenite phase field. Such microstructure refinement or (nitride) strengthening of Fe14Cr alloys can be achieved on powders milled for much less time as compared to previously reported (oxide dispersion) strengthening of Fe14Cr-W-Ti ferritic steels. (C) 2022 The Authors. Published by Elsevier B.V.

Exchange coupling in a SrFe12O19 - Fe3O4 nanocomposite magnet was explored in this study. The composition, microstructure, local structure and magnetic properties were investigated by XRD, SEM, Mossbauer spectroscopy, and SQUID magnetometry. The magnetoplumbite SrFe12O19 and spinel Fe3O4 structures were verified by X-ray diffraction. The morphology of the composite reveals the characteristics of the two components. The hyperfine parameters allowed the identification of the Wyckoff positions of the iron ions corresponding to the involved phases. The magnetic measurements of the composite, showing a single-phase-like magnetic hysteresis loop, confirmed the exchange coupling between the hard and soft magnetic phases.