Publications

Currently, there is a considerable time-lag in the industrialisation of innovative technological solutions for the functionalization of osseous implants, with ever-demanding healthcare requirements (e.g., controlled release of therapeutic ions, match of biomaterial degradation - bone growth rates, antimicrobial efficiency). As third-generation biomaterials, phosphate bio-glasses (PBGs) have demonstrated an ability to stimulate specific biological responses from tissue to molecular level, by successfully coupling bioactive and resorbable material properties. Here, radio-frequency magnetron sputtered (RF-MS) PBGs were explored as sacrificial resorbable layers for prospective biomedical implant designs. A PBG powder with a 50-P2O5, 35-CaO, 10-Na2O and 5-Fe2O3 composition (mol%) was used as source (target) material. The influence of the argon working pressure (0.2-1 Pa) - one of the most prominent RF-MS variables - on the morphology, structure, uniformity, composition, degradation rate and cytocompatibility of PBG films was investigated. The engineered modification of physical-chemical and biological features of the PBG sputtered films was multi-parametrically surveyed by AFM, EDXS, spectroscopic ellipsometry, GIXRD, FTIR spectroscopy measurements and in vitro assays. Results suggested that the film thickness, composition, density and structure were preserved over a uniformity region having a diameter of similar to 30 mm, irrespective of sputtering pressure. The network connectivity and the surface porosity of the films were found to have antagonistic roles with respect to the in vitro degradation performance. The possibility of fine tuning the composition, structure and thereby biological interaction of the PBG films by conveniently modifying the sputtering pressure was shown (i.e., permitting their complete controlled degradation, without cytotoxic effects). This work is the first to show in vitro cytocompatibility outcomes of sputtered PBG films and their cross-area uniformity, and thus, it could prove to be an important technological step in their future biomedical application and suggest implications for future industrial scale-up.

Cu-Fe-Sn-S films were obtained on indium tin oxide / glass substrates by a low-cost electrodeposition using an aqueous solution of CuSO4, FeSO4, SnSO4, and Na2S2O3 at room temperature followed by high-temperature sulfurization (500 degrees C) in argon flow. A range of cathodic potentials have been used for electrodeposition, those being chosen after a preliminary cyclic voltammetry study. The coatings were characterized using X-ray diffraction, Raman spectroscopy, scanning electron microscopy, energy dispersive spectroscopy, X-ray Photoelectron Spectroscopy and conventional spectroscopy (diffuse reflectance and specular transmission). The results are discussed with respect to the used applied potential.

We report a novel strategy to enhance the dielectric breakdown strength and the energy storage performance of lead-free relaxor ferroelectric ceramics through the fabrication of semiconductor/relaxor 0-3 type composites based on 0.6Ba(Zr0.2Ti0.8)O-3-0.4(Ba0.7Ca0.3)TiO3 [BZCT] and ZnO. X-ray diffraction (XRD), Raman spectroscopy, and scanning electron microscopy (SEM) measurements confirm the formation of semiconductor/relaxor 0-3 type composites, in which ZnO particles are randomly distributed at the grain boundaries of BZCT. Further, the XRD analysis suggests a structural phase change from a tetragonal to a pseudocubic phase as the ZnO content increases from 0 to 5 wt. % in BZCT/ZnO composites. The pseudocubic phase favors the relaxor behavior of the composites as is evident from dielectric studies. The polarization-electric field (P-E) loops reveal the ferroelectric nature of the BZCT/ZnO composites. The energy storage properties of BZCT/ZnO composite ceramics as a function of different wt. % of ZnO are found to be optimum at 1 wt. % with a recoverable energy density of 2.61 J/cm(3) and an efficiency of 74.2%, at an electric field of 282 kV/cm. Besides, an enhancement of 166% in the electric breakdown and 220% in the recoverable energy density was achieved compared to the BZCT ceramics due to the improved density and the large value of Delta P = P-m - P-r (25.55 mu C/cm(2)). Therefore, this work evidences that the formation of the semiconductor/relaxor 0-3 type composites can be an effective way to significantly improve the energy storage performance of lead-free relaxor ferroelectric ceramics. (C) 2020 The Authors. Publishing services by Elsevier B.V. on behalf of Vietnam National University, Hanoi.

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 dynamic method was developed to evaluate the components in the equivalent circuit of a ferroelectric capacitor. The method is based on the application of short trapezoidal voltage pulses of variable amplitude and the analysis of the resulting current by considering the ferroelectric capacitor as a parallel R-p-C-p equivalent circuit. The values of R-p and C-p components are obtained in relation to different stages of polarization switching as the amplitude of the applied pulses increases. The most important result obtained by applying the present method is the evidence of an abrupt decrease of the R-p value (about 2 orders of magnitude) at the coercive voltage, while the equivalent C-p does not present a dramatic variation during polarization switching. This is interpreted in the context of negative capacitance obtained for ferroelectrics when polarization passes through zero value. The results obtained by using the proposed dynamic characterization method that will be referred to as "dynamic dielectric characterization", are in good agreement with those obtained by classic capacitance-voltage measurements. A method to stabilize the negative capacitance for longer periods of time is also presented by adding an external resistance in series with the ferroelectric capacitor.

The thermal behavior of Cu-doped TiO2 gels obtained by the sol-gel method was investigated by thermogravimetric and differential thermal analysis (TG/DTG/DTA) and differential scanning calorimetry (DSC) measurements. The comparative investigation of the structure and morphology of the as-prepared gels and of the nanopowders obtained by annealing them was realized by transmission electron microscopy (TEM), Fourier transmission infrared spectroscopy (FTIR), X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS). Significant differences were noticed depending on the amount of dopant (0.5 or 2.0 mol % CuO). A higher dopant concentration resulted in a more complex decomposition of the sample. This behavior was associated with the formation of various molecular species in the sol-gel solutions before gelation, determined by the different amount of the dopant used.

Phase-change memories have reached an advanced degree of maturity, although, to be able to meet the increasing storage demand, multilevel capability is needed. A GeTe memristor is obtained in an amorphous state and it is subjected to a specific thermal treatment which initiates the transition toward the crystalline state. It is found that this crystalline state initialization process is highly beneficial for subsequently obtaining a large number of intermediate resistive states between the high and low resistive states. Multiple resistance levels are achieved by operating the devices in both DC sweeps and rectangular pulse modes in the low-voltage subthreshold regime. The conduction is modeled using a space charge limited conduction model, showing three distinct conduction regions in the high resistive state which merge toward a single conduction region as the low resistive state is approached. The obtained memristors can be used as multilevel nonvolatile memories or as synapses in neuromorphic computing.

We explore higher order dynamical effects in the transport through a two-dimensional nanoscale electron system embedded in a three-dimensional far-infrared photon cavity. The nanoscale system is considered to be a short quantum wire with a single circular quantum dot defined in a GaAs heterostructure. The whole system, the external leads and the central system are placed in a constant perpendicular magnetic field. The Coulomb interaction of the electrons, the paraand diamagnetic electron-photon interactions are all treated by a numerically exact diagonalization using step-wise truncations of the appropriate many-body Fock spaces. We focus on the difference in transport properties between a description within an electric dipole approximation and a description including all higher order terms in a single photon mode model. We find small effects mostly caused by an electrical quadrupole and a magnetic dipole terms that depend strongly on the polarization of the cavity field with respect to the transport direction and the photon energy. When the polarization is aligned along the transport direction we find indications of a weak self-induction that we analyze and compare to the classical counterpart, and the self-energy contribution of high-order interaction terms to the states the electrons cascade through on their way through the system. Like expected the electron-photon interaction is well described in the dipole approximation when it is augmented by the lowest order diamagnetic part for a nanoscale system in a cavity in an external magnetic field.

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.