National Institute Of Materials Physics - Romania

The osteogenic ions Ca2+ P5+, Mg2+, and antimicrobial ion Ga3+ were homogenously dispersed into a 1.45 mu m thick phosphate glass coating by plasma assisted sputtering onto commercially pure grade titanium. The objective was to deliver therapeutic ions in orthopaedic/dental implants such as cementeless endoprostheses or dental screws. The hardness 4.7 GPa and elastic modulus 69.7 GPa, of the coating were comparable to plasma sprayed hydroxyapatite/dental enamel, whilst superseding femoral cortical bone. To investigate the manufacturing challenge of translation from a target to vapour condensed coating, structural/compositional properties of the target (P51MQ) were compared to the coating (P40PVD) and a melt-quenched equivalent (P40MQ). Following condensation from P51MQ to P40PVD, P2O5 content reduced from 48.9 to 40.5 mol%. This depoly-merisation and reduction in the P-O-P bridging oxygen content as determined by P-31 NMR, FTIR and Raman spectroscopy techniques was attributed to a decrease in the P2O5 network former and increases in alkali/alkali-earth cations. P40PVD appeared denser (3.47 vs. 2.70 g cm(-3)) and more polymerised than it's compositionally equivalent P40MQ, showing that structure/ mechanical properties were affected by manufacturing route.

We report on Matrix-Assisted Pulsed Laser Evaporation (MAPLE) deposition of Carbon thin films, simple or reinforced with intended concentrations of Ag and Si. A KrF* (lambda = 248 nm, tau(FWHM) < 25 ns, v = 10 Hz) excimer laser was used for irradiation. The effect of a post-deposition thermal treatment in vacuum was studied. Besides detailed morphological, compositional, structural and pull-out adherence characterizations, the potential of the carbonaceous films for medical applications was investigated in vitro by anti-biofilm and cytocompatibility assays. The microscopic images evidenced no delaminations. Micro-Raman spectroscopy revealed a graphitization tendency depending on preparation conditions, thermal treatment and reinforcing agents' presence. Adherence values improved considerably after thermal treatment. In vitro biological evaluation showed that the films containing similar to 1.85 at.% Ag were non-cytotoxic for MG63 cells, while eliciting a limited antimicrobial activity. The increase of Ag content to 3.6 at.% results in a significant enhancement of antimicrobial activity, whilst maintaining the cytotoxic action and adherence characteristics at acceptable levels. We propose a new class of metamaterials based on C reinforced with Ag and Si obtained by MAPLE for medical applications, i.e. the prevention and treatment of various infections associated with biofilms developed on implants and other medical equipments. (C) 2018 Elsevier B.V. All rights reserved.

We report on the synthesis by PLD of simple and lithium-doped biological-origin hydroxyapatite (HA) films. The role of doping reagents (Li2CO3, Li3PO4) on the morphology, structure, chemical composition, bonding strength and cytocompatibility of the films was investigated. SEM investigations of the films evidenced a surface morphology consisting of particles with mean diameters of (5-7) mu m. GIXRD analyses demonstrated that the synthesized structures consisted of HA phase only, with different degrees of crystallinity, mainly influenced by the doping reagent type. After only three days of immersion in simulated body fluid, FTIR spectra showed a remarkable growth of a biomimetic apatitic film, indicative of a high biomineralization capacity of the coatings. EDS analyses revealed a quasi-stoichiometric target-to-substrate transfer, the values inferred for the Ca/P ratio corresponding to a biological apatite. All synthesized structures displayed a hydrophilic behavior, suitable for attachment of osteoblast cells. In vitro cell viability tests showed that the presence of Li2CO3 and Li3PO4 as doping reagents promoted the hMSC growth on film surfaces. Taking into consideration these enhanced characteristics, corroborated with a low fabrication cost generated by sustainable resources, one should consider the lithium-doped biological-derived materials as promising prospective solutions for a next generation of coated implants with rapid osteointegration. (C) 2018 Elsevier B.V. All rights reserved.

Processing calcium-rich natural resources, such as marble and mussel seashells, into biomimetic products could constitute an environmentally-friendly and economically sustainable alternative given their geographical widespread. Hitherto, their value for biomedicine was demonstrated only for seashells, with the technological exploitation approaches still facing challenges with respect to the identification of generic synthesis parameters capable to allow the reproducible and designed synthesis of calcium phosphate at an industrial-ready level. In this study was targeted the optimization of Rathje synthesis method for the fabrication of biogenic calcium phosphates, by conveniently adjusting the chemical composition of employed reagents. It was shown that post-synthesis heat-treatment of compacted powders is the key step for inducing structural transformations suitable to attain biomimetic products for reconstructive orthopedic applications. The sintered materials have been multi-parametricallyevaluated from morpho-compositional, structural, wettability, mechanical and cytocompatibility points of view and the results have been cross-examined and discussed. Convenient and efficient preparation routes to produce biogenic hydroxyapatite have been identified. The functional performances of the as-prepared biogenic ceramics endorse their use as a solid and inexpensive alternative source material for the fabrication of various bone regenerative products and implant coatings. (C) 2017 Elsevier B.V. All rights reserved.

Comparative studies employing Deep Level Transient Spectroscopy and C-V measurements have been performed on recombination-enhanced reactions between defects of interstitial type in boron doped silicon diodes irradiated with alpha-particles. It has been shown that self-interstitial related defects which are immobile even at room temperatures can be activated by very low forward currents at liquid nitrogen temperatures. Their activation is accompanied by the appearance of interstitial carbon atoms. It has been found that at rather high forward current densities which enhance BiOi complex disappearance, a retardation of C-i annealing takes place. Contrary to conventional thermal annealing of the interstitial boron-interstitial oxygen complex, the use of forward current injection helps to recover an essential part of charge carriers removed due to irradiation. Published by AIP Publishing.

This work focuses on the kinetic mechanisms responsible for the annealing behavior of radiation cluster-related defects with impact on the electrical performance of silicon sensors. Such sensors were manufactured on high resistivity n-type standard float-zone (STFZ) and oxygen enriched float-zone (DOFZ) material and had been irradiated with mono-energetic electrons of 3.5 MeV energy and fluences of 3 x 10(14) cm(-2) and 6 x 10(14) cm (-2). After irradiation, the samples were subjected either to isochronal or isothermal heat treatments in the temperature range from 80 degrees C to 300 degrees C. The specific investigated defects are a group of three deep acceptors [H(116 K), H(140 K), and H(152 K)] with energy levels in the lower half of the band gap and a shallow donor E(30 K) with a level at 0.1 eV below the conduction band. The stability and kinetics of these defects at high temperatures are discussed on the basis of the extracted activation energies and frequency factors. The annealing of the H defects takes place similarly in both types of materials, suggesting a migration rather than a dissociation mechanism. On the contrary, the E(30 K) defect shows a very different annealing behavior, being stable in STFZ even at 300 degrees C, but annealing-out quickly in DOFZ material at temperatures higher than 200 degrees C, with a high frequency factor of the order of 10(13) s(-1). Such a behavior rules out a dissociation process, and the different annealing behavior is suggested to be related to a bistable behavior of the defect. Published by AIP Publishing.

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.