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.

Four batches of cerium oxide powders (with nanocrystallite size of 6.9 nm-572 nm) were prepared from four precursor nanopowders by thermal decomposition of Ce-propionate and annealing in air between 250 degrees C-1200 degrees C for 10 min-240 min. Ceria formation reactions, structure, vibrational, luminescence and magnetic properties were investigated by differential scanning calorimetry, x-ray diffraction, electron microscopy, infrared spectroscopy, photoluminescence and SQUID. All the samples exhibit room temperature ferromagnetism, RTFM, (with coercivity, H-c, of 8 Oe - 121 Oe and saturation magnetization, M-s, of up to 6.7*10(-3) emu/g) and a broad defect-related photoluminescence, PL, emission in the visible range. The samples derived from the same precursor show M-s proportional to the peak area of defect-related PL emission whereas this is not valid for the samples derived from the different precursors. An improvement of ferromagnetism and intensity of defect-related PL emission was observed when annealing the products in which nanocrystalline cerium oxide coexists with Ce - oxicarbonate traces, Ce2O2CO3. The experimental results were explained based on the following considerations: room temperature ferromagnetism was induced by the defective ceria with high concentration of oxygen vacancies generated by decomposition of Ce-propionate; oxygen vacancies of the starting precursor nanopowders could be redistributed (at the surfaces/grain boundaries, GBs) upon heating under conditions that promote an inert local environment; the decomposition of Ce2O2CO3 residues can provide an excess of oxygen vacancies at the nanoparticles surfaces or GBs, which can induce or enhance ferromagnetism; surfaces/GBs rather than bulk defects appear responsible for RTFM - this can explain the (often reported in literature) inconsistency between oxygen vacancies concentration and M-s. (C) 2018 Elsevier B.V. All rights reserved.

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.

It is shown that the dielectric and piezoelectric properties of Ba(Ti0.8Zr0.2)O-3-x(Ba0.7Ca0.3)TiO3 (x = 0.45) (BCTZ 45) epitaxial thin films have a nontrivial dependence on film thickness. BCTZ 45 epitaxial films with different thicknesses (up to 400 nm) have been deposited on SrTiO3 by pulsed laser deposition and investigated by different combined techniques: conventional and off-axis X-ray diffraction, high resolution transmission electron microscopy and dielectric and piezoforce microscopy. The changes occurring in epitaxial films when their thickness increases have been attributed to a partial relaxation of misfit strain, driving the induced tetragonal symmetry in very thin films to the original rhombohedral symmetry of the bulk material in the thickest film, which influences directly and indirectly the dielectric and piezoelectric properties.

Thermoluminescent measurements between 40 and 300 C revealed two traps in the irradiated Alq(3) powder synthetized from Al(OH)(3), at 0.8 and 1.1 eV below the conduction band. These two traps have been assigned with the Alq(3) facial and meridional isomers and the trapping process stand for a long time after the switching off the irradiation source. The spectra recorded an hour after switching recover 60% from the photoluminescence and also decreasing the TL signals. A theoretical model was proposed in order to explain the trapping and detrapping processes in both meridional and facial Alq(3) isomers based on the XPS measurements for the HOMO, LUMO, ionization potential and optical bandgap, completed with the DFT calculated parameters and similar experimental results concerning the evidences of the triplet states in Alq(3) compound.

A new bisimidazolium salt with dodecyl sulfate as counterion has been designed and prepared. This salt shows a SmA phase that is stable at room temperature. The new ionic liquid crystal (ILC) was characterized by H-1 NMR, C-13 NMR and IR spectroscopy. Its liquid crystalline properties were analyzed by polarizing optical microscopy (POM), differential scanning calorimetry (DSC) and powder X-ray diffraction (XRD) studies. The dielectric spectra of the ILC doped with different concentrations of carbon nanotubes (CNT) were recorded over a wide frequency and temperature range of 10(-1) to 10(7) Hz and 293-338 K, respectively. The values of the activation energy were found in the range of 0.46-0.61 eV; the characteristic time was obtained by fitting the spectra of the dielectric loss with the Havriliak-Negami functions. As a result of doping the ILC with CNT, the electric conductivity increases significantly. Ionic conductivity is dominant and it was indirectly observed through the electrode polarization (EP) effect. The very high dielectric permittivity values and the decrease of the electric conductivity at low frequencies confirm the presence of EP.

Electro-optical devices that work in a similar fashion as PDLCs (polymer-dispersed liquid crystals), produced from cellulose acetate (CA) electrospun fibers deposited onto indium tin oxide coated glass and a nematic liquid crystal (E7), were studied. CA and the CA/liquid crystal composite were characterized by multiple investigation techniques, such as polarized optical microscopy, dielectric spectroscopy and impedance measurements. Dielectric constant and electric energy loss were studied as a function of frequency and temperature. The activation energy was evaluated and the relaxation time was obtained by fitting the spectra of the dielectric loss with the Havriliak-Negami functions. To determine the electrical characteristics of the studied samples, impedance measurements results were treated using the Cole-Cole diagram and the three-element equivalent model.

The paper is focused on the investigation of the properties of some organic heterostructures deposited on patterned AZO electrodes. In the first step, 2D patterned arrays based on commercially photoresist were fabricated on glass substrates using nanoimprint litography. Next, on these periodic nanostructures, the transparent AZO layers were deposited by pulsed laser deposition. Further, heterostructures consisting in organic thin films such as 4,7 diphenyl-1,10-phenanthroline (BPhen) (electron transport layer), N,N'-di(1-naftalenil)-N,N'-diafenil-(1,1'-bifenil)-4,4'-diamina (alpha-NPD) (hole transport layer) and arylenevinylene oligomers (3,3-bis (N-hexylcarbazole)vinylbenzene (P13) and 1,4-bis [4-(N,N-diphenylamino)phenylvinyl] benzene (P78)) were obtained by matrix assisted pulsed laser evaporation. The fabricated multilayer organic structures have been investigated from optical (UV-VIS spectroscopy), morphological (scanning electron microscopy and atomic force microscopy) and electrical (I-V characteristics) point of view. An improvement in the current value recorded on the samples prepared on nanostructured electrode was recorded. The results evidence the possibility to integrate these heterostructures in organic electronic devices.

Clean technologies using the principles of green chemistry have attracted the attention of scientists in the last decade. Our work was focused on building advanced silver-based materials using an eco-friendly and convenient method. Two types of silver nanoparticles were synthesized using aqueous extracts of orange (Citrus sinensis) and grapefruit (Citrus paradisi) peels. Hybrid entities consisting of these bionanosilver particles and biomimetic membranes were "green" prepared and studied by spectral methods (UV-Vis absorption and emission, and FTIR-ATR spectroscopy). The morphology of silver-containing materials was analyzed by AFM images and their physical stability was checked by zeta potential measurements. Also, their antioxidant and antimicrobial properties were evaluated.

This paper presents electric and electro-optic studies conducted on a new composite, namely hydroxypropylcellulose network with liquid crystal fillings. The composite was manufactured using the electrospinning method, and deposited on indium tin oxide glass. In terms of electric characterization, the samples were subjected to impedance spectroscopy, their equivalent circuit model was deduced, and the corresponding electric parameters were computed based on the Cole-Cole diagrams and frequency plots of the two impedance components. In terms of electro-optic studies, the optical transmission of the sample under a varying steady-state alternative regime voltage was recorded, and the saturation threshold field was determined. Also, the switching times of the sample with respect to a step signal were determined.