National Institute Of Materials Physics - Romania

The bone remodeling field has shifted focus towards the delineation of products with two main critical attributes: internal architectures capable to promote fast cell colonization and good mechanical performance. In this paper, Luffa-fibers and graphene nanoplatelets were proposed as porogen template and mechanical reinforcing agent, respectively, in view of framing 3D products by a one-stage polymer-free process. The ceramic matrix was prepared through a reproducible technology, developed for the conversion of marble resources into calcium phosphates (CaP) powders. After the graphene incorporation (by mechanical and ultrasonication mixing) into the CaP matrix, and Luffa-fibers addition, the samples were evaluated in both as-admixed and thermally-treated form (compact/porous products) by complementary structural, morphological, and compositional techniques. The results confirmed the benefits of the two agents' addition upon the compact products' micro-porosity and the global mechanical features, inferred by compressive strength and elastic modulus determinations. For the porous products, overall optimal results were obtained at a graphene amount of <1 wt.%. Further, no influence of graphene on fibers' ability to generate at high temperatures internal interconnected-channels-arrays was depicted. Moreover, its incorporation led to a general preservation of structural composition and stability for both the as-admixed and thermally-treated products. The developed CaP-reinforced structures sustain the premises for prospective non- and load-bearing biomedical applications.

A simple view of ferroelectricity is proposed for a thin film with uniform polarization oriented perpendicular to its surface, starting from the assumption that this situation is always accompanied by charge accumulation in the outer metal electrodes, in the contamination layers or near the surface, in the ferroelectric film itself. Starting with the formula derived for an "elemental" dipole moment in the film, simple statistical mechanics allows one to derive hysteresis cycles, and their dependence on temperature starting with only two parameters: the dielectric constant of the material and the maximum value of the dipole moment of a unit cell. Values obtained for Curie temperatures and coercive fields agree well with experiments. "Exact" energy dependencies on the asymmetry parameter are derived, and their connection with the Landau-Ginsburg-Devonshire is proven. By considering also the dipolar interaction in a continuous model, in addition to the ordering energy in the presence of surface charge accumulation, one may estimate the distribution of the polarization inside the film and the validity of the hypothesis of uniform polarization.

For successful bone remodelling, the implantable 3D structures require suitable internal architectures which can be achieved by the use of fibres as natural templates. The ability of fibres to generate complex configurations for 3D bioceramic products was preliminary reported by sacrificial fibrous-porogen method. This study aims to demonstrate the safe-prospect of repurposing natural-fibres (i.e. luffa, hemp, wool) for embedment into a calcium phosphate (CaPs) matrix prepared through a completely reproducible route, and the beneficial influence of fibres upon structural, topographic and mechanical features of CaPs-products, since a complete assessment of the fibres-combustion-products resulted after thermal treatment was not yet disclosed. The complex investigation program based on i) thermo-gravimetric (TGA-DTG), ii) structural (XRD, FTIR-ATR), iii) morpho-compositional (SEM/EDS) and, most importantly, iv) biological cytotoxicity assays of fibres-derived chars, clearly indicated that luffa-fibres are the safest (>95% cell-survival) to be considered for bioceramic porous-orthopaedic-implants. Further, as exposed by nano-CT, the high temperature pyrolysis of luffa-fibres led to 3D interconnected channels inside the products, which allows a suitable vascularization and osteointegration. The topographic reconstruction of channels-inside-surface revealed a secondary 3D network of micro-pores. Along with the mechanical features, the novel bioceramic porous structures stand as reliable bone-repair alternatives.

The influence of the partial substitution of Fe by Si and thermal treatments on the structural, magnetic and magnetostrictive properties of the Fe67.5Pd30.5Si2 rapidly solidified ribbons has been investigated. A remarkable decrease in the martensite transformation temperature, with similar to 65 K lower than that of the Fe-Pd archetype alloy, is observed in the as-prepared ribbons. The thermal treatments shift the martensite transformation temperatures upward, with approximately 13 K for the higher thermal treatment. Also, these induce an improvement in the crystallinity in these ribbons with high texture and an increase in the crystallite size as a result of reducing the internal defects and stress. The thermodynamic considerations discussed in the frame of the Clapeyron-Clausius relation by using the calorimetric and thermomagnetic measurements (up to 7 T) reveal a weak influence of the magnetic fields on the martensitic transformation temperatures (similar to 0.5 K/T). The magnetostriction decrease with temperature under small magnetic fields was discussed, beside an unusual behaviour in the technically saturated domain. This behaviour is based on the coexistence of the ordinary and forced magnetostrictions, the last one increasing faster with the temperature decreasing.

In this work, new films containing composite materials based on blends of thermoplastic polymers of the polyurethane (TPU) and polyolefin (TPO) type, in the absence and presence of BaTiO3 nanoparticles (NPs) with the size smaller 100 nm, were prepared. The vibrational properties of the free films depending on the weight ratio of the two thermoplastic polymers were studied. Our results demonstrate that these films are optically active, with strong, broad, and adjustable photoluminescence by varying the amount of TPU. The crystalline structure of BaTiO3 and the influence of thermoplastic polymers on the crystallization process of these inorganic NPs were determined by X-ray diffraction (XRD) studies. The vibrational changes induced in the thermoplastic polymer's matrix of the BaTiO3 NPs were showcased by Raman scattering and FTIR spectroscopy. The incorporation of BaTiO3 NPs in the matrix of thermoplastic elastomers revealed the shift dependence of the photoluminescence (PL) band depending on the BaTiO3 NP concentration, which was capable of covering a wide visible spectral range. The dependencies of the dielectric relaxation phenomena with the weight of BaTiO3 NPs in thermoplastic polymers blends were also demonstrated.

Isocyanate-free composite coating can improve radiative cooling, energy storage and harvesting applications. This study reports the development and use of a isocyanate-free green surface coating(GSC) matrix derived from (2,2,6,6-tetramethylpiperidin-1-yl)oxy radical (TEMPO)-oxidized cellulose-(3-Aminopropyl)trimethoxysilane (APTMS)-ZnO nanoparticles-green polymer matrix that possesses upto similar to 220 degrees C thermal stability. The GSC exhibited excellent UV block and IR active capacity while achieving good coating hardness. The NMR, TGA-DTG and Pencil hardness studies revealed that this attribute by GSC was due to the formation of uniform crosslinking and reinforcement network. Using electrochemical impedance spectroscopy, the GSC had a low resistance. A high charge transfer resistance of similar to 15.826 k Omega was measured using electrochemical impedance spectroscopy for the GSC, high enough to attenuate photon radiation, making GSC material stable for application. Also, UV-weathering study was performed to investigate coating stability of the GSC. This is the first time application of TEMPO-cellulose based reinforcement of the green polymer matrix for the development of GSC through convergent approach to functional macromolecules. The study opens an opportunity of utilizing green material in energy applications, especially in windows shielding by a sufficient attenuation of photon radiations.

Using Raman scattering and FTIR spectroscopy, new optical evidence for the assembly of sensors based on reduced graphene oxide (RGO) and polydiphenylamine (PDPA) for the electrochemical detection of the epidermal growth factor receptor (EGFR) are reported. The assembly process of the RGO sheets electrochemical functionalized with PDPA involves the chemical adsorption of 1,4-phenylene diisothiocyanate (PDITC), followed by an incubation with protein G in phosphate buffer (PB) solution and after that the interaction with EGFR antibodies solution. Taking into account the changes reported by Raman scattering and FTIR spectroscopy, a chemical mechanism of the assembling process for this sensor is proposed. The preliminary testing of the electrochemical activity of the sensors based on RGO and PDPA was reported by cyclic voltammetry.

A composite material with applications in optoelectronics has been investigated. Pulsed laser deposition CdSe-doped glass film was prepared by the combinatorial deposition from two targets, namely pure CdSe and glass belonging to the 20Li(2)O-10Al(2)O(3)-7BaO-2La(2)O(3)-2ZnO-59P(2)O(5)system. Exciton peaks in the Vis domain, related to electron-hole pairs transitions from the valence band to the conduction band, were revealed in the optical absorption spectra of the CdSe-doped film. CdSe quantum dots (QDs) band gap energy depends on the CdSe quantum confinement effect. CdSe-doped film photoluminescence exhibits peaks in the red domain assigned to CdSe transitions from the excited state to the ground state. The size of CdSe nanoclusters, determined from x-ray diffraction is correlated with scanning electron microscopy-energy dispersive x-ray spectroscopy and atomic force microscopy results. Vibration modes specific both to CdSe QDs and to the vitreous network have been evidenced by Fourier transform infrared and Raman spectroscopy.

Y2O3:Yb(3+)5 at% ceramics have been synthesized by the reactive sintering method using different commercial yttria powders (Alfa-Micro, Alfa-Nano, and ITO-V) as raw materials. It has been shown that all Y(2)O(3)starting powders consist from agglomerates up to 5-7 mu m in size which are formed from 25-60 nm primary particles. High-energy ball milling allows to significantly decreasing the median particle sizeD(50)below 500 nm regardless of the commercial powders used. Sintering experiments indicate that powder mixtures fabricated from Alfa-Nano yttria powders have the highest sintering activity, while (Y0.86La0.09Yb0.05)(2)O(3)ceramics sintered at 1750 degrees C for 10 h are characterized by the highest transmittance of about 45%. Y2O3:Yb(3+)ceramics have been obtained by the reactive sintering at 1750-1825 degrees C using Alfa-Nano Y(2)O(3)powders and La2O3+ZrO(2)as a complex sintering aid. The effects of the sintering temperature on densification processes, microstructure, and optical properties of Y2O3:Yb(3)(+)5 at% ceramics have been studied. It has been shown that Zr(4)(+)ions decrease the grain growth of Y2O3:Yb(3+)ceramics for sintering temperatures 1750-1775 degrees C. Further increasing the sintering temperature was accompanied by a sharp increase of the average grain size of ceramics referred to changes of structure and chemical composition of grain boundaries, as well as their mobility. It has been determined that the optimal sintering temperature to produce high-dense yttria ceramics with transmittance of 79%-83% and average grain size of 8 mu m is 1800 degrees C. Finally, laser emission at similar to 1030.7 nm with a slope efficiency of 10% was obtained with the most transparent Y2O3:Yb(3+)5 at% ceramics sintered.

Hydroxyapatite Ca-10(PO4)(6)(OH)(2) (HAp) is an important bioactive material for bone tissue reconstruction, due to its highly thermodynamic stability at a physiological pH without bio-resorption. In the present study, the Ag:HAp and the corresponding Ag:HAp + D-3 thin films (similar to 200 nm) coating were obtained by vacuum deposition method on Ti substrate. The obtained samples were exposed to different UV irradiation times, in order to investigate the UV light action upon thin films, before considering this method for the thin film's decontamination. The effects of UV irradiation upon Ag:Hap + D-3 are presented for the first time in the literature, marking a turning point for understanding the effect of UV light on composite biomaterial thin films. The UV irradiation induced an increase in the initial stages of surface roughness of Ag:HAp thin film, correlated with the modifications of XPS and FTIR signals. The characteristics of thin films measured by AFM (RMS) analysis corroborated with XPS and FTIR investigation highlighted a process of recovery of the thin film's properties (e.g., RMS), suggesting a possible adaptation to UV irradiation. This process has been a stage to a more complicated UVA rapid degradation process. The antifungal assays demonstrated that all the investigated samples exhibited antifungal properties. Moreover, the cytotoxicity assays revealed that the HeLa cells morphology did not show any alterations after 24 h of incubation with the Ag:HAp and Ag:HAp + D-3 thin films.