National Institute Of Materials Physics - Romania

Complex physico-chemical investigations have been performed on white inlaid substance used in the orna-mentation of prehistoric clay artefacts from southern Romania ceramics from the Early Chalcolithic, up to the Middle/Late Bronze Age. Structural and morphological investigations of the white pigments have showed hundreds of nm up to microns size particles with calcite and hydroxyapatite (ash bone) as dominant components. The calcite was found on Early Chalcolithic pigment vessels while those where hydroxyapatite was dominant from the Middle/Late Bronze Age. FTIR spectra revealed the biogenic source of the hydroxyapatite (i.e. cremated animal bone) and the crystallinity degree values agrees with the expected temperatures of firing of the ancient furnaces; the calcite-based pigments were supposed to be filled post firing. The EPR was not able to able to provide a clear assignment of the cremated animal bones but thermoluminescence showed various sources of calcite.

Grazing incidence X-ray scattering (GIXRS) patterns of thin solid films based on non-stoichiometric chalcogenide glasses (ChG) from the pseudo - binary system (GeS4)x(AsS3)1-x were studied with a focus on the First Sharp Diffraction Peak (FSDP), assigned to the middle range order (MRO) of the glassy material. The films were grown using explosive thermal evaporation in vacuum (10-4 Pa) of pulverized ChG, prepared from previously synthesized bulk glasses, onto mono-crystalline silicon substrates. Scanning Electron Microscopy (SEM) and EnergyDispersive X-ray (EDX) spectroscopy were used to examine the morphology and elemental composition of the films, which were found to have similar composition to the bulk glasses. However, it was revealed that the molecular structure of the grown amorphous films differs from that of the initial ChG bulk material, as indicated by changes in the composition-dependent position and width of the FSDP. Additionally, the intensities of the FSDP in the films were higher compared to those of the bulk samples, suggesting that the molecular-like structure of ChGs is more pronounced in the form of thin films grown from the vapor phase.

The purpose of this work was to obtain an elastic composite material from polymer powders (polyurethane and polypropylene) with the addition of BaTiO3 until 35% with tailored dielectric and piezoelectric features. The filament extruded from the composite material was very elastic but had good features to be used for 3D printing applications. It was technically demonstrated that the 3D thermal deposition of composite filament with 35% BaTiO3 was a convenient process for achieving tailored architectures to be used as devices with functionality as piezoelectric sensors. Finally, the functionality of such 3D printable flexible piezoelectric devices with energy harvesting features was demonstrated, which can be used in various biomedical devices (as wearable electronics or intelligent prosthesis), generating enough energy to make such devices completely autonomous only by exploiting body movements at variable low frequencies.

Two neutral copper(I) halide complexes ([Cu(BTU)(2)X], X = Cl, Br) were prepared by the reduction of the corresponding copper(II) halides (chloride or bromide) with a benzoylthiourea (BTU, N-(3,4-diheptyloxybenzoyl)-N '-(4-heptadecafluorooctylphenyl)thiourea) ligand in ethanol. The two copper(I) complexes show a very interesting combination of 2D supramolecular structures, liquid crystalline, emission, and 1D ionic conduction properties. Their chemical structure was ascribed based on ESI-MS, elemental analysis, IR, and NMR spectroscopies (H-1 and C-13), while the mesomorphic behavior was analyzed through a combination of differential scanning calorimetry (DSC), polarizing optical microscopy (POM), and powder X-ray diffraction (XRD). These new copper(I) complexes have mesomorphic properties and exhibit a hexagonal columnar mesophase over a large temperature range, more than 100 K, as evidenced by DSC studies and POM observations. The thermogravimetric analysis (TG) indicated a very good thermal stability of these samples up to the isotropization temperatures and over the whole temperature range of the liquid crystalline phase existence. Both complexes displayed a solid-state emission with quantum yields up to 8% at ambient temperature. The electrical properties of the new metallomesogens were investigated by variable temperature dielectric spectroscopy over the entire temperature range of the liquid crystalline phase. It was found that the liquid crystal phases favoured anhydrous proton conduction provided by the hydrogen-bonding networks formed by the NH horizontal ellipsis X moieties (X = halide or oxygen) of the benzoylthiourea ligand in the copper(I) complexes. A proton conductivity of 2.97 x 10(-7) S.cm(-1) was achieved at 430 K for the chloro-complex and 1.37 x 10(-6) S.cm(-1) at 440K for the related bromo-complex.

We simulated numerically and demonstrated experimentally that the thermal emittance of a metasurface consisting of an array of rectangular metallic meta-atoms patterned on a layered periodic dielectric structure grown on top of a metallic layer can be tuned by changing several parameters. The resonance frequency, designed to be in the near-infrared spectral region, can be tuned by modifying the number of dielectric periods, and the polarization and incidence angle of the incoming radiation. In addition, the absorbance/emittance value at the resonant wavelength can be tuned by modifying the orientation of meta-atoms with respect to the illumination direction.

In the view of the advantages of using P, N, Si and graphene oxide (GO) for the development of flame retardants materials, a multi-structure synergistic composite was synthesized by grafting a novel nitrogen-containing polyhedral oligomeric silsesquioxane (HAK) and 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) on the surface of GO nanosheet. In the first step, 2-hydroxyethyl acrylate was selectively reacted, and then, HAK was synthetized by the condensation of the aza-Michael addition product with 3-(methacryloyloxy)propyltrimethoxysilane. Finally, the GO obtained by an innovative variant of Marcano-Tour improved exfoliation method was functionalized, first with DOPO, and then with HAK. The structural, morphological and surface properties of GO and GO-DOPO-HAK were investigated by means of XRD, TEM-EDX, FT-IR, Raman, zeta potential and XPS techniques, and it was evidenced the functionalization of GO with DOPO, and then with HAK. The performed microscale combustion calorimetry (MCC) and TG measurements indicated a great potential of the GO-DOPO-HAK as flame retardant material as the obtained residual weight for this sample was found to be the highest one compared to the other investigated samples. MCC analyses further revealed a major decrease in heat release capacity (HRC) and a significant increase in char yield, results that confirm the great potential of GO-DOPO-HAK as flame retardancy material. [GRAPHICS] .

Novel biomaterials with promising bone regeneration potential, derived from rich, renewable, and cheap sources, are reported. Thus, thin films were synthesized from marine-derived (i.e., from fish bones and seashells) hydroxyapatite (MdHA) by pulsed laser deposition (PLD) technique. Besides the physical-chemical and mechanical investigations, the deposited thin films were also evaluated in vitro using dedicated cytocompatibility and antimicrobial assays. The morphological examination of MdHA films revealed the fabrication of rough surfaces, which were shown to favor good cell adhesion, and furthermore could foster the in-situ anchorage of implants. The strong hydrophilic behavior of the thin films was evidenced by contact angle (CA) measurements, with values in the range of 15-18 degrees. The inferred bonding strength adherence values were superior (i.e., similar to 49 MPa) to the threshold established by ISO regulation for high-load implant coatings. After immersion in biological fluids, the growth of an apatite-based layer was noted, which indicated the good mineralization capacity of the MdHA films. All PLD films exhibited low cytotoxicity on osteoblast, fibroblast, and epithelial cells. Moreover, a persistent protective effect against bacterial and fungal colonization (i.e., 1- to 3-log reduction of E. coli, E. faecalis, and C. albicans growth) was demonstrated after 48 h of incubation, with respect to the Ti control. The good cytocompatibility and effective antimicrobial activity, along with the reduced fabrication costs from sustainable sources (available in large quantities), should, therefore, recommend the MdHA materials proposed herein as innovative and viable solutions for the development of novel coatings for metallic dental implants.

We studied here the influence of Li+ ions on the benzene rings of nematic mixture E7, which is electrochemically adsorbed onto gold electrode surface, to highlight the ability of this mixture for the applications in the field of the rechargeable Li+-ion batteries. Raman spectra support the changes observed in electrochemical analyses while contact angle measurements show that wetting properties of E7 layer were modified after deposition of this mixture onto gold support and the doping with Li+ ions.

We studied here the influence of Li+ ions on the benzene rings of nematic mixture E7, which is electrochemically adsorbed onto gold electrode surface, to highlight the ability of this mixture for the applications in the field of the rechargeable Li+-ion batteries. Raman spectra support the changes observed in electrochemical analyses while contact angle measurements show that wetting properties of E7 layer were modified after deposition of this mixture onto gold support and the doping with Li+ ions.

Nanocomposite films based on macrocyclic compounds (zinc phthalocyanine (ZnPc) and 5,10,15,20-tetra(4-pyridyl) 21H,23H-porphyrin (TPyP)) and metal oxide nanoparticles (ZnO or CuO) were deposited by matrix-assisted pulsed laser evaporation (MAPLE). 1,4-dioxane was used as a solvent in the preparation of MAPLE targets that favor the deposition of films with a low roughness, which is a key feature for their integration in structures for optoelectronic applications. The influence of the addition of ZnO nanoparticles (similar to 20 nm in size) or CuO nanoparticles (similar to 5 nm in size) in the ZnPc:TPyP mixture and the impact of the added metal oxide amount on the properties of the obtained composite films were evaluated in comparison to a reference layer based only on an organic blend. Thus, in the case of nanocomposite films, the vibrational fingerprints of both organic compounds were identified in the infrared spectra, their specific strong absorption bands were observed in the UV-Vis spectra, and a quenching of the TPyP emission band was visible in the photoluminescence spectra. The morphological analysis evidenced agglomerated particles on the composite film surface, but their presence has no significant impact on the roughness of the MAPLE deposited layers. The current density-voltage (J-V) characteristics of the structures based on the nanocomposite films deposited by MAPLE revealed the critical role played by the layer composition and component ratio, an improvement in the electrical parameters values being achieved only for the films with a certain type and optimum amount of metal oxide nanoparticles.