Dr. George STAN

Background: Hepatocellular carcinoma is associated with high mortality and increasing incidence. Sorafenib, a cornerstone of therapy for advanced hepatocellular carcinoma, presents certain disadvantages, including low bioavailability and poor water solubility. This work describes a new strategy for sorafenib-targeted delivery aimed at improving treatment efficiency and reducing side effects. Methods: Magnetic nanoparticles coated with azelaic acid were modified with aptamer molecules that specifically recognize human liver cancer cell line HepG2, ensuring specificity for the tumor tissue. The nanoparticles were further loaded with sorafenib. The obtained drug delivery system was extensively characterized using UV-Vis spectrophotometry, transmission electron microscopy, X-ray diffraction, Fourier-transform infrared spectroscopy, X-ray photoelectron spectroscopy, and electrochemical impedance spectroscopy. Results: The drug delivery system demonstrated a higher release of sorafenib at acidic pH compared to pH 7.4. The cell internalization of the bare and aptamer-modified magnetic nanoparticles was assessed in HepG2 and human normal foreskin fibroblasts BJ cell lines, demonstrating that the aptamer significantly enhances internalization in tumor cells, while having no impact on healthy cells. Conclusions: The sorafenib-modified nanoparticles exhibited excellent cytocompatibility with BJ cells across all tested concentrations, while showing cytotoxicity towards HepG2 cells at higher concentrations, confirming the selectivity of the system.

Biodegradable templates are sought for targeted antibiotic administration/delivery in bone infections to avoid detrimental reactions during bone regeneration. We investigated two key-aspects in this direction: 1) the optimal antibiotic delineation, with thermal stability equivalent to the temperature involved for templates preparation and 2) the antibacterial templates development by a two-step homogenization process. The selected antibiotic - ampicillin (AMP) was mechanically and then thermally mixed with the prime materials: poly(lactic acid) (PLA) - the polymeric matrix, biogenic bovine bone-derived hydroxyapatite (HA, particles <40 mu m), and graphene nanoplatelets (GnP, micrometric range). For the first time, all materials were used in simultaneous modulated ratios for the synthesis of PLA/AMP (1-5 wt.%)/HA (0-30 wt.%)/GnP (0-3 wt.%) composites. The influence of the concomitant materials modulation was surveyed through several assays. The FTIR-ATR spectroscopy depicted a three-level model of overlapping structures asserting the solid molecular cross-linking between all materials, without structural alterations induced to any material (XRD analysis). The addition of AMP to the PLA matrix caused a slight particle conglomeration, alleviated through GnP addition. The microporous HA particles supported the adhesion to the PLA matrix and promoted the AMP particles' entrapment/attachment. Linked to the enhanced wettability of the composite materials, the phosphate buffered saline solution (PBS) degradation profiles revealed a pronounced burst during the first 14-28 days of incubation and a long-term, low-level process hereafter. Thus, the formation of pores and cavities were signalled along with the HA particles' fragmentation. The released AMP (percentage) pictured an ascending trendline during the 24 h of analysis, at all targeted ratios. The preservation of AMP features at 200 degrees C was endorsed by the strong antibacterial activity of composite materials against Staphylococcus aureus (S. Aureus) growth and the medium response against Escherichia coli (E. Coli) - the higher the drug release, the higher the inhibitory effect on bacteria evolution.

Due to the importance of buffer layers in interface engineering, the development of more variants and the rational design of materials have a significant influence on the performance of optoelectronic devices. This study provides a strategy to increase device performance by facilitating efficient charge transfer and defect passivation by combining the properties of eco-friendly materials (adenine, cytosine, guanine, thymine, and uracil) with the physicochemical properties of metal oxides. The aim of this paper was to investigate the interaction of zinc oxide (ZnO) nanostructures (seed, nanoparticles, and nanowires) with nucleobase layers and to discuss their potential applications as organic-inorganic interfacial bilayers. The impact is analyzed from structural, morphological, optical, and electrical points of view. Nucleobase-ZnO nanostructure layers present high optical transparency in the visible range. Electrical measurements confirmed that the high surface area of nanowires can enhance interactions with nucleobases, leading to better charge transfer. The results showed that these nucleobase-ZnO nanostructure layers are promising interface materials for enhancing optoelectronic device performance through interfacial charge transport and light management, while enabling the design of environmentally friendly devices.

Developing new glass electrolytes with the necessary room-temperature ionic conductivity (similar to 10(-3) Scm(-1)) for solid-state batteries, especially sodium-ion (Na+) batteries, has been impeded by the lack of a clear relationship between composition, structure, and conductivity in glass materials. This study highlights the impact of the mixed glass formers on the structure, Na+-ion dynamics, and glass conductivity. To this end, we substituted SiO2 for P2O5 in sodium alumino-phosphate glass while maintaining a constant molar concentration of Al2O3 and Na2O. A detailed analysis combining molecular simulations and experiments revealed that the glass containing 15 mol% SiO2 exhibited the highest DC ionic conductivity of similar to 9 x 10(-6) Scm(-1) at 473 K, followed by a decrease for 20 mol% SiO2. To understand this behavior, microscopic characteristic length such as critical hopping distance and Na+ diffusion coefficients were correlated with structural changes using AC conductivity analysis. Altogether, we elucidate the composition-dependent Na+ ion dynamics in the alumino-phosphate glass system, with factors like mobile charge carrier concentration, ion mobility, and coulombic forces influenced by the structure of different glass compositions.

Synthetic bone graft substitutes, including calcium phosphates (CaP), bioactive glasses (BG), and their composites with biopolymer matrices are attracting interest for bone tissue repair and regeneration. A key challenge is accurately replicating the biological structure and functionality of natural bone and optimizing the porous structure to match trabecular bone. This has been addressed by doping CaPs with therapeutic ions and using scaffolding methods like polymeric sponge replication and different additive manufacturing techniques. Biomimetic approaches employing naturally occurring porous biominerals with pore sizes comparable to those of trabecular bone, offer promising alternatives. This work reviews the hydrothermal transformation of cuttlefish bone (CB) into CaP scaffolds, while preserving its original porous structure, producing hydroxyapatite (HA, Ca10(PO4)6(OH)2), tricalcium phosphate (TCP, Ca3(PO4)2), and biphasic CaPs, both undoped and therapeutic ion-doped, constructs. Coating such biomimetic scaffolds with sol-gel-derived BG and biopolymers produces multifunctional bone graft substitutes with enhanced mechanical and biological properties. Moreover, polymeric coatings can act as drug reservoirs, enabling controlled release of therapeutic agents. The review highlights that integrating biomimetic strategies with advanced coating solutions holds great promise for creating multifunctional scaffolds that mimic nature and improve therapeutic outcomes in bone tissue engineering.

Synthetic bone graft substitutes, including calcium phosphates (CaP), bioactive glasses (BG), and their composites with biopolymer matrices are attracting interest for bone tissue repair and regeneration. A key challenge is accurately replicating the biological structure and functionality of natural bone and optimizing the porous structure to match trabecular bone. This has been addressed by doping CaPs with therapeutic ions and using scaffolding methods like polymeric sponge replication and different additive manufacturing techniques. Biomimetic approaches employing naturally occurring porous biominerals with pore sizes comparable to those of trabecular bone, offer promising alternatives. This work reviews the hydrothermal transformation of cuttlefish bone (CB) into CaP scaffolds, while preserving its original porous structure, producing hydroxyapatite (HA, Ca10(PO4)6(OH)2), tricalcium phosphate (TCP, Ca3(PO4)2), and biphasic CaPs, both undoped and therapeutic ion-doped, constructs. Coating such biomimetic scaffolds with sol-gel-derived BG and biopolymers produces multifunctional bone graft substitutes with enhanced mechanical and biological properties. Moreover, polymeric coatings can act as drug reservoirs, enabling controlled release of therapeutic agents. The review highlights that integrating biomimetic strategies with advanced coating solutions holds great promise for creating multifunctional scaffolds that mimic nature and improve therapeutic outcomes in bone tissue engineering.

Bioactive glasses (BGs) are known for their selective ability to (i) form a mechanically strong interfacial bond with hard (bone) or soft tissues (gingivae or cartilages) (i.e., silica-, silica-phosphate-, phosphate-, boratephosphate-, or silica-phosphate-borate-based BGs); or (ii) serve as reservoirs for fast-release of therapeutic (osteogenic, angiogenic, anticarcinogenic, or antimicrobial) ions (i.e., phosphate-based BGs and mesoporous BGs). The strength of the bone bond yielded by the osteoproductive-capable BGs is generally equivalent to, or higher than the bone strength. The resorbability of phosphate-based BG is dependent on the content of network formers and cross-linkers. All BGs elicit excellent biochemical compatibility. However, their fracture toughness is typically less than and the elastic modulus is greater than those of bone, indicating that most BGs have suboptimal biomechanical compatibility when used in load-bearing applications. One promising approach to overcome this problem is the development of BGs in coating form, applied to the surface of load-bearing endosseous implants. This work critically assesses BG thin-layers fabricated by the radio-frequency magnetron sputtering method, an industry-ready large-scale physical vapour deposition technology. It is demonstrated that, despite the relative lack of attention paid to this technology, it enables the development of unique BG coatings with efficacious therapeutic capabilities. Here, we present an overview of the most relevant developments achieved thus far, along with the remarkable advantages, drawbacks to overcome, and future perspectives with the intention of highlighting the vast possibilities of this specific field of research.

Over the past two decades, the CICECO-hub scientists have devoted substantial efforts to advancing bioactive inorganic materials based on calcium phosphates and alkali-free bioactive glasses. A key focus has been the deliberate incorporation of therapeutic ions like Mg, Sr, Zn, Mn, or Ga to enhance osteointegration and vascularization, confer antioxidant properties, and impart antimicrobial effects, marking significant contributions to the field of biomaterials and bone tissue engineering. Such an approach is expected to circumvent the uncertainties posed by methods relying on growth factors, such as bone morphogenetic proteins, parathyroid hormone, and platelet-rich plasma, along with their associated high costs and potential adverse side effects. This comprehensive overview of CICECO-hub ' s significant contributions to the forefront inorganic biomaterials across all research aspects and dimensionalities (powders, granules, thin films, bulk materials, and porous structures), follows a unified approach rooted in a cohesive conceptual framework, including synthesis, characterization, and testing protocols. Tangible outcomes [injectable cements, durable implant coatings, and bone graft substitutes (scaffolds) featuring customized porous architectures for implant fixation, osteointegration, accelerated bone regeneration in critical-sized bone defects] were achieved. The manuscript showcases specific biofunctional examples of successful biomedical applications and effective translations to the market of bone grafts for advanced therapies.

The synergistic piezoelectric and osteoconductive properties of barium titanate (BT) and hydroxyapatite (HA) could stir the development of a new generation of synthetic bone graft substitutes, with capability for rapid and safe osseointegration. The research focused on two concurrent approaches for coupling the BT and HA materials: (i) conventional sintering of BT-HA powder mixtures; and (ii) functionalization of pre-sintered BT with HA coatings using magnetron sputtering (MS). Irrespective of the BT/HA ratios ranging from 95/5 to 80/20 wt%, nanocrystalline or highly-crystallized nature of the powders, sub-micron- or micron-sized particle dimensions, and sintering temperature, it was observed that the BT-HA reactivity cannot be prevented above 800 degrees C. At higher temperatures in the range of 1000-1300 degrees C, HA undergoes decomposition and extensively reacts with BT, leading to the formation of several secondary phases such as CaTiO3, Ba2Ca(PO4)2, BaCa6(PO4)4O, BaCa(PO3)4, and beta-Ca2P2O7. As a consequence, the cytocompatibility assessed in fibroblast and osteoblast cell cultures, as well as the piezoelectric response, were significantly altered. Applying HA coatings by MS to the sintered BT ceramics successfully preserved their piezoelectric properties, while also providing an unaltered cytocompatible and osteogenic-prone surface. The HA coatings were fully crystallized at post-deposition annealing temperatures of 550 and 700 degrees C, achieving crystalline qualities comparable to HA powders sintered at 1100 and 1200 degrees C, respectively. No reactivity events between BT and HA were observed. Partial reactivity was only noticeable upon annealing at 1000 degrees C. Therefore, it is suggested that the HA coating of BT is effective in seamlessly coupling the piezoelectric and osteogenic properties of the two constituents without compromise.

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.

The attraction towards Ti and its alloys reside in their superior mechanical and tribological features, as compared to CaPs, which are renowned for their compositional and structural features similar to those of natural bones. However, Ti-based materials suffer from limited biocompatibility and inertness when implanted for extended periods. As such, surface modification with ceramic coatings is required in order to achieve proper biomedical features and enhance their overall behavior in the human body. Hence, this study outlined for the first time the prospect of coating several Ti6Al4V substrates (disks) with bovine-bone derived hydroxyapatite (HA) by laser cladding technique with pre-placed slurry. During laser processing the input materials merge depending on the heating rate/temperature and clad materials. The proposed sample preparation set-up, followed for the first time in this study, involved the concomitant modulation of two parameters: the natural HA ratio (100 wt%, and 50 wt % HA + 50 wt% Ti blends) and laser beam power (500-1000 W range). The laser beam was applied after the ceramic slurries (prepared HA/HA-based blends mixed with polyvinyl alcohol) were placed inside the priorly machined channels on the metallic Ti disks. Partially overlapped cladding tracks (similar to 30% overlapping ratio) resulted and the investigations were further performed in cross-section view. The structural analyses confirmed the formation of calcium titanate as main phase for all samples and the arrest of HA only for those prepared with 100% HA ratio at low to medium laser powers. In addition, the morpho-compositional evaluation revealed the formation of a fully ceramic coating only for the latter sample sets. Further, the surface wettability (contact angle and surface free energy) and Vickers micro-hardness results led to the selection of the optimal technological parameters for the development of ceramic cladded layers with prospect compatibility with regenerative med-icine applications.

Sub-stochiometric nickel oxide (NiOx) films were investigated as a hole selective contact option in silicon (Si) heterojunction solar cells. Numerical simulations were carried out to evaluate the impacts of the NiOx electronic properties variations and the NiOx/Si interface defect density (D-it) on device performance. Simulation data suggest that the best performance is achievable for wide bandgaps (E-g) and corresponding high valence band edge (E-VB) positions in the NiOx films. Overall, in simulations, the performance remains practically unchanged for the nickel vacancy concentrations [V-Ni] = 10(17)-10(21 )cm(-3), assuming high E-VB and low D-it. The experimental data measured using NiOx films prepared by radio-frequency magnetron sputtering reveal that the increase in [V-Ni] lifts the conductivity, concurrently decreasing E-g and E-VB. As a result, we concluded that the performance of the fabricated sputtered NiOx/Si heterojunction solar cell is limited by high D-it as well as narrow E-g and low E-VB.

This work was devoted to the first multi-parametric unitary comparative analysis of a selection of sintered piezoceramic materials synthesised by solid-state reactions, aiming to delineate the most promising biocompatible piezoelectric material, to be further implemented into macro-porous ceramic scaffolds fabricated by 3D printing technologies. The piezoceramics under scrutiny were: KNbO3, LiNbO3, LiTaO3, BaTiO3, Zr-doped BaTiO3, and the (Ba0.85Ca0.15)(Ti0.9Zr0.1)O-3 solid solution (BCTZ). The XRD analysis revealed the high crystallinity of all sintered ceramics, while the best densification was achieved for the BaTiO3-based materials via conventional sintering. Conjunctively, BCTZ yielded the best combination of functional properties-piezoelectric response (in terms of longitudinal piezoelectric constant and planar electromechanical coupling factor) and mechanical and in vitro osteoblast cell compatibility. The selected piezoceramic was further used as a base material for the robocasting fabrication of 3D macro-porous scaffolds (porosity of similar to 50%), which yielded a promising compressive strength of similar to 20 MPa (higher than that of trabecular bone), excellent cell colonization capability, and noteworthy cytocompatibility in osteoblast cell cultures, analogous to the biological control. Thereby, good prospects for the possible development of a new generation of synthetic bone graft substitutes endowed with the piezoelectric effect as a stimulus for the enhancement of osteogenic capacity were settled.

This work evaluates the effects of manganese (Mn) doping on the morpho-structural features, mechanical performance, and in vitro biological response of beta-tricalcium phosphate (beta-TCP) derived bioceramics for bone tissue engineering applications. Five different Mn doping levels (i.e., 0.01%, 0.05%, 0.1%, 0.5%, and 1 wt.%) were investigated, with the beta-TCP-based bioceramics being sintered at four temperatures (i.e., 1000, 1100, 1200, and 1300 degrees C). A densification improvement was induced when using Mn in excess of 0.05 wt.%; the densification remained stationary in the sintering temperature range of 1200 - 1300 degrees C. The structural analyses evidenced that all samples sintered at 1000 and 1100 degrees C were composed of beta-TCP as major phase and hydroxyapatite (HA) as a minor constituent (similar to 4-6 wt.%). At the higher temperatures (1200 and 1300 degrees C), the formation of alpha-TCP was signalled at the expense of both beta-TCP and HA. The Mn doping was evidenced by lattice parameters changes. The evolution of the phase weights is linked to a complex inter-play between the capacity of the compounds to incorporate Mn and the thermal decomposition kinetics. The Mn doping induced a reduction in the mechanical performance (in terms of compressive strength, Vickers hardness and elastic modulus) of the beta-TCP-based ceramics. The metabolic activity and viability of osteoblastic cells (MC3T3-E1) for the ceramics were studied in both powder and compacted pellet form. Ceramics with Mn doping levels lower than 0.1 wt.% yielded a more favorable microenvironment for the osteoblast cells with respect to the undoped beta-TCP. No cytotoxic effects were recorded up to 21 days. The Mn-doped beta-TCPs showed a significant increase (p < 0.01) in alkaline phosphatase activity with respect to pure beta-TCP.

Anodization was used to obtain a nanotubular TiO2 photoanode on F-SnO2 glass. Subsequent annealing in the CH4 atmosphere promoted the C-doping and improved the crystallinity of the TiO2 nanotubes. The pulsed laser deposition was applied to cover the nanotubes with Bi2O3, serving as a hole transport material. X-ray photoelectron spectroscopy analyses of the doped samples reveal a shift in the valence band's maximum position towards lower binding energy as compared to those observed for the undoped samples (annealed in the air). The doping positively affects the absorption by shifting the absorption edge to 567 nm. I-V measurements under illumination show that the C-doping of TiO2 increases the current density following the absorbance results. The highest open circuit voltage was reached for the samples with the 300 degrees C-deposited Bi2O3 layer, pointing to better quality of the p-n junction, hence of the contact between Bi2O3 and TiO2. This in situ annealing provided the formation of close contact between Bi2O3 and TiO2, which enabled a faster charge transport as compared to the contact obtained with no annealing or even with post annealing.

Ag/Ga were incorporated into resorbable orthopaedic phosphate bioactive glasses (PBG, containing P, Ca, Mg, Na, and Fe) thin films to demonstrate their potential to limit growth of Staphylococcus aureus and Escherichia coli in post-operative prosthetic implantation. Dual target consecutive co-sputtering was uniquely employed to produce a 46 nm Ag:PBG composite observed by high resolution TEM to consist of uniformly dispersed similar to 5 nm metallic Ag nano-particles in a glass matrix. Ga3+ was integrated into a phosphate glass preform target which was magnetron sputtered to film thicknesses of similar to 400 or 1400 nm. All coatings exhibited high surface energy of 75.4-77.3 mN/m, attributed to the presence of hydrolytic P-O-P structural surface bonds. Degradation profiles obtained in deionized water, nutrient broth and cell culture medium showed varying ion release profiles, whereby Ga release was measured in 1400 nm coating by ICP-MS to be similar to 6, 27, and 4 ppm respectively, fully dissolving by 24 h. Solubility of Ag nanoparticles was only observed in nutrient broth (similar to 9 ppm by 24 h). Quantification of colony forming units after 24 h showed encouraging antibacterial efficacy towards both S. aureus (4-log reduction for Ag:PBG and 6-log reduction for Ga-PBG approximate to 1400 nm) and E. coli (5-log reduction for all physical vapour deposited layers) strains. Human Hs27 fibroblast and mesenchymal stem cell line in vitro tests indicated good cytocompatibility for all sputtered layers, with a marginal cell proliferation inertia in the case of the Ag:PBG composite thin film. The study therefore highlights the (i) significant manufacturing development via the controlled inclusion of metallic nanoparticles into a PBG glass matrix by dual consecutive target co-sputtering and (ii) potential of PBG resorbable thin-film structures to incorporate and release cytocompatible/antibacterial oxides. Both architectures showed prospective bio-functional performance for a future generation of endo-osseous implant-type coatings.

We report on hydroxyapatite (HA) of biological-origin doped with lithium carbonate (LiC) and lithium phosphate (LiP) coatings synthesized by Pulsed laser deposition onto Ti6Al4V substrates fabricated by the Additive manufacturing technique. A detailed comparison from the structural, morphological, chemical composition, wetting behavior and bonding strength standpoints of as-deposited (NTT) and post-deposition thermal-treated (TT) coatings at temperatures ranging from 400 to 700 degrees C (i.e., TT400-TT700), was performed. Structural investigations indicated a complete crystallization of the initially amorphous HA-based layers at temperatures in excess of 500 degrees C. The morphological analyses emphasized the rough appearance of the film surfaces, consisting of particulates whose dimensions increased at higher temperatures, with an emphasis on LiC coatings. AFM investigations evidenced rough surfaces, with a clear tendency to increase in corrugation with the applied temperature, in the case of LiC coatings. A hydrophobic behavior was observed for control, NTT and TT400 samples, whilst a radical shift towards hydrophilicity was demonstrated for both types of structures at higher temperatures. In the case of TT500-TT700 coatings, the pull-out adherence values increased considerably compared to control ones. Taking into consideration the obtained results, the positive influence of post-deposition thermal treatments (performed at higher temperatures) on the physical-chemical and mechanical properties of LiC and LiP coatings was indicated. Alongside these improved characteristics observed at elevated temperatures, the sustainable nature of the used BioHA materials should recommend them as viable alternatives to synthetic HA ones for bone implant applications.

The incorporation of therapeutic-capable ions into bioactive glasses (BGs), either based on silica (SBGs) or phosphate (PBGs), is currently envisaged as a proficient path for facilitating bone regeneration. In conjunction with this view, the single and complementary structural and bio-functional roles of CuO and Ga2O3 (in the 2-5 mol% range) were assessed, by deriving a series of SBG and PBG formulations starting from the parent glass systems, FastOs (R) BG -38.5SiO2-36.1CaO-5.6P2O5-19.2MgO-0.6CaF2, and 50.0P2O5-35.0CaO-10.0Na2O-5.0 Fe2O3 (mol%), respectively, using the process of melt-quenching. The inter-linked physico-chemistry -biological response of BGs was assessed in search of bio-functional triggers. Further light was shed on the structural role -as network former or modifier -of Cu and Ga, immersed in SBG and PBG matrices. The preliminary biological performance was surveyed in vitro by quantification of Cu and Ga ion release under homeostatic conditions, cytocompatibility assays (in fibroblast cell cultures) and antibacterial tests (against Staphylococcus aureus). The similar (Cu) and dissimilar (Ga) structural roles in the SBG and PBG vitreous networks governed their release. Namely, Cu ions were leached in similar concentrations (ranging from 10-35 ppm and 50-110 ppm at BG doses of 5 and 50 mg/mL, respectively) for both type of BGs, while the release of Ga ions was 1-2 orders of magnitude lower in the case of SBGs (i.e., 0.2-6 ppm) compared to PBGs (i.e., 9-135 ppm). This was attributed to the network modifier role of Cu in both types of BGs, and conversely, to the network former (SBGs) and network modifier (PBGs) roles of Ga. All glasses were cytocompatible at a dose of 5 mg/mL, while at the same concentration the antimicrobial efficiency was found to be accentuated by the coupled release of Cu and Ga ions from SBG. By collective assessment, the most prominent candidate material for the further development of implant coatings and bone graft substitutes was delineated as the 38.5SiO2-34.1CaO-5.6P2O5-16.2MgO-0.6CaF2-2.0CuO-3.0Ga2O3 (mol%) SBG system, which yiel-ded moderate Cu and Ga ion release, excellent cytocompatibility and marked antibacterial efficacy. (c) 2021 The Chinese Ceramic Society. Production and hosting by Elsevier B.V. This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).

Bi-phasic calcium phosphates (BCPs) are considered prominent candidate materials for the fabrication of bone graft substitutes. Currently, supplemental cation-doping is suggested as a powerful path to boost biofunctionality, however, there is still a lack of knowledge on the structural role of such substituents in BCPs, which in turn, could influence the intensity and extent of the biological effects. In this work, pure and Mg- and Sr-doped BCP scaffolds were fabricated by robocasting from hydrothermally synthesized powders, and then preliminarily tested in vitro and thoroughly investigated physically and chemically. Collectively, the osteoblast cell culture assays indicated that all types of BCP scaffolds (pure, Sr- or Sr-Mg-doped) delivered in vitro performances similar to the biological control, with emphasis on the Sr-Mg-doped ones. An important result was that double Mg-Sr doping obtained the ceramic with the highest beta-tricalcium phosphate (beta-TCP)/hydroxyapatite mass concentration ratio of similar to 1.8. Remarkably, Mg and Sr were found to be predominantly incorporated in the beta-TCP lattice. These findings could be important for the future development of BCP-based bone graft substitutes since the higher dissolution rate of beta-TCP enables an easier release of the therapeutic ions. This may pave the road toward medical devices with more predictable in vivo performance.

The surface physico-chemistry of metallic implants governs their successful long-term functionality for orthopedic and dentistry applications. Here, we investigated the feasibility of harmoniously combining two of the star materials currently employed in bone treatment/restoration, namely, calcium-phosphate-based bioceramics (in the form of coatings that have the capacity to enhance osseointegration) and titanium alloys (used as bulk implant materials due to their mechanical performance and lack of systemic toxicity). For the first time, bovine-bone-derived hydroxyapatite (BHA) was layered on top of Ti6Al4V substrates using powder injection laser cladding technology, and then subjected, in this first stage of the research, to an array of physical-chemical analyses. The laser processing set-up involved the conjoined modulation of the BHA-to-Ti ratio (100 wt.% and 50 wt.%) and beam power range (500-1000 W). As such, on each metallic substrate, several overlapped strips were produced and the external surface of the cladded coatings was further investigated. The morphological and compositional (SEM/EDS) evaluations exposed fully covered metallic surfaces with ceramic-based materials, without any fragmentation and with a strong metallurgical bond. The structural (XRD, micro-Raman) analyses showed the formation of calcium titanate as the main phase up to maximum 800 W, accompanied by partial BHA decomposition and the consequential advent of tetracalcium phosphate (markedly above 600 W), independent of the BHA ratio. In addition, the hydrophilic behavior of the coatings was outlined, being linked to the varied surface textures and phase dynamism that emerged due to laser power increment for both of the employed BHA ratios. Hence, this research delineates a series of optimal laser cladding technological parameters for the adequate deposition of bioceramic layers with customized functionality.

The use of resorbable magnesium alloys in the design of implants represents a new direction in the healthcare domain. Two main research avenues are currently explored for developing or improving metallic biomaterials: (i) increase of their corrosion resistance by designed compositional and structural modifications, and (ii) functionalization of their surfaces by coating with ceramic or polymeric layers. The main objective of this work was to comparatively assess bio-functional coatings (i.e., highly-crystallized hydroxyapatite and silica-rich glass) deposited by radio-frequency magnetron sputtering (RF-MS) on a biodegradable Mg-0.8Ca alloy (0.8 wt.% of Ca). After probing their morphology (by scanning electron microscopy) and structure (by Fourier transform infrared spectroscopy and grazing incidence X-ray diffraction), the corrosion resistance of the RF-MS coated Mg-0.8Ca substrates was electrochemically tested (in synthetic biological media with different degrees of biomimicry), and their cytocompatibility was assessed in osteoblast and fibroblast cell cultures. By collective assessment, the most promising performances, in terms of mass loss (similar to 7% after 12 days), hydrogen release rate (similar to 6 mL/cm(2) after 12 days), electrochemical corrosion parameters and cytocompatibility, were obtained for the crystalline HA coating.

Pure Ti films deposited by radio-frequency magnetron sputtering on FTO glass were anodized to fabricate TiO2 nanotubes (NTs) arrays. The TiO2 NTs/FTO samples were sintered at 450, 550 and 630 degrees C, in ambient air. The thermal treatment did not influence the crystal phase composition, preserving in all cases the anatase single phase. As expected, the crystalline anatase quality improved with the annealing temperature. Nevertheless, slight differences in nanotubular morphology, such as the appearance of grains inside the walls, were observed in the case of the sample sintered at 630 degrees C. Chemical analysis by X-ray Photoelectron Spectroscopy of annealed samples revealed the presence of Sn inside TiO2 NTs, due to diffusion of Sn from the substrate to TiO2. For the substrate was used FTO glass whose top layer consists of SnO2 doped with F. Rutherford Backscattering Spectrometry and Time-of-Flight Elastic Recoil Detection Analysis were carried out to study the elemental depth profile of the films. It was found that the temperature of sintering controls the Sn diffusion inside TiO2 film. Sn atoms diffuse towards the TiO2 NTs surface for the samples annealed at 450 and 550 degrees C. The diffusion is however hindered in the case of the heat treatment at 630 degrees C. Besides, the Ti diffusion into the SnO2 underlayer was observed, together with the formation of TiO2/SnO2 interfaces. One then expected but not a great difference in absorption between samples, since all contained anatase phase, as confirmed by Diffuse Reflectance Spectroscopy. A higher amount of Sn was however detected for the sample annealed at 550 degrees C, which accounts for a slight red absorption shift. The importance of controlling the annealing parameters of the anodized TiO2/FTO structures was highlighted through the formation of TiO2-SnO2 interfaces and the Sn insertion from FTO, which can play an essential role in increasing the photoperformances of TiO2 NTs/FTO based structures of photovoltaic cells.

The structural role of V in 28Li(2)O-72SiO(2) (in mol%) lithium silicate glass doped with 0.5 mol% V2O5 was assessed using Si-29 and V-51 Nuclear Magnetic Resonance (NMR), Fourier-transform infrared (FTIR), and X-ray photoelectron (XPS) spectroscopy techniques. Despite the low amount of V2O5 used, the structural information obtained or deduced from the statistical analysis of the NMR data could explain the evolution of glass properties after V2O5 addition. The XPS results indicated that all vanadium exists in 5+ oxidation state. Both the Si-29 NMR and FTIR data point toward an increase in the polymerization of the silicate network, caused by the V2O5 acting as network former, capable to form various QVn tetrahedral units (for n = 0, 1, and 2) in the glasses. These QVn units, which are similar to phosphate units, scavenge the Li+ ions and cause the silicate network to polymerize. However, in an overall balance, the entire glass network is depolymerized due to the additional nonbridging oxygens contributed by the vanadium polyhedra. The addition of vanadium causes the network to expand and increases the ionic conductivity.

The commercially ubiquitous liquid electrolytes for lithium-ion batteries have several shortcomings in terms of safety. Therefore, development of solid electrolytes, especially those that are glass-based, has been gaining increasing interest in recent times. However, the fundamental understanding of the changes in the glass structure and the corresponding changes in the properties due to the addition of dopants is necessary for the development of glasses. Therefore, here, we report a study on the role of vanadium on the glass structure, ionic conduction, crystallization behavior, and other properties of lithium silicate-based glasses (23Li(2)O-2.64K(2)O-2.64Al(2)O(3)-71.72SiO(2)) as a solid electrolyte for high-temperature Li-ion battery applications. Furthermore, we proposed a mathematical model to describe/quantify the ion-conducting channels' connectivity in glasses. The experimental glass structures were assessed using Si-29, V-51, Al-27 nuclear magnetic resonance, Fourier transform infrared, and ultraviolet-visible spectroscopy techniques. The ionic conductivity was measured by impedance spectroscopy, and the crystallization behavior was studied by optical microscopy and X-ray diffraction. Furthermore, molecular dynamics simulations were also used to gain structural insights of the glasses. In the designed compositions, the addition of vanadium decreased the overall concentration of Li+ ions. However, the results revealed that the ionic conductivity improved with the addition of vanadium in spite of a decrease in the number of charge carriers. This suggests that vanadium makes the pathways easier for the conducting ions. Thus, we conclude that vanadium modifies the conduction channels to promote better hoping of the ions from one site to another.

The discovery of multifunctional properties related to electro-activity of organic systems of biomolecules is important for a variety of applications, especially for devices in the realm of biocompatible sensors and/or bioactuators. A further step towards such applications is to prepare thin films with the required properties. Here, the investigation is focused on the characterization of films of guanine and cytosine nucleobases, prepared by thermal evaporation-an industrial accessible deposition technique. The cytosine films have an orthorhombic non-centrosymmetric structure and grow in two interconnected nanostructured fractal patterns, of nearly equal proportion. Piezoresponse force microscopy images acquired at room temperature on the cytosine films display large zones with antiparallel alignment of the vertical components of the polarization vector. Guanine films have a dense nano-grained morphology. Our studies reveal electrical polarization switching effects which can be related to ferroelectricity in the films of guanine molecules. Characteristic ferroelectric polarization-electric-field hysteresis loops showing large electrical polarization are observed at low temperatures up to 200 K. Above this temperature, the guanine films have a preponderant paraelectric phase containing residual or locally induced nano-scopic ferroelectric domains, as observed by piezoresponse force microscopy at room temperature.

Thin AlN piezoelectric layers have been deposited on high resistivity Si and glass substrates by reactive RF magnetron sputtering, in order to manufacture one-port gigahertz operating surface acoustic wave (SAW)-type resonators to be used as temperature sensors. The growth morphology surface topography, crystallographic structure, and crystalline quality of the AlN layers have been analyzed. Advanced nanolithographic techniques have been used to manufacture structures having interdigitated transducers with fingers and finger interdigit spacing width in the range of 250-170 nm. High resonance frequency ensures the increase of the sensitivity, but also of its normalized value, the temperature coefficient of frequency (TCF). The resonance frequency shift versus temperature has been measured in the -267 degrees C-+150 degrees C temperature range, using a cryostat setup adapted for on wafer microwave measurements up to 50 GHz. The sensitivity and the TCF were determined in the 25 degrees C-150 degrees C temperature range.

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.

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.

A successful bone-graft-controlled healing entails the development of novel products with tunable compositional and architectural features and mechanical performances and is, thereby, able to accommodate fast bone in-growth and remodeling. To this effect, graphene nanoplatelets and Luffa-fibers were chosen as mechanical reinforcement phase and sacrificial template, respectively, and incorporated into a hydroxyapatite and brushite matrix derived by marble conversion with the help of a reproducible technology. The bio-products, framed by a one-stage-addition polymer-free fabrication route, were thoroughly physico-chemically investigated (by XRD, FTIR spectroscopy, SEM, and nano-computed tomography analysis, as well as surface energy measurements and mechanical performance assessments) after sintering in air or nitrogen ambient. The experiments exposed that the coupling of a nitrogen ambient with the graphene admixing triggers, in both compact and porous samples, important structural (i.e., decomposition of beta-Ca-3(PO4)(2) into alpha-Ca-3(PO4)(2) and alpha-Ca2P2O7) and morphological modifications. Certain restrictions and benefits were outlined with respect to the spatial porosity and global mechanical features of the derived bone scaffolds. Specifically, in nitrogen ambient, the graphene amount should be set to a maximum 0.25 wt.% in the case of compact products, while for the porous ones, significantly augmented compressive strengths were revealed at all graphene amounts. The sintering ambient or the graphene addition did not interfere with the Luffa ability to generate 3D-channels-arrays at high temperatures. It can be concluded that both Luffa and graphene agents act as adjuvants under nitrogen ambient, and that their incorporation-ratio can be modulated to favorably fit certain foreseeable biomedical applications.

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.

Cation-substituted hydroxyapatite (HA), standalone or as a composite (blended with polymers or metals), is currently regarded as a noteworthy candidate material for bone repair/regeneration either in the form of powders, porous scaffolds or coatings for endo-osseous dental and orthopaedic implants. As a response to the numerous contradictions reported in literature, this work presents, in one study, the physico-chemical properties and the cytocompatibility response of single cation-doped (Ce, Mg, Sr or Zn) HA nanopowders in a wide concentration range (0.5-5 at.%). The modification of composition, morphology, and structure was multiparametrically monitored via energy dispersive X-ray, X-ray photoelectron, Fourier-transform infrared and micro-Raman spectroscopy methods, as well as by transmission electron microscopy and X-ray diffraction. From a compositional point of view, Ce and Sr were well-incorporated in HA, while slight and pronounced deviations were observed for Mg and Zn, respectively. The change of the lattice parameters, crystallite size, and substituting cation occupation factors either in the Ca(I) or Ca(II) sites were further determined. Sr produced the most important HA structural changes. The in vitro biological performance was evaluated by the (i) determination of leached therapeutic cations (by inductively coupled plasma mass spectrometry) and (ii) assessment of cell behaviour by both conventional assays (e.g., proliferation-3-(4,5-dimethyl thiazol-2-yl) 5-(3-carboxymethoxyphenyl)-2-(4-sulfophenyl)-2H-tetrazolium assay; cytotoxicity-lactate dehydrogenase release assay) and, for the first time, real-time cell analysis (RTCA). Three cell lines were employed: fibroblast, osteoblast, and endothelial. When monophasic, the substituted HA supported the cells' viability and proliferation without signs of toxicity. The RTCA results indicate the excellent adherence of cells. The study strived to offer a perspective on the behaviour of Ce-, Mg-, Sr-, or Zn-substituted HAs and to deliver a well-encompassing viewpoint on their effects. This can be highly important for the future development of such bioceramics, paving the road toward the identification of candidates with highly promising therapeutic effects.

Glasses from lithium-aluminum-zinc-boron-phosphorous oxide system co-doped with terbium (Tb3+) and dysprosium (Dy3+) oxides were studied for magneto-optical applications in lasers. The Fourier Transform Infrared and Raman Spectroscopy complementary analysis suggested the depolymerization of the borophosphate glass network by adding and increasing the rare-earth (RE) oxide content. Main UV-vis absorption maxima of Tb and Dy ions were identified at 348 and 1266 nm. Spectroscopic ellipsometry indicated a maximum refractive index of 1.56, at 400 nm, for the highest RE content. The Verdet constant amplified by increasing the RE content, reaching for the 9 mol% RE co-doped sample a value of -0.075 min/Oe/cm at 630 nm. The Faraday rotation angle was additionally confirmed by using a Faraday Cell Device, being also related to the specific paramagnetic behavior evidenced by Superconducting Quantum Interference Device magnetometry. The magneto-optical properties recommend such vitreous co-doped materials for magneto-optical devices.

This Special Issue was devoted to developments made in Physical Vapour Deposited (PVD) biomedical coatings for various healthcare applications. The scrutinized PVD methods were Radio-Frequency Magnetron Sputtering (RF-MS), Cathodic Arc Evaporation, Pulsed Electron Deposition and its variants, Pulsed Laser Deposition, and Matrix Assisted Pulsed Laser Evaporation (MAPLE), due to their great promise especially in the dentistry and orthopaedics. These methods have yet to gain traction for industrialization and large-scale application in biomedicine. A new generation of implant coatings can be made available by the (1) incorporation of organic moieties (e.g., proteins, peptides, enzymes) into thin films by innovative methods such as combinatorial MAPLE, (2) direct coupling of therapeutic agents with bioactive glasses or ceramics within substituted or composite layers via RF-MS, or (3) by innovation in high energy deposition methods such as arc evaporation or pulsed electron beam methods.

Bovine hydroxyapatite (BHA) and BHA blended with clinoptilolite (CLIN) and alumina (Al2O3) coatings were synthesized using pulsed laser deposition (PLD) with a KrF* excimer laser source (lambda = 248 nm, tau(FWHM) <= 25 ns). Physical-chemical characteristics and the potential use of coatings for preventing bacteria adhesion and biofilm formation were investigated. Optimized PLD conditions were selected for coatings with rough morphologies, suitable for good cell adhesion and implant anchorage and good replication of the source target composition. The crystallinity of composite coatings was progressively decreasing with the augment of the Al2O3 and CLIN contents, which in turn can facilitate an efficacious release of active components. Al2O3- and CLIN-containing coatings exhibited high cytocompatibility and specific antibiofilm profiles, preventing the initiation and maturation of bacterial biofilms. Optimum biological activity profiles associated with the use of sustainable and/or inexpensive materials are, in our opinion, of key importance for the future development of performant implant coatings, which should he perfectly compatible with the surrounding tissue while preventing postsurgical endogenous or nosocomial infections.

Titanium diffusion in tungsten is an undesirable phenomenon that may cause the drop of mechanical and thermal fatigue properties of tungsten base material and components in future fusion reactors. To avoid such as problematic, the effectiveness of two different diffusion coatings, deposited onto W base materials by means of RF magnetron sputtering (Cr and V layers), has been studied to analyze its impact on the operative brazing aspects of the W-Eurofer joints. Coatings with two different thicknesses were deposited over tungsten base material prepared using different surface roughness (0.08 and 0.09 mu m). The results indicated that Ti diffusion into tungsten base material after the brazing process was suppressed in all cases while the consecution of full metallic continuity was reached. However, both Cr and V layers were dissolved during the brazing process due to the high solubility of both elements into beta-Ti. Mechanical properties of the joints dropped especially when Cr is used but a strength higher than 100 MPa was obtained in the case of using V layers.

The dextran-thyme magnesium-doped hydroxyapatite (10MgHAp-Dex-thyme) composite layers were prepared by a dip-coating procedure from stable suspensions and further analyzed for the first time. Different characterization techniques were employed to explore the physical-chemical features of the 10MgHAp-Dex-thyme suspensions and derived coatings. Information regarding the 10MgHAp-Dex-thyme suspensions was extracted on the basis of dynamic light scattering, zeta potential, and ultrasound measurements. The crystalline quality of the biocomposite powders-resulting after the centrifugation of suspensions-and the layers deposited on glass was assessed by X-ray diffraction in symmetric and grazing incidence geometries, respectively. The chemical structure and presence of functional groups were evaluated for both powder and coating by Fourier transform infrared spectroscopy in attenuated total reflectance mode. The extent of the antimicrobial effect range of the biocomposite suspensions and coatings was tested against different Gram-positive and Gram-negative bacteria (Staphylococcus aureus, Enterococcus faecalis, Escherichia coli, and Pseudomonas aeruginosa) and fungus (Candida albicans) strains with promising results.

We fabricated Sn-doped TiO2 nanotubular film via annealing of anodized TiO2 nanotubes grown on F-SnO2 (FTO) glass. Annealing was carried out at 500 degrees C in ambient air. Anatase crystal structure was achieved with no change in nanotubular morphology in respect to as-anodized amorphous TiO(2 )nanotubes. The X-ray photoelectron spectroscopy analysis revealed Sn on the surface of TiO2 film, following the thermal treatment, probably caused by the diffusion from FTO glass. Depth profile examination of the film chemical composition was conducted by elastic recoil detection analysis, which showed that in addition to the diffusion of Sn from FTO, diffusion of Ti to FTO concurrently occurred. Thus, a higher concentration of Sn was found at the bottom of the tubes, while a lower concentration was present on the tubes' surface top. This explains the improved optical response revealed by a diffuse reflectance spectroscopy. The absorption enhancement demonstrated that Sn-doped TiO2 film was efficient in the degradation of methyl orange dye under visible light.

Silica-based bioactive glasses (SBG) hold great promise as bio-functional coatings of metallic endo-osseous implants, due to their osteoproductive potential, and, in the case of designed formulations, suitable mechanical properties and antibacterial efficacy. In the framework of this study, the FastOs(R)BG alkali-free SBG system (mol%: SiO2-38.49, CaO-36.07, P2O5-5.61, MgO-19.24, CaF2-0.59), with CuO (2 mol%) and Ga2O3 (3 mol%) antimicrobial agents, partially substituting in the parent system CaO and MgO, respectively, was used as source material for the fabrication of intentionally silica-enriched implant-type thin coatings (similar to 600 nm) onto titanium (Ti) substrates by radio-frequency magnetron sputtering. The physico-chemical and mechanical characteristics, as well as the in vitro preliminary cytocompatibility and antibacterial performance of an alkali-free silica-rich bio-active glass coating designs was further explored. The films were smooth (R-RMS < 1 nm) and hydrophilic (water contact angle of similar to 65 degrees). The SBG coatings deposited from alkali-free copper-gallium co-doped FastOs(R)BG-derived exhibited improved wear performance, with the coatings eliciting a bonding strength value of similar to 53 MPa, Lc3 critical load value of similar to 4.9 N, hardness of similar to 6.1 GPa and an elastic modulus of similar to 127 GPa. The Cu and Ga co-doped SBG layers had excellent cytocompatibility, while reducing after 24 h the Staphylococcus aureus bacterial development with 4 orders of magnitude with respect to the control situations (i.e., nutritive broth and Ti substrate). Thereby, such SBG constructs could pave the road towards high-performance bio-functional coatings with excellent mechanical properties and enhanced biological features (e.g., by coupling cytocompatibility with antimicrobial properties), which are in great demand nowadays.

Aim of this research was to evaluate the effect of an improved processing thermal method of calcium phosphates obtained from a natural source of high availability (i.e. cyprinids bones). Thereby, the sinterability of the naturally-derived ceramics has been explored. The samples were characterized before and after sintering in terms of surface features (morphology, roughness, wettability and surface energy), weight loss, shrinking, composition, structure, and mechanical properties. The results showed that the initial processing has a significant effect on the sintering outcomes: the morphology and mechanical features were clearly influenced by the processing temperature, while minor effects were observed on the surface and structure properties. Therefore, the study unveils suitable strategies for controlling the characteristics of cost-effective bioceramics and opens up new perspectives for the sustainable manufacturing of highly valuable biomedical products from abundant carp fish bones.

We report on new biomaterials with promising bone and cartilage regeneration potential, from sustainable, cheap resources of fish origin. Thin films were fabricated from fish bone-derived bi-phasic calcium phosphate targets via pulsed laser deposition with a KrF * excimer laser source (lambda = 248 nm, tau(FWHM) <= 25 ns). Targets and deposited nanostructures were characterized by SEM and XRD, as well as by Energy Dispersive X-ray (EDX) and FTIR spectroscopy. Films were next assessed in vitro by dedicated cytocompatibility and antimicrobial assays. Films were Ca-deficient and contained a significant fraction of beta-tricalcium phosphate apart from hydroxyapatite, which could contribute to an increased solubility and an improved biocompatibility for bone regeneration applications. The deposited structures were biocompatible as confirmed by the lack of cytotoxicity on human gingival fibroblast cells, making them promising for fast osseointegration implants. Pulsed laser deposition (PLD) coatings inhibited the microbial adhesion and/or the subsequent biofilm development. A persistent protection against bacterial colonization (Escherichia coli) was demonstrated for at least 72 h, probably due to the release of the native trace elements (i.e., Na, Mg, Si, and/or S) from fish bones. Progress is therefore expected in the realm of multifunctional thin film biomaterials, combining antimicrobial, anti-inflammatory, and regenerative properties for advanced implant coatings and nosocomial infections prevention applications.

Powders of beta-tricalcium phosphate [beta-TCP, beta-Ca-3(PO4)(2)] and composite powders of beta-TCP and polyvinyl alcohol (PVA) were synthesized by using wet precipitation methods. First, the conditions for the preparation of single phase beta-TCP have been delineated. In the co-precipitation procedure, calcium nitrate and diammonium hydrogen phosphate were used as calcium and phosphorous precursors, respectively. The pH of the system was varied in the range 7-11 by adding designed amounts of ammonia solution. The filtered cakes were desiccated at 80 degrees C and subsequently calcined at different temperatures in the range between 700-1100 degrees C. Later on, rifampicin form II was used to produce drug-loaded beta-TCP and PVA/beta-TCP powders. All the synthesized materials have been characterized from morphological (by scanning electron microscopy) and structural-chemical (by X-ray diffraction and Fourier transform infrared spectroscopy) point of view. The drug loading capacity of the selected pure beta-TCP powder has been assessed. The biological performance (cytocompatibility in fibroblast cell culture and antibacterial efficacy against Escherichia coli and Staphylococcus aureus) has been tested with promising results. Application perspectives of the designed drug-bioceramic-polymer blends are advanced and discussed. [GRAPHICS] .

In this study, the results about the influence of the surface morphology of layers based on montmorillonite (MMT) and silver (Ag) on antimicrobial properties are reported. The coating depositions were performed in the plasma of a radio frequency (RF) magnetron sputtering discharge. The studied layers were single montmorillonite layers (MMT) and silver/montmorillonite multilayers (MMT-Ag) obtained by magnetron sputtering technique with a different surface thickness. The resultant MMT-Ag biocomposite multilayers exhibited a uniform distribution of constituent elements and enhanced antimicrobial properties against fungal biofilm development. Glow-discharge optical emission spectroscopy (GDOES) analysis revealed the formation of MMT-Ag biocomposite multilayers following the deposit of a silver layer for an MMT layer that was initially deposited on a Si substrate. The surface morphology and thickness evaluation of deposited biocomposite layers were performed by scanning electron microscopy (SEM). A qualitative analysis of the chemical composition of thin layers was performed and the elements O, Ag, Mg, Fe, Al, and Si were identified in the MMT-Ag biocomposite multilayers. The in vitro antifungal assay proved that the inhibitory effect against the growth of Candida albicans ATCC 101231 CFU was more emphasized in the case of MMT-Ag biocomposite multilayers that in the case of the MMT layer. Cytotoxicity studies performed on HeLa cells showed that the tested layers did not show significant toxicity at the time intervals during which the assay was performed. On the other hand, it was observed that the MMT layers exhibited slightly higher biocompatible properties than the MMT-Ag composite layers.

The present work describes a new simple procedure for the direct immobilization of biomolecules on Ni electrodes using magnetic Ni nanoparticles (NiNPs) as biomolecule carriers. Ni electrodes were fabricated by electroplating, and NiNPs were chemically synthesized. The chemical composition, crystallinity, and granular size of Ni electrodes, NiNP, and NiNP-modified Ni electrodes (NiNP/Ni) were determined by X-ray diffraction, scanning electron microscopy, and X-ray photoelectron spectroscopy (XPS). The electrochemical characterization of Ni electrodes by cyclic voltammetry and electrochemical impedance spectroscopy confirmed the existence of nickel oxides, hydroxides, and oxohydroxide films at the surface of Ni. Magnetic characterization and micromagnetic simulations were performed in order to prove that the magnetic force is responsible for the immobilization process. Further, Ni electrodes were employed as amperometric sensors for the detection of hydrogen peroxide because it is an important performance indicator for a material to be applied in biosensing. The working principle for magnetic immobilization of the enzyme-functionalized NiNP, without the use of external magnetic sources, was demonstrated for glucose oxidase (GOx) as a model enzyme. XPS results enabled to identify the presence of GOx attached to the NiNP (GOx-NiNP) on Ni electrodes. Finally, glucose detection and quantification were evaluated with the newly developed GOx-NiNP/Ni biosensor by amperometry at different potentials, and control experiments at different electrode materials in the presence and absence of NiNP demonstrated their importance in the biosensor architecture.

A series of seven alkali-free silica-based bioactive glasses (SBG) with ZnO and/or SrO additives (in concentrations of 0-12 mol%) were synthesized by melt-quenching, aiming to delineate a candidate formulation possessing (i) a coefficient of thermal expansion (CTE) similar to the one of titanium (Ti) and its medical grade super alloys (crucial for the future development of mechanically adherent implant-type SBG coatings) and (ii) antibacterial efficiency, while (iii) conserving a good cytocompatibility. The SBGs powders were multi-parametrically evaluated by X-ray diffraction, Fourier transform infrared and micro-Raman spectroscopy, dilatometry, inductively coupled plasma mass spectrometry, antibacterial (against Staphylococcus aureus and Escherichia coli strains) suspension inhibition and agar diffusion tests, and human mesenchymal stem cells cytocompatibility assays. The results showed that the coupled incorporation of zinc and strontium ions into the parent glass composition has a combinatorial and additive benefit. In particular, the "Z6S4" formulation (mol%: SiO2-38.49, CaO-32.07, P2O5-5.61, MgO-13.24, CaF2-0.59, ZnO-6.0, SrO-4.0) conferred strong antimicrobial activity against both types of strains, minimal cytotoxicity combined with good stem cells viability and proliferation, and a CTE (similar to 8.7 x 10(-6) x degrees C-1) matching well those of the Ti-based implant materials.

Ti6Al4V cranial prostheses in the form of patterned meshes were 3D printed by selective laser melting in an argon environment; using a CO2 laser source and micron-sized Ti6Al4V powder as the starting material. The size and shape of prostheses were chosen based on actual computer tomography images of patient skull fractures supplied in the framework of a collaboration with a neurosurgery clinic. After optimizations of scanning speed and laser parameters, the printed material was defect-free (as shown by metallographic analyses) and chemically homogeneous, without elemental segregation or depletion. The prostheses were coated by radio-frequency magnetron sputtering (RF-MS) with a bioactive thin layer of hydroxyapatite using a bioceramic powder derived from biogenic resources (Bio-HA). Initially amorphous, the films were converted to fully-crystalline form by applying a post-deposition thermal-treatment at 500 degrees C/1 h in air. The X-ray diffraction structural investigations indicated the phase purity of the deposited films composed solely of a hexagonal hydroxyapatite-like compound. On the other hand, the Fourier transform infrared spectroscopic investigations revealed that the biological carbonatation of the bone mineral phase was well-replicated in the case of crystallized Bio-HA RF-MS implant coatings. The in vitro acellular assays, performed in both the fully inorganic Kokubo's simulated body fluid and the biomimetic organic-inorganic McCoy's 5A cell culture medium up to 21 days, emphasized both the good resistance to degradation and the biomineralization capacity of the films. Further in vitro tests conducted in SaOs-2 osteoblast-like cells showed a positive proliferation rate on the Bio-HA RF-MS coating along with a good adhesion developed on the biomaterial surface by elongated membrane protrusions.

We report on the influence of dilute doping combined with the processing conditions on the morphological, structural, chemical states, photoluminescence and magnetic properties of Zn1-xNixO nanopowders. Ni doping changes the ZnO powder morphology from randomly-aggregated nanocrystals to densely-packed nanocrystals arranged in columnar particles, modifies the high-energy-component of O1 s spectrum and increases the modified Auger parameter in XPS, enhances the blue photoluminescence (PL) emission, suppresses the green PL emission and the intensity of the g = 1.997 EPR signal. Ni-ZnO nanostructures show room-temperature ferro-magnetism (implying they can serve as dilute magnetic semiconductors). The saturation magnetization, crystallite size and microstrain increase with the doping level; the c-axis constant and unit cell volume decrease, however, being unexpectedly higher with respect to a (reference) ZnO powder with a relaxed lattice. We demonstrate that the investigated properties were controlled by both (dilute) doping level and donor native defects produced by non-equilibrium (oxygen-deficiency and high rate of) ZnO formation.

The bone remodeling research field has shifted focus towards sustainable, eco-friendly and reproducible manufacturing technologies of 3D structures. It is now accepted that a suitable internal architecture and an active interface between the 3D structure and host bone-tissue constitute the two most critical traits for a successful bone tissue engineering application. A completely reproducible synthesis set-up was recently developed for calcium phosphate (CaP) bioceramics preparation from natural highly available marble and seashells. The influence of the pressing force in the fabrication process of porous 3D scaffolds derived from such CaPs by a sacrificial porogen method using natural fibers is here investigated. The fiber-ceramic based-products underwent thermal processing, followed by surface and volume features characterization. After fibers' thermal removal, interconnected 3D channels were obtained, which could allow a suitable in vivo irrigation and implant-associated negative side-effects prevention. This method provides the prospect of tunable HA/beta-TCP content in the case of both precursors' derived-scaffolds. The morphological results revealed the internal and external pores dimensions, modulated through different pressing forces that led to a controlled total porosity, evidenced by computed tomography techniques. Further, the wettability and mechanical features supported the advance of the novel porous-ceramic-structure designs as reliable bone reconstruction alternatives.

Laser melting deposition is a 3D printing method usually studied for the manufacturing of machine parts in the industry. However, for the medical sector, although feasible, applications and actual products taking advantage of this technique are only scarcely reported. Therefore, in this study, Ti6Al4V orthopedic implants in the form of plates were 3D printed by laser melting deposition. Tuning of the laser power, scanning speed and powder feed rate was conducted, in order to obtain a continuous deposition after a single laser pass and to diminish unwanted blown powder, stuck in the vicinity of the printed elements. The fabrication of bone plates is presented in detail, putting emphasis on the scanning direction, which had a decisive role in the 3D printing resolution. The printed material was investigated by optical microscopy and was found to be dense, with no visible pores or cracks. The metallographic investigations and X-ray diffraction data exposed an unusual biphasic alpha+beta structure. The energy dispersive X-ray spectroscopy revealed a composition very similar to the one of the starting powder material. The mapping of the surface showed a uniform distribution of elements, with no segregations or areas with deficient elemental distribution. The in vitro tests performed on the 3D printed Ti6Al4V samples in osteoblast-like cell cultures up to 7 days showed that the material deposited by laser melting is cytocompatible.

Recently, a large spectrum of biomaterials emerged, with emphasis on various pure, blended, or doped calcium phosphates (CaPs). Although basic cytocompatibility testing protocols are referred by International Organization for Standardization (ISO) 10993 (parts 1-22), rigorous in vitro testing using cutting-edge technologies should be carried out in order to fully understand the behavior of various biomaterials (whether in bulk or low-dimensional object form) and to better gauge their outcome when implanted. In this review, current molecular techniques are assessed for the in-depth characterization of angiogenic potential, osteogenic capability, and the modulation of oxidative stress and inflammation properties of CaPs and their cation- and/or anion-substituted derivatives. Using such techniques, mechanisms of action of these compounds can be deciphered, highlighting the signaling pathway activation, cross-talk, and modulation by microRNA expression, which in turn can safely pave the road toward a better filtering of the truly functional, application-ready innovative therapeutic bioceramic-based solutions.

Calcium carbonate from marble and seashells is an eco-friendly, sustainable, and largely available bioresource for producing natural bone-like calcium phosphates (CaPs). Based on three main objectives, this research targeted the: (i) adaptation of an indirect synthesis route by modulating the amount of phosphorus used in the chemical reaction, (ii) comprehensive structural, morphological, and surface characterization, and (iii) biocompatibility assessment of the synthesized powdered samples. The morphological characterization was performed on digitally processed scanning electron microscopy (SEM) images. The complementary 3D image augmentation of SEM results also allowed the quantification of roughness parameters. The results revealed that both morphology and roughness were modulated through the induced variation of the synthesis parameters. Structural investigation of the samples was performed by Fourier transform infrared spectroscopy and X-ray diffraction. Depending on the phosphorus amount from the chemical reaction, the structural studies revealed the formation of biphasic CaPs based on hydroxyapatite/brushite or brushite/monetite. The in vitro assessment of the powdered samples demonstrated their capacity to support MC3T3-E1 pre-osteoblast viability and proliferation at comparable levels to the negative cytotoxicity control and the reference material (commercial hydroxyapatite). Therefore, these samples hold great promise for biomedical applications.

Ferroelectric field effect transistors (FeFETs) based on lead zirconate titanate (PZT) ferroelectric material and amorphous-indium-gallium-zinc oxide (a-IGZO) were developed and characterized. The PZT material was processed by a sol-gel method and then used as ferroelectric gate. The a-IGZO thin films, having the role of channel semiconductor, were deposited by radio-frequency magnetron sputtering, at a temperature of similar to 50 degrees C. Characteristics of a typical field effect transistor with SiO2 gate insulator, grown on highly doped silicon, and of the PZT-based FeFET were compared. It was proven that the FeFETs had promising performances in terms of I-on/I-off ratio (i.e., 10(6)) and IDS retention behavior.

Obtaining nanoscale materials has allowed for the miniaturization of components, which has led to the possibility of achieving more efficient devices with faster functions and much lower costs. While hydroxyapatite [HAp, Ca-10(PO4)(6)(OH)(2)] is considered the most widely used material for medical applications in orthopedics, dentistry, and general surgery, the magnesium (Mg) is viewed as a promising biodegradable and biocompatible implant material. Furthermore, Mg is regarded as a strong candidate for developing medical implants due to its biocompatibility and antimicrobial properties against gram-positive and gram-negative bacteria. For this study, magnesium-doped hydroxyapatite (Ca10-xMgx (PO4)(6) (OH)(2), x(Mg) = 0.1), 10MgHAp, suspensions were successfully obtained by an adapted and simple chemical co-precipitation method. The information regarding the stability of the nanosized 10MgHAp particles suspension obtained by zeta-potential analysis were confirmed for the first time by a non-destructive ultrasound-based technique. Structural and morphological studies of synthesized 10MgHAp were conducted by X-ray diffraction (XRD), Fourier-transform infrared (FTIR) spectroscopy in attenuated total reflectance (ATR) mode and scanning electron microscopy (SEM). The XRD analysis of the 10MgHAp samples confirmed that a single crystalline phase associated to HAp with an average grain size about 93.3 nm was obtained. The FTIR-ATR spectra revealed that the 10MgHAp sample presented broader IR bands with less visible peaks when compared to a well-crystallized pure HAp. The SEM results evidenced uniform MgHAp nanoparticles with spherical shape. The antimicrobial activity of the 10MgHAp suspension against gram-positive strains (Staphylococcus aureus ATCC 25923, Enterococcus faecalis ATCC 29212), gram-negative strains (Escherichia coli ATCC 25922, Pseudomonas aeruginosa ATCC 27853), as well as a fungal strain (Candida albicans ATCC 90029) were evaluated.

We report on the fabrication of dye-sensitized solar cells with a TiO2 buffer layer between the transparent conductive oxide substrate and the mesoporous TiO2 film, in order to improve the photovoltaic conversion efficiency of the device. The buffer layer was fabricated by pulsed laser deposition whereas the mesoporous film by the doctor blade method, using TiO2 paste obtained by the sol-gel technique. The buffer layer was deposited in either oxygen (10 Pa and 50 Pa) or argon (10 Pa and 50 Pa) onto transparent conducting oxide glass kept at room temperature. The cross-section scanning electron microscopy image showed differences in layer morphology and thickness, depending on the deposition conditions. Transmission electron microscopy studies of the TiO2 buffer layers indicated that films consisted of grains with typical diameters of 10 nm to 30 nm. We found that the photovoltaic conversion efficiencies, determined under standard air mass 1.5 global (AM 1.5G) conditions, of the solar cells with a buffer layer are more than two times larger than those of the standard cells. The best performance was reached for buffer layers deposited at 10 Pa O-2. We discuss the processes that take place in the device and emphasize the role of the brush-like buffer layer in the performance increase.

The bone regeneration field targeted lately the development of new products based on precursors of natural origin. This study aimed to obtain the optimal design of polymer-ceramic composites for guided bone regeneration application from cellulose acetate (CA) and hydroxyapatite (HA) by varying three relevant parameters: the amount of HA powder added to the CA matrix (in the 20-40 wt% range), the HA particles size (max. 20 mu m vs. max. 40 mu m) and the homogenization time required for HA powder dispersion in the CA matrix (1 min vs. 4 min). For polymer-ceramic film structures preparation, the phase inversion by immersion in water method was used. This involved the deposition of composite solution (i.e. CA with 20-40 wt% HA) on a glass support, followed by sizing it at a thickness of 0.2 mm. The obtained film structures were investigated in terms of morphocompositional and structural properties. The surface features evaluation was achieved by surface wettability, roughness, water permeation, protein retention and in vitro evaluation of MC3T3-E1 morphology and viability. Further, ceramic particle distribution throughout samples volume was provided by computed tomography methods. These investigations targeted the validation of the prepared composite film structures as viable solutions for guided bone regeneration.

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.

The discovery of bioactive glasses (BGs) in the late 1960s by Larry Hench et al. was driven by the need for implant materials with an ability to bond to living tissues, which were intended to replace inert metal and plastic implants that were not well tolerated by the body. Among a number of tested compositions, the one that later became designated by the well-known trademark of 45S5 Bioglass (R) excelled in its ability to bond to bone and soft tissues. Bonding to living tissues was mediated through the formation of an interfacial bone-like hydroxyapatite layer when the bioglass was put in contact with biological fluids in vivo. This feature represented a remarkable milestone, and has inspired many other investigations aiming at further exploring the in vitro and in vivo performances of this and other related BG compositions. This paradigmatic example of a target-oriented research is certainly one of the most valuable contributions that one can learn from Larry Hench. Such a goal-oriented approach needs to be continuously stimulated, aiming at finding out better performing materials to overcome the limitations of the existing ones, including the 45S5 Bioglass (R). Its well-known that its main limitations include: (i) the high pH environment that is created by its high sodium content could turn it cytotoxic; (ii) and the poor sintering ability makes the fabrication of porous three-dimensional (3D) scaffolds difficult. All of these relevant features strongly depend on a number of interrelated factors that need to be well compromised. The selected chemical composition strongly determines the glass structure, the biocompatibility, the degradation rate, and the ease of processing (scaffolds fabrication and sintering). This manuscript presents a first general appraisal of the scientific output in the interrelated areas of bioactive glasses and glass-ceramics, scaffolds, implant coatings, and tissue engineering. Then, it gives an overview of the critical issues that need to be considered when developing bioactive glasses for healthcare applications. The aim is to provide knowledge-based tools towards guiding young researchers in the design of new bioactive glass compositions, taking into account the desired functional properties.

High-performance bioceramics are required for preventing failure and prolonging the life-time of bone grafting scaffolds and osseous implants. The proper identification and development of materials with extended functionalities addressing socio-economic needs and health problems constitute important and critical steps at the heart of clinical research. Recent findings in the realm of ion-substituted hydroxyapatite (HA) could pave the road towards significant developments in biomedicine, with an emphasis on a new generation of orthopaedic and dentistry applications, since such bioceramics are able to mimic the structural, compositional and mechanical properties of the bone mineral phase. In fact, the fascinating ability of the HA crystalline lattice to allow for the substitution of calcium ions with a plethora of cationic species has been widely explored in the recent period, with consequent modifications of its physical and chemical features, as well as its functional mechanical and in vitro and in vivo biological performance. A comprehensive inventory of the progresses achieved so far is both opportune and of paramount importance, in order to not only gather and summarize information, but to also allow fellow researchers to compare with ease and filter the best solutions for the cation substitution of HA-based materials and enable the development of multi-functional biomedical designs. The review surveys preparation and synthesis methods, pinpoints all the explored cation dopants, and discloses the full application range of substituted HA. Special attention is dedicated to the antimicrobial efficiency spectrum and cytotoxic trade-off concentration values for various cell lines, highlighting new prophylactic routes for the prevention of implant failure. Importantly, the current in vitro biological tests (widely employed to unveil the biological performance of HA-based materials), and their ability to mimic the in vivo biological interactions, are also critically assessed. Future perspectives are discussed, and a series of recommendations are underlined.

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.

The demand of calcium phosphate bioceramics for biomedical applications is constantly increasing. Efficient and cost-effective production can be achieved using naturally derived materials. In this work, calcium phosphate powders, obtained from dolomitic marble and Mytilus galloprovincialis seashells by a previously reported and improved Rathje method were used to fabricate microporous pellets through cold isostatic pressing followed by sintering at 1200 degrees C. The interaction of the developed materials with MC3T3-E1 pre-osteoblasts was explored in terms of cell adhesion, morphology, viability, proliferation, and differentiation to evaluate their potential for bone regeneration. Results showed appropriate cell adhesion and high viability without distinguishable differences in the morphological features. Likewise, the pre-osteoblast proliferation overtime on both naturally derived calcium phosphate materials showed a statistically significant increase comparable to that of commercial hydroxyapatite, used as reference material. Furthermore, evaluation of the intracellular alkaline phosphatase activity and collagen synthesis and deposition, used as markers of the osteogenic ability of these bioceramics, revealed that all samples promoted pre-osteoblast differentiation. However, a seashell-derived ceramic demonstrated a higher efficacy in inducing cell differentiation, almost equivalent to that of the commercial hydroxyapatite. Therefore, data obtained demonstrate that this naturally sourced calcium-phosphate material holds promise for applications in bone tissue regeneration.

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.

In the current work we present AlN/Si based Surface Acoustic Wave (SAW) devices exploited as high sensitivity temperature sensors. The experimental results show that the resonance frequency varies between 3.2 and 5.5 GHz, depending on the finger/Interdigit spacing width and metal thickness. The temperature measurements were performed between -250 degrees C and +150 degrees C in a cryostat. The sensitivities were investigated between 24-150 degrees C and the values were compared to the results obtained for similar GaN/Si based SAW structures.

Hydroxyapatite-starch composites solidify rapidly via jellification, making them suitable candidates for robocasting. However, many aspects related to hydroxyapatite powder characteristics, hydroxyapatite-starch interaction, and composites composition and properties need to be aligned with robocasting requirements to achieve a notable improvement in the functionality of printed scaffolds intended for bone regeneration. This article presents a preliminary evaluation of hydroxyapatite-starch microcomposites. Thermal analysis of the starting powders was performed for predicting composites' behavior during heat-induced densification. Also, morphology, mechanical properties, and hydroxyapatite-starch interaction were evaluated for the jellified composites and the porous bodies obtained after conventional sintering, for different starch additions, and for ceramic particle size distributions. The results indicate that starch could be used for hydroxyapatite consolidation in limited quantities, whereas the composites shall be processed under controlled temperature. Due to a different mechanical behavior induced by particle size and geometry, a wide particle size distribution of hydroxyapatite powder is recommended for further robocasting ink development.

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 the fabrication of silicon-reinforced carbon (C: Si) structures by combinatorial pulsed laser deposition to search for the best design for a new generation of multi-functional coated implants. The synthesized films were characterized from the morphological, structural, compositional, mechanical and microbiological points of view. Scanning electron microscopy revealed the presence, on top of the deposited layers, of spheroid particulates with sizes in the micron range. No microcracks or delaminations were observed. Energy dispersive x-ray spectroscopy and grazing incidence x-ray diffraction pointed to the existence of aC to Si compositional gradient from one end of the film to the other. Raman investigation revealed a relatively high sp(3) hybridization of up to 80% at 40-48 mm a part from the edge with higher Ccontent. Si addition was demonstrated to significantly increase C: Si film bonding to the substrate, with values above the ISO threshold for coatings to be used in high-loading biomedical applications. Surface energy studies pointed to an increase in the hydrophilic character of the deposited structures along with Si content up to 52 m Nm(-1'). In certain cases, the Si-reinforced Ccoatings elicited an antimicrobial biofilm action. The presence of Si was proven to be benign to HEp-2 cells of human origin, without interfering with their cellular cycle. On this basis, reliable C: Si structures with good adherence to the substrate and high efficiency against microbial biofilms can be developed for implant coatings and other advanced medical devices.

Synthetic physiological fluids are currently used as a first in vitro bioactivity assessment for bone grafts. Our understanding about the interactions taking place at the fluid-implant interface has evolved remarkably during the last decade, and does not comply with the traditional International Organization for Standardization/final draft International Standard 23317 protocol in purely inorganic simulated body fluid. The advances in our knowledge point to the need of a true paradigm shift toward testing physiological fluids with enhanced biomimicry and a better understanding of the materials' structure-dissolution behavior. This will contribute to "upgrade" our vision of entire cascades of events taking place at the implant surfaces upon immersion in the testing media or after implantation. Starting from an osteoinductive bioglass composition with the ability to alleviate the oxidative stress, thin bioglass films with different degrees of polymerization were deposited onto titanium substrates. Their biomineralization activity in simulated body fluid and in a series of new inorganic-organic media with increasing biomimicry that more closely simulated the human intercellular environment was compared. A comprehensive range of advanced characterization tools (scanning electron microscopy; grazing-incidence X-ray diffraction; Fourier-transform infrared, micro-Raman, energy-dispersive, X-ray photoelectron, and surface-enhanced laser desorption/ionization time-of-flight mass spectroscopies; and cytocompatibility assays using mesenchymal stem cells) were used. The information gathered is very useful to biologists, biophysicists, clinicians, and material scientists with special interest in teaching and research. By combining all the analyses, we propose herein a step forward toward establishing an improved unified protocol for testing the bioactivity of implant materials.

The new opportunities introduced by the large development of the IoT (internet of things) are increasing the demand for sensors to be located as close as possible to the supervised process. The Aluminum Nitride (AIN) is one of the most promising materials for sensors due to its piezoelectric, excellent mechanical properties, chemical inertness and high melting point. Due to these material properties, the AlN sensors are suitable to operate in high temperature and harsh environment conditions and therefore are very promising to be employed in industrial applications. In this article are presented the studies conducted on several Aluminum Nitride-Coated Steel structures with the goal of producing sensors embedded in the ball bearings, bearings and other mobile parts of machine tools. The experiments were conducted on simple coatings structures without lubricating materials and the obtained results are promising, demonstrating that, with some limitations the AIN could be used in such applications.

Hydroxyapatite is a calcium phosphate intensively proposed as a bone substitution material because of its resemblance to the constituents of minerals present in natural bone. Since hydroxyapatite's properties are mainly adequate for nonload bearing applications, different solutions are being tested for improving these properties and upgrading them near the target values of natural bone. On the other hand, starch (a natural and biodegradable polymer) and its blends with other polymers have been proposed as constituents in hydroxyapatite mixtures due to the adhesive, gelling, and swelling abilities of starch particles, useful in preparing well dispersed suspensions and consolidated ceramic bodies. This article presents the perspectives of incorporating starch and starch blends in hydroxyapatite materials. Based on the role of starch within the materials, the review covers its use as (i) a polymeric matrix in hydroxyapatite composites used as adhesives, bone cements, bone waxes, drug-delivery devices or scaffolds and (ii) a sacrificial binder for fabrication of porous hydroxyapatite scaffolds. The suitability of these materials for bone reconstruction has becomes a reachable aim considering the recent advancements in ceramic fabrication and the current possibilities of controlling the processing parameters.

Aluminum Nitride (AlN) thin films were synthesized on Si (100) wafers at 450 degrees C by pulsed laser deposition. A polycrystalline AlN target was multipulsed irradiated in a nitrogen ambient, at different laser pulse repetition rate. Grazing Incidence X-Ray Diffraction and Atomic Force Microscopy analyses evidenced nanocrystallites with a hexagonal lattice in the amorphous AlN matrix. The thickness and optical constants of the layers were determined by infrared spectroscopic ellipsometry. The optical properties were studied by Fourier Transform Infrared reflectance spectroscopy in polarised oblique incidence radiation. Berreman effect was observed around the longitudinal phonon modes of the crystalline AlN component. Angular dependence of the A(1)LO mode frequency was analysed and connected to the orientation of the particles' optical axis to the substrate surface normal. The role of the laser pulse frequency on the layers' properties is discussed on this basis. (C) 2016 Elsevier B.V. All rights reserved.

Tungsten trioxide (WO3) thin films were grown by pulsed laser deposition (PLD) with the aim to be applied in gas sensors. The films were studied by atomic force microscopy (AFM), X-ray diffraction (XRD), Fourier transform infrared (FTIR) spectroscopy and profilometry. To study the gas sensing behavior of these WO3 films, they were deposited on quartz resonators and the quartz crystal microbalance (QCM) method was applied to analyze their gas sensitivity. Synthesis of tetragonal-WO3 films starting from a target with predominantly monoclinic WO3 phase was observed. The films deposited at 300 degrees C presented a surface topology favorable for the sorption properties, consisting of a film matrix with protruding craters/cavities. QCM prototype sensors with such films were tested for NO2 sensing. The PLD grown WO3 thin films show good sensitivity and fast reaction at room temperature, even in as-deposited state. With the presented technology, the manufacturing of QCM gas sensors is simple, fast and cost-effective, and it is also suitable for energy-effective portable equipment for on-line monitoring of environmental changes. (C) 2017 Elsevier B.V. All rights reserved.

Tungsten trioxide (WO3) is a widely studied material for electrochromic applications. The structure, morphology and optical properties of WO3 thin films, grown by matrix assisted pulsed laser evaporation (MAPLE) from monoclinic WO3 nano-sized particles, were investigated for their possible application as electrochromic layers. A KrF* excimer (lambda = 248 nm, .zeta(FWHM)=25 ns) laser source was used in all experiments. The MAPLE deposited WO3 thin films were studied by atomic force microscopy (AFM), grazing incidence X-ray diffraction (GIXRD) and Fourier transform infrared spectroscopy (FTIR). Cyclic voltammetry measurements were also performed, and the coloring and bleaching were observed. The morpho-structural investigations disclosed the synthesis of single-phase monoclinic WO3 films consisting of crystalline nano-grains embedded in an amorphous matrix. All thin films showed good electrochromic properties, thus validating application of the MAPLE deposition technique for the further development of electrochromic devices.

We report on the synthesis by Pulsed Laser Deposition of simple and Ti doped hydroxyapatite thin films of biological (ovine dentine) origin. Detailed physical, chemical, mechanical and biological investigations were performed. Morphological examination of films showed a surface composed of spheroidal particulates, of micronic size. Compositional analyses pointed to the presence of typical natural doping elements of bone, along with a slight non-stoichiometry of the deposited films. Structural investigations proved the monophasic hydroxyapatite nature of both simple and Ti doped films. Ti doping of biological hydroxyapatite induced an overall downgrade of the films crystallinity together with an increase of the films roughness. It is to be emphasized that bonding strength values measured at film. Ti substrate interface were superior to the minimum value imposed by International Standards regulating the load-bearing implant coatings. In vitro tests on Ti doped structures, compared to simple ones, revealed excellent biocompatibility in human mesenchymal stem cell cultures, a higher proliferation rate and a good cytocompatibility. The obtained results aim to elucidate the overall positive role of Ti doping on the hydroxyapatite films performance, and demonstrate the possibility to use this novel type of coatings as feasible materials for future implantology applications. (C) 2017 Elsevier B.V. All rights reserved.

Aluminum Nitride (AlN) has been long time being regarded as highly interesting material for developing sensing applications (including biosensors and implantable sensors). AlN, due to its appealing electronic properties, is envisaged lately to serve as a multi-functional biosensing platform. Although generally exploited for its intrinsic piezoelectricity, its surface morphology and mechanical performance (elastic modulus, hardness, wear, scratch and tensile resistance to delamination, adherence to the substrate), corrosion resistance and cytocompatibility are also essential features for high performance sustainable biosensor devices. However, information about AlN suitability for such applications is rather scarce or at best scattered and incomplete. Here, we aim to deliver a comprehensive evaluation of the morpho-structural, compositional, mechanical, electrochemical and biological properties of reactive radio-frequency magnetron sputtered AlN nanostructured thin films with various degrees of c-axis texturing, deposited at a low temperature (similar to 50 degrees C) on Si (100) substrates. The inter-conditionality elicited between the base pressure level attained in the reactor chamber and crystalline quality of AlN films is highlighted. The potential suitability of nanostructured AlN (in form of thin films) for the realization of various type of sensors (with emphasis on bio-sensors) is thoroughly probed, thus unveiling its advantages and limitations, as well as suggesting paths to safely exploit the remarkable prospects of this type of materials.

This work reports on the unprecedented magnetron sputtering deposition of submicrometric hollow cones of bioactive glass at low temperature in the absence of any template or catalyst. The influence of sputtering conditions on the formation and development of bioglass cones was studied. It was shown that larger populations of well-developed cones could be achieved by increasing the argon sputtering pressure. A mechanism describing the growth of bioglass hollow cones is presented, offering the links for process control and reproducibility of the cone features. The composition, structure, and morphology of the as-synthesized hollow cones were investigated by energy dispersive spectroscopy (EDS), Fourier transform infrared spectroscopy (FTIR), grazing incidence geometry X-ray diffraction (GIXRD), scanning electron microscopy (SEM), and transmission electron microscopy (TEM)-selected area electron diffraction (SAED). The in vitro biological performance, assessed by degradation tests (ISO 10993-14) and cytocompatibility assays (ISO 10993-5) in endothelial cell cultures, was excellent. This allied with resorbability and the unique morphological features make the submicrometer hollow cones interesting candidate material devices for focal transitory permeabilization of the blood brain barrier in the treatment of carcinoma and neurodegenerative disorders.

We report a study on the biocompatibility vs. thickness in the case of titanium nitride (TiN) films synthesized on 410 medical grade stainless steel substrates by pulsed laser deposition. The films were grown in a nitrogen atmosphere, and their in vitro cytotoxicity was assessed according to ISO 10993-5 [1]. Extensive physical-chemical analyses have been carried out on the deposited structures with various thicknesses in order to explain the differences in biological behavior: profilometry, scanning electron microscopy, atomic force microscopy, X-ray photoelectron spectroscopy (XPS), X-ray diffraction and surface energy measurements. XPS revealed the presence of titanium oxynitride beside TiN in amounts that vary with the film thickness. The cytocompatibility of films seems to be influenced by their TiN surface content. The thinner films seem to be more suitable for medical applications, due to the combined high values of bonding strength and superior cytocompatibility.

Background: We evaluated the Bovine hydroxyapatite (BHA) structure. BHA powder was admixed with 5 and 10 wt% natural pumice (NP). Compression strength, Vickers micro hardness, Fourier transform infrared spectroscopy, scanning electron microscopy (SEM) and X-ray diffraction studies were performed on the final NP-BHA composite products. The cells proliferation was investigated by MTT assay and SEM. Furthermore, the antimicrobial activity of NP-BHA samples was interrogated. Results: Variances in the sintering temperature (for 5 wt% NP composites) between 1000 and 1300 degrees C, reveal about 700 % increase in the microhardness (similar to 100 and 775 HV, respectively). Composites prepared at 1300 degrees C demonstrate the greatest compression strength with comparable result for 5 wt% NP content (87 MPa), which are significantly better than those for 10 wt% and those that do not include any NP (below 60 MPa, respectively). Conclusion: The results suggested the optimal parameters for the preparation of NP-BHA composites with increased mechanical properties and biocompatibility. Changes in micro-hardness and compression strength can be tailored by the tuning the NP concentration and sintering temperature. NP-BHA composites have demonstrated a remarkable potential for biomedical engineering applications such as bone graft and implant.

We report on the selection by combinatorial pulsed laser deposition of Silver-doped Carbon structures with reliable physical-chemical characteristics and high efficiency against microbial biofilms. The investigation of the films was performed by scanning electron microscopy, high resolution atomic force microscopy, energy dispersive X-Ray Spectroscopy, X-ray diffraction, Raman spectroscopy, bonding strength "pull-out" tests, and surface energy measurements. In vitro biological assays were carried out using a large spectrum of bacterial and fungal strains, i.e., Staphylococcus aureus, Staphylococcus epidermidis, Pseudomonas aeruginosa, Enterococcus faecalis and Candida albicans. The biocompatibility of the films obtained was evaluated on MG63 mammalian cell cultures. The optimal combination with reasonable physical-chemical properties, efficient protection against microbial colonization and beneficial effects on human cells was found for Silver-doped Carbon films containing 2 to 7 at.% silver. These mixtures can be used to fabricate safe and efficient coatings of metallic implants, with the goal to decrease the risk of implant associated biofilm infections which are difficult to treat and often responsible for implant failure. (C) 2016 Elsevier B.V. All rights reserved.

Bioactive materials play an increasingly important role in the biomaterials industry, and are extensively used in a range of applications, including biodegradable metallic implants. We report on Bioactive Glasses (BG) films deposition by pulsed laser techniques onto biodegradable substrates. The BG coatings were obtained using a KrF* excimer laser source (lambda= 248 nm, t(FWHM) <= 25 ns). Their thickness has been determined by Profilometry measurements, whilst their morphology has been analysed by Scanning Electron Microscopy (SEM). The obtained coatings fairly preserved the targets composition and structure, as revealed by Energy Dispersive X-Ray Spectroscopy, Grazing Incidence X-Ray Diffraction, and Fourier Transform Infra-Red Spectroscopy analyses.

Chitosan/biomimetic apatite thin films were grown in mild conditions of temperature and pressure by Combinatorial Matrix-Assisted Pulsed Laser Evaporation on Ti, Si or glass substrates. Compositional gradients were obtained by simultaneous laser vaporization of the two distinct material targets. A KrF* excimer (lambda = 248 nm, tau(FWHM) = 25 ns) laser source was used in all experiments. The nature and surface composition of deposited materials and the spatial distribution of constituents were studied by SEM, EDS, AFM, GIXRD, FTIR, micro-Raman, and XPS. The antimicrobial efficiency of the chitosan/biomimetic apatite layers against Staphylococcus aureus and Escherichia coli strains was interrogated by viable cell count assay. The obtained thin films were XRD amorphous and exhibited a morphology characteristic to the laser deposited structures composed of nanometric round shaped grains. The surface roughness has progressively increased with chitosan concentration. FTIR, EDS and XPS analyses indicated that the composition of the BmAp-CHT C-MAPLE composite films gradually modified from pure apatite to chitosan. The bioevaluation tests indicated that S. aureus biofilm is more susceptible to the action of chitosanrich areas of the films, whilst the E. coli biofilm proved more sensible to areas containing less chitosan. The best compromise should therefore go, in our opinion, to zones with intermediate-to-high chitosan concentration which can assure a large spectrum of antimicrobial protection concomitantly with a significant enhancement of osseointegration, favored by the presence of biomimetic hydroxyapatite. (C) 2016 Elsevier B.V. All rights reserved.

Aluminum Nitride (AlN) films were deposited at 450 degrees C in nitrogen ambient at a pressure of 0.1 Pa and at a laser incident fluence of similar to 3 J/cm(2) and pulse repetition rate of 40 Hz. Grazing Incidence X-ray Diffraction patterns evidenced the presence of nanocrystallites in the amorphous AlN matrix. In the FTIR spectra the characteristic Reststrahlen band of AlN crystal with a hexagonal lattice is observed but it is quite broadened (950-550 cm(-1)). The angular dependence of the reflectance spectra in p-polarised incidence radiation demonstrates the sensitivity of the A(1)LO phonon mode of the AlN nanocrystallites to their orientation toward the normal to the substrate surface. With decrease of the incidence beam angle the intensity of the A(1)LO phonon mode diminishes and softening of the resonance frequency occurs.

The aim of this study was to evaluate the adhesion of different bioceramic coatings deposited by radio frequency magnetron sputtering on the biodegradable implant-type magnesium-calcium (MgCa) alloys. Hydroxyapatite (HA) and bioactive glass (BG) were chosen as coating materials, due to their remarkable biological potential. The morphology, composition, structure and adhesion of the deposited thin coatings was characterized by scanning electron microscopy, atomic force microscopy, energy dispersive X-ray spectroscopy, grazing incidence X-ray diffraction, Fourier transform infrared spectroscopy and pull-out adherence measurements. A variation of the coating-to-substrate adhesion has been recorded and correlated with the physico-chemical results. The bonding strength values of the coatings were promising (being superior to the ISO13779-2:2008 fabrication standard for load-bearing biomedical coatings), and thus, encourage us to further proceed with the biological evaluation of the HA or BG coatings-MgCa substrate couples.

Hydroxyapatite (HA) is a consecrated biomaterial for bone reconstruction. In the form of thin films deposited by pulsed laser technologies, it can be used to cover metallic implants aiming to increase biocompatibility and osseointegration rate. HA of animal origin (bovine, BHA) reinforced with MgF2 (2 wt.%) or MgO (5 wt.%) were used for deposition of thin coatings with improved adherence, biocompatibility and antimicrobial activity. For pulsed laser deposition experiments, a KrF* (lambda = 248 nm, T-EWHM <= 25 ns) excimer laser source was used. The deposited structures were characterized from a physical-chemical point of view by X-Ray Diffraction, Fourier Transform Infra-Red Spectroscopy, Scanning Electron Microscopy in top- and cross-view modes, Energy Dispersive X-Ray Spectroscopy and Pull-out adherence tests. The microbiological assay using the HEp-2 cell line revealed that all target materials and deposited thin films are non-cytotoxic. We conducted tests on three strains isolated from patients with dental implants failure, i.e. Microccocus sp., Enterobacter sp. and Candida albi cans sp. The most significant anti-biofilm effect against Microcococcus sp. strain, at 72 h, was obtained in the presence of BHA:MgO thin films. For Enterobacter sp. strain a superior antimicrobial activity at 72 h was noticed, in respect with simple BHA or Ti control. The enhanced antimicrobial performances, correlated with good cytocompatibility and mechanical properties recommend these biomaterials as an alternative to synthetic HA for the fabrication of reliable implant coatings for dentistry and other applications. (C) 2015 Elsevier B.V. All rights reserved.

Bioactive composites of bovine derived hydroxyapatite and boron containing bioactive glass were doped with 5, 10 and 15 wt.% lanthanum oxide (La2O3). Results showed that at low sintering temperatures (800 degrees C) the doping oxide of La2O3 promoted transformation to crystalline phases. Formation of secondary phases, such as rhenanite, NaCaPO4, and calcium silicate, Ca2SiO4, were also found. La was found to act as modifier and influenced the viscosity. The increase of La2O3 content led to decrease of pore size. Porosity amount 48.1 %, at 15-240 mu m size range were reduced, to 34.4 %, with 5-80 mu m size range and particle sizes of 0.3-6 mu m to 0.09-2 mu m, respectively. In addition to that compression strength (MPa) and microhardness (HV) of the performed composite bioceramics were in the range of 25 - 110 MPa, and 121 - 364 HV, respectively. Our investigations suggested that the porosity type has a strong influence on the compressive strength and microhardness properties of the final bioceramic products.

We report on multi-stage pulsed laser deposition of aluminum nitride (AlN) on Si (100) wafers, at different temperatures. The first stage of deposition was carried out at 800 degrees C, the optimum temperature for AlN crystallization. In the second stage, the deposition was conducted at lower temperatures (room temperature, 350 degrees C or 450 degrees C), in ambient Nitrogen, at 0.1 Pa. The synthesized structures were analyzed by grazing incidence X-ray diffraction (GIXRD), transmission electron microscopy (TEM), atomic force microscopy and spectroscopic ellipsometry (SE). GIXRD measurements indicated that the two-stage deposited AlN samples exhibited a randomly oriented wurtzite structure with nanosized crystallites. The peaks were shifted to larger angles, indicative for smaller inter-planar distances. Remarkably, TEM images demonstrated that the high-temperature AlN "seed" layers (800 degrees C) promoted the growth of poly-crystalline AlN structures at lower deposition temperatures. When increasing the deposition temperature, the surface roughness of the samples exhibited values in the range of 0.4-2.3 nm. SE analyses showed structures which yield band gap values within the range of 4.0-5.7 eV. A correlation between the results of single and multi-stage AlN depositions was observed. (C) 2015 Elsevier B.V. All rights reserved.

The degradation of thin-film transistors (TFTs) caused by the self-heating effect constitutes a problem to be solved for the next generation of displays. Aluminum nitride (AlN) is a viable alternative for gate dielectric of TFTs due to its good thermal conductivity, matching coefficient of thermal expansion to indium-gallium-zinc-oxide, and excellent stability at high temperatures. Here, AlN thin films of different thicknesses were fabricated by a low temperature reactive radio-frequency magnetron sputtering process, using a low cost, metallic Al target. Their electrical properties have been thoroughly assessed. Furthermore, the 200 nm and 500 nm thick AlN layers have been integrated as gate-dielectric in transparent TFTs with indium-gallium-zinc-oxide as channel semiconductor. Our study emphasizes the potential of AlN thin films for transparent electronics, whilst the functionality of the fabricated field-effect transistors is explored and discussed. (C) 2016 Elsevier B.V. All rights reserved.

Restoration of damaged bone tissue involves two traditional approaches: tissue grafting and alloplastic replacement. Recently, their limitations led to the development of tissue engineering, which uses degradable porous supports named "scaffolds". These porous structures (used both for tissue engineering and classic bone substitution applications) with customizable designs may be constructed by solid freeform fabrication (SFF) techniques. SFF uses various synthetic materials and may be adapted for creating ceramic-based scaffolds, which became popular due to increased demands for bone substitution materials. Among these materials, naturally derived ceramics are suitable candidates for bone replacement due to their resemblance with the mineral bone. Innovative optimization routes for preparing naturally derived ceramics with modulated properties implies the management of key parameters involved in heat treatment of animal hard tissues: temperature, heating environment, and cooling conditions. Both powders and bulk pieces are evaluated with complementary techniques that focus on compositional, morphological, and structural features. Finally, qualitative and quantitative biological assay in relevant cell culture of the compacted powders may assist extensive testing programs for further evaluation of different ceramic scaffolds. All these results contribute to effective assessment of ceramics tuning strategies and to subsequent modulation of their enhanced properties and long-term functionality.

The chemical modification of the niobium (Nb) surface after irradiation with femtosecond laser pulses was investigated by scanning electron microscopy coupled with energy dispersive spectroscopy, atomic force microscopy, grazing incidence X-ray diffraction, and micro-Raman spectroscopy. The physical-chemical analyses indicated that the laser treatment results in oxidation of the Nb surface, as well as in the formation of Nb hydrides. Remarkably, after the samples' washing in ethanol, a strong Surface-Enhanced Raman Scattering (SERS) signal originating from the toluene residual traces was evidenced. Further, it was observed that the laser irradiated Nb surface is able to provide a SERS enhancement of similar to 1.3 x 10(3) times for rhodamine 6G solutions. Thus, for the first time it was shown that Nb/Nb oxide surfaces could exhibit SERS functionality, and so one can expect applications in biological/biochemical screening or for sensing of dangerous environmental substances. (C) 2015 AIP Publishing LLC.

Titanium films sputtered on FTO glass were used for obtaining highly oriented titania nanotubes via anodization technique. Then, pulsed laser deposition of CdS was carried out for sensitizing of similar to 60 nm wide titania nanotubes by applying 50, 100, 150 or 200 subsequent laser pulses. Scanning electron microscopy was used to indicate which samples had the open nanotubular structure of titania preserved after the deposition of CdS. Energy dispersive spectroscopy showed that a higher number of applied laser pulses results in the increase of Cd and S quantity within samples. Pulsed laser deposition technique was also employed for the fabrication of PbS counter electrode. I-V characteristics of the photovoltaic cells consisting the obtained electrodes were measured and compared under one-sun illumination. The photovoltaic cell with photoanode sensitized with CdS by applying 150 laser pulses showed the highest current density and voltage among the investigated cell.

We report on thin film deposition by matrix-assisted pulsed laser evaporation of simple hydroxyapatite (HA) or silver (Ag) doped HA combined with the natural biopolymer organosolv lignin (Lig) (Ag:HA-Lig). Solid cryogenic target of aqueous dispersions of Ag:HA-Lig composite and its counterpart without silver (HA-Lig) were prepared for evaporation using a KrF* excimer laser source. The expulsed material was assembled onto TiO2/Ti substrata or silicon wafers and subjected to physical-chemical investigations. Smooth, uniform films adherent to substratum were observed. The chemical analyses confirmed the presence of the HA components, but also evidenced traces of Ag and Lig. Deposited HA was Ca deficient, which is indicative of a film with increased solubility. Recorded X-ray Diffraction patterns were characteristic for amorphous films. Lig presence in thin films was undoubtedly proved by both X-ray Photoelectron and Fourier Transform Infra-Red Spectroscopy analyses. The microbiological evaluation showed that the newly assembled surfaces exhibited an inhibitory activity both on the initial steps of biofilm forming, and on mature bacterial and fungal biofilm development. The intensity of the antibiofilm activity was positively influenced by the presence of the Lig and/or Ag, in the case of Staphylococcus aureus, Pseudomonas aeruginosa and Candida famata biofilms. The obtained surfaces exhibited a low cytotoxicity toward human mesenchymal stem cells, being therefore promising candidates for fabricating implantable biomaterials with increased biocompatibility and resistance to microbial colonization and further biofilm development.

Electric and pyroelectric properties of AIN layers deposited on Si substrates with different resistivities were investigated. The dielectric constant was found to be around 12, while the conductance determined from dc current measurements was found to be in the 10(-9) to 10(-19) S range. The pyroelectric measurements were performed in voltage mode using two types of IR sources: a laser diode with 800 nm wavelength and a black body at 700 degrees C. A peculiar behavior was observed for the signal recorded when the laser diode was used as IR source. It was found that the Si substrate is introducing a signal component, due to the photogenerated carriers, which is adding to the pyroelectric signal generated by the AIN layer. This component is strongly dependent on the resistivity of the Si substrate. For strongly doped Si (Si++) the signal generated into the substrate represents only 10% of the recorded pyroelectric voltage. For electronic grade Si the signal generated into the substrate is about 100 times larger than the pyroelectric signal generated in the AIN layer. This effect can be used as an optical amplification of the pyroelectric signal. The frequency dependence observed for the pyroelectric signal recorded when the black body is used as IR source is typical for a pyroelectric detector. A value as large as 12.4 degrees C m(-2) K-1 was obtained for the pyroelectric coefficient using for estimation the constant signal at low modulation frequencies of the IR beam. However, the value of the pyroelectric coefficient is strongly affected by the electrical conductance of the AIN layer. As the conductance is frequency dependent it results that the value of the pyroelectric coefficient is frequency dependent, the value from above being valid only for very small frequencies of the temperature variation. It was also found that the electric and pyroelectric properties are dependent on the crystalline quality of the AIN layer. (C) 2015 Elsevier B.V. All rights reserved.

Bioactive glasses are currently considered the suitable candidates to stir the quest for a new generation of osseous implants with superior biological/functional performance. In congruence with this vision, this contribution aims to introduce a reliable technological recipe for coating fairly complex 3D-shaped implants (e.g. dental screws) with uniform and mechanical resistant bioactive glass films by the radio-frequency magnetron sputtering method. The mechanical reliability of the bioactive glass films applied to real Ti dental implant fixtures has been evaluated by a procedure comprised of "cold" implantation in pig mandibular bone from a dead animal, followed by immediate tension-free extraction tests. The effects of the complex mechanical strains occurring during implantation were analysed by scanning electron microscopy coupled with electron dispersive spectroscopy. Extensive biocompatibility assays (MTS, immunofluorescence, Western blot) revealed that the bioactive glass films stimulated strong cellular adhesion and proliferation of human dental pulp stem cells, without promoting their differentiation. The ability of the implant coatings to conserve a healthy stem cell pool is promising to further endorse the fabrication of new osseointegration implant designs with extended lifetime. (C) 2015 Elsevier Ltd. All rights reserved.

Hard carbon thin films were synthesized on Si (100) and quartz substrates by the Pulsed Laser Deposition (PLD) technique in vacuum or methane ambient to study their suitability for applications requiring high mechanical resistance. The deposited films' surface morphology was investigated by scanning electron microscopy, crystalline status by X-ray diffraction, packing and density by X-ray reflectivity, chemical bonding by Raman and X-ray photoelectron spectroscopy, adherence by pull-out measurements and mechanical properties by nanoindentation tests. Films synthesized in vacuum were a-C DLC type, while films synthesized in methane were categorized as a-C:H. The majority of PLD films consisted of two layers: one low density layer towards the surface and a higher density layer in contact with the substrate. The deposition gas pressure played a crucial role on films thickness, component layers thickness ratio, structure and mechanical properties. The films were smooth, amorphous and composed of a mixture of sp(3)-sp(2) carbon, with sp(3) content ranging between 50% and 90%. The thickness and density of the two constituent layers of a film directly determined its mechanical properties.

Thermo-ionic Vacuum Arc evaporation method was selected for the synthesis of Fe/Cu/Ni/Cu multilayer structures on Si (1 0 0) substrates. The aim of the study was the preparation and characterization of structures featuring a giant magnetoresistance effect. This was accomplished by inducing the formation of nanosized ferromagnetic crystallites in multilayer nonmagnetic solutions via atomic inter-diffusion processes by the tuning of deposition parameters. Layer-by-layer and inter-diffused type structures were prepared and comparatively analyzed by scanning electron microscopy, X-ray microanalysis, atomic force microscopy, X-ray diffraction and high-resolution transmission electron microscopy coupled with selected area electron diffraction. We presented the influence of the microstructure on electric and magnetic properties of the submicron-sized multilayers. The dependence of the electric resistance and the magnetoresistance on the composition, structure, morphology and roughness of the layers was established. We obtained an electric resistance value of 1.22 Omega for the layer-by-layer type structure, and 0.46 Omega for the inter-diffusion designed structure. Using the atomic inter-diffusion we succeeded in achieving an improvement of the magnetoresistive effect, from 0.1% to 2.3%. (C) 2015 Elsevier B.V. All rights reserved.

We report the deposition by Matrix Assisted Pulsed Laser Evaporation (MAPLE) technique of biomimetic nanocrystalline apatite coatings on titanium substrates, with potential application in tissue engineering. The targets were prepared from metastable, nanometric, poorly crystalline apatite powders, analogous to mineral bone, synthesized through a biomimetic approach by double decomposition process. For the deposition of thin films, a KrF* excimer laser source was used (lambda = 248 nm, tau(FWHM) <= 25 ns). The analyses revealed the existence, in synthesized powders, of labile non-apatitic mineral ions, associated with the formation of a hydrated layer at the surface of the nanocrystals. The thin film analyses showed that the structural and chemical nature of the nanocrystalline apatite was prevalently preserved. The perpetuation of the non-apatitic environments was also observed. The study indicated that MAPLE is a suitable technique for the congruent transfer of a delicate material, such as the biomimetic hydrated nanohydroxyapatite. (C) 2013 Elsevier B.V. All rights reserved.

Hydroxyapatite (HA) is a widely used biomaterial for implant thin films, largely recognized for its excellent capability to chemically bond to hard tissue inducing the osteogenesis without immune response from human tissues. Nowadays, intense research efforts are focused on development of antimicrobial HA doped thin films. In particular, HA doped with Ag (Ag:HA) is expected to inhibit the attachment of microbes and contamination of metallic implant surface. We herewith report on nano-sized HA and Ag:HA thin films synthesized by pulsed laser deposition on pure Ti and Ti modified with 100 nm diameter TiO2 nanotubes (fabricated by anodization of Ti plates) substrates. The HA-based thin films were characterized by SEM, AFM, EDS, FUR, and XRD. The cytotoxic activity was tested with HEp2 cells against controls. The antifungal efficiency of the deposited layers was tested against the Candida albicans and Aspergillus niger strains. The Ti substrates modified with TiO2 nanotubes covered with Ag:HA thin films showed the highest antifungal activity. (C) 2013 Elsevier B.V. All rights reserved.

Bioactive glasses are osteoproductive-type inorganic materials possessing the highest indices of bioactivity in both bulk and thin film forms. The prerequisites for reliable implant-type coatings are both their biological and mechanical performances. Whilst the bioglass films' structural, chemical and biological properties have been studied extensively, information about their mechanical performance is scarce. Here, transmission electron microscopy, energy dispersive X-ray spectroscopy, Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, nanoindentation and pull-out measurements were employed to assess the morphological, chemical, structural and mechanical properties of the bioglass films deposited onto Ti substrates by radio-frequency magnetron sputtering (RF-MS). The biological safety of the thin bioglass films was evaluated preliminarily in vitro by investigating the adherence, proliferation and cytotoxicity of fibroblast cells cultivated on their surface. Our study emphasize the versatility of RF-MS, showing how bioglass films' features such as composition, structure, bonding strength, hardness, elastic modulus and biological response can be conveniently adapted by tuning the RF-MS working conditions, and therefore demonstrating the unexplored potential of this deposition technique for preparing quality biomimetic glass coatings. (C) 2013 Elsevier B. V. All rights reserved.

In this paper, we report on the structural, optical, and electrical properties of a wide compositional range of AlxIn1-xN thin layers deposited on glass and polyethylene terephthalate substrates. AlxIn1-xN layers of controlled composition were obtained by a simple reactive magnetron co-sputtering protocol, using a single aluminium target with indium insets, by varying the Al/In target surface area ratio, and the composition of the deposition atmosphere. The relevant physical properties were investigated and discussed. It is shown that the texture of the thin films is dependent on the cation ratio, while the bowing parameters of lattice constants and band gap values are larger than those of epitaxial layers. (C) 2014 AIP Publishing LLC.

Magnetic and electrical properties of the nanostructured ZnO films are affected by the nonrandom distribution of impurities in the film due to segregation at grain boundaries (GBs) or extended defects. However, mapping the nature and distribution of the impurities in the film is not trivial. Here we demonstrate a simple, statistically relevant, and nondestructive procedure of quantitative determination of the paramagnetic impurities segregated at the GBs in nanostructured semiconducting and insulating films. From correlated electron paramagnetic resonance and transmission electron microscopy investigations, we determined the localization of trace amounts of Mn2+ ions, present as native impurities in a ZnO film deposited by magnetron sputtering at room temperature. In the as-deposited ZnO film, the Mn2+ ions were all localized in nanosized pockets of highly disordered ZnO dispersed between nanocrystalline columns. After the samples had been annealed in air at >400 degrees C, the size of the intercrystalline region decreased and the diffusion in GBs was activated, resulting in the localization of a portion of the Mn2+ ions in the peripheral atomic layers of the ZnO columns neighboring the GBs. The proportion of Mn2+ ions still localized at the GBs after annealing at 600 degrees C was 37%. The proposed method for the assessment of the presence and nature of impurities and the quantitative evaluation of their distribution in semiconducting and insulating nanostructures is expected to find direct applications in nanotechnology, in the synthesis and quality assurance of thin films for spintronics and opto- and nanoelectronics.

Bioglasses (BG) are the inorganic materials exhibiting the highest indices of bioactivity. Their appliance as films for bio-functionalization of metallic implant surfaces has been regarded as an optimal solution for surpassing their limited bulk mechanical properties. This study reports on magnetron sputtering of alkali-free BG thin films by varying the target-to-substrate working distance, which proved to play an important role in determining the films' properties. Post deposition heat-treatments at temperatures slightly above the glass transformation temperature were then applied to induce inter-diffusion processes at the BG/titanium substrate interface and strengthening the bonding as determined by pull-out adherence measurements. The morphological and structural features assessed by SEM-EDS, XRD, and FTIR revealed a good correlation between the formations of inter-metallic titanium silicide phases and the films' bonding strength. The highest mean value of pull-out adherence (60.3 +/- 4.6 MPa), which is adequate even for load-bearing biomedical applications, was recorded for films deposited at a working distance of 35 mm followed by a heat-treatment at 750 degrees C for 2 h in air. The experimental findings are explained on the basis of structural, compositional and thermodynamic considerations. (C) 2013 Elsevier B.V. All rights reserved.

Commercially pure titanium (CP-Ti) offers a good corrosion resistance and tissue tolerance. The interfacial phenomena between biomaterial and biological fluids depend especially on surface chemistry, energy, roughness and topography of the implant Different methods are used to modify CP-Ti surface in order to improve its bonding properties to bone tissue. Besides the mechanical approaches, chemical etching and chemical oxidation, there are also other procedures improving the biocornpatibility. One of the most important involves the deposition of a bioceramic thin layer on the metallic surface. A bioceramics frequently used is hydroxyapatite (HA), the mineral component of the bone. In this paper. the main objective was to study the effects of different surface pretreatments on adherence of hydroxyapatite layer obtained by electrochemical method. The CP-Ti substrate was used in different treated states of the surface. The applicability of the electrochemical technique is relieved by the fact that it is a very rapid method, requires relatively low temperatures, being also very versatile. The obtained coatings were studied by scanning electron microscopy (SEM) associated with EDX (Energy dispersive X-ray spectroscopy, X-ray diffraction method (XRD). The adherence of the layers was evaluated by the "pull-out" test. The quality of the coating (morphology and adhesion properties) is decisively influenced by the electrochemical parameters and also by the surface state.

Adhesion to substrate and antimicrobial efficiency of pulsed laser-deposited ZnO nanostructures were significantly increased by interposing a buffer nano-layer of hydrophobin. The hydrophobin interlayer increased by eight times the ZnO film resilience to wash in water, while in alkaline or acidic artificial sweat, it increased by 2 and 1.2 times, respectively, as compared to textiles covered with ZnO films only. Hydrophobin boosted the biocide effect of ZnO nanostructured films in case of Candida albicans and mold mix inoculum cultures by 50 and 30 %, respectively. An interpretation of these phenomena is advanced based upon the results of the structural investigations.

Reconstructive surgery of bone defects in the calvarium makes use of a multitude of biological and artificial materials. Due to the increased number of such medical casuistry in the recent years, a special attention was dedicated to the biocompatibility and osteointegrative properties of various types of biomaterials. Titanium emerged to be a promising cranioplasty material due to its excellent mechanical properties and biocompatibility. However, the way the host calvarial bone reacts to the titanium implant has not been fully understood. Here, we evaluate the influence of cranial bone substrate on the osteoconduction and osseointegration of titanium mesh implants. The pattern of bone tissue reaction in the areas of contact with metallic implant is analyzed by means of bone density measurements on the computer tomography images. Twenty-eight patients underwent cranioplasty with titanium mesh implants for bone cranial defects due to different aetiology. With the aid of visual analogue scales, the patients' status (osteointegration degree, comfort and cosmetics) was evaluated after 3 - 14 months since surgery (implantation).

This paper reports on the experimental realization and characterization of a wireless sensing system for machine-tool condition based monitoring. The system comprises a vibration sensor, an ARDUINO Leonardo development board and an RM 42 Blue tooth module. The sensing principle is based on a vibration sensor which includes a piezoelectric AlN layer deposited by sputtering on a flexible stainless steel foil. The functional testing of the sensor using a test stand for asynchronous engines equipped with frequency convertors is demonstrated.

We report on the synthesis of advanced nanostructured hydroxyapatite (HA) thin films onto 3D titanium (Ti) mesh substrates by Pulsed Laser Deposition method. Morphological and structural investigations as well as pull-out tests proved the stoichiometric transfer of crystalline HA films along with their good adherence. In vivo tests were performed on 12 patients (six with simple Ti mesh, six with Ti mesh biofunctionalized with HA). The tomodensitometry analysis of the cranial control scans evidenced the process of osseogenesis. For four patients with implanted HA/Ti mesh structures, the modification of the value obtained on Hounsfield scale was observed at the level of implant, proving the progress of osseointegration. We conclude that the structures exhibit excellent bonding strength and functionality, and are suitable for neurosurgical applications.

Radio-frequency Plasma Enhanced Chemical Vapour Deposition (in different methane dilutions) was used to synthesize adherent and haemocompatible diamond-like carbon (DLC) films on medical grade titanium substrates. The improvement of the adherence has been achieved by interposing a functional buffer layer with graded composition TixTiC1-x (x = 0-1) synthesized by magnetron co-sputtering. Bonding strength values of up to similar to 67 MPa have been measured by pull-out tests. Films with different sp(3)/sp(2) ratio have been obtained by changing the methane concentration in the deposition chamber. Raman spectroscopy, X-ray photoelectron spectroscopy and X-ray diffraction were employed for the physical-chemical characterization of the samples. The highest concentration of sp(3)-C (similar to 87 %), corresponding to a lower DLC surface energy (28.7 mJ/m(2) ), was deposited in a pure methane atmosphere. The biological response of the DLC films was assayed by a state-of-the-art biological analysis method (surface enhanced laser desorption/ionization-time of flight mass spectroscopy), in conjunction with other dedicated testing techniques: Western blot and partial thromboplastin time. The data support a cause-effect relationship between sp(3)-C content, surface energy and coagulation time, as well as between platelet-surface adherence properties and protein adsorption profiles.

We report on the synthesis of novel ovine and bovine derived hydroxyapatite thin films on titanium substrates by pulsed laser deposition for a new generation of implants. The calcination treatment applied to produce the hydroxyapatite powders from ovine/bovine bones was intended to induce crystallization and to prohibit the transmission of diseases. The deposited films were characterized by scanning electron microscopy, X-ray diffraction, Fourier transform infrared spectroscopy, and energy dispersive X-ray spectroscopy. Pull-off adherence and profilometry measurements were also carried out. X-ray diffraction ascertained the polycrystalline hydroxyapatite nature of the powders and films. Fourier transform infrared spectroscopy evidenced the vibrational bands characteristic to a hydroxyapatite material slightly carbonated. The micrographs of the films showed a uniform distribution of spheroidal particulates with a mean diameter of similar to 2 mu m. Pull-off measurements demonstrated excellent bonding strength values between the hydroxyapatite films and the titanium substrates. Because of their physical-chemical properties and low cost fabrication from renewable resources, we think that these new coating materials could be considered as a prospective competitor to synthetic hydroxyapatite used for implantology applications. (C) 2012 Elsevier B.V. All rights reserved.

A new HA/Y2O3:alpha Al2O3 system was obtained by the deposition of a hydroxyapatite thin layer (similar to 150 nm), by magnetron sputtering, onto sintered substrates of low yttria (150 ppm) doped alumina. The yttria doped alumina was synthesized from very pure nanopowders, by mechanical homogenization, followed of pressing, sintering and different annealing regimes, in order to obtain bodies with various degree of nano-micro-structuration. TEM/HRTEM, SEM and EDS morpho-compositional analysis techniques were used to characterize the yttria doped alumina substrate and the hydroxyapatite superficial layer. The interfacial bonding strength between the sintered substrate and the hydroxyapatite thin film was analyzed by SEM. The evolution of the grains growth of the Y2O3:alpha Al2O3 substrate samples, with and without the hydroxyapatite covering layer is observed and discussed. A strong structural interdependence between the covering layer and the sintered substrate was emphasized. The grains' growth behaviour of the studied samples showed a linear evolution. A mathematical model for the grain growth process description was built, the grain size being interpreted as a random variable having a log-normal or Weibull probability density function.

The article reports on the tilted growth of textured aluminium nitride thin films obtained by radio-frequency magnetron sputtering onto 50 mm diameter Si (111) wafers, in reactive atmosphere, in a planar sputtering system without tilting the substrate and with no additional sputtering geometry alterations. The films were investigated using, X-ray diffraction, spectroscopic ellipsometry and scanning electronic microscopy, done by local measurements on the wafer surface, at different distances from the centre. A progressive increase of the tilt angle when moving away from the sample centre has been found. The maximum tilt angle of the columnar AlN crystallites, obtained near the edges of the wafer, is about 7 degrees. The results showed also that tilting is associated with smaller thickness and larger dispersion of the c axis orientation. Synthesizing inclined c axis AlN films should allow the fabrication of surface acoustic wave devices based on shear waves for liquid sensor applications.

Transparent ZnO films are synthesized by RF-magnetron sputtering (1.78 MHz) onto glass substrates, using a mild-pressed ZnO powder target. The depositions were carried at three inert argon pressures (0.25 Pa, 0.30 Pa, and 0.45 Pa) at two substrate temperatures (100 degrees C and 400 degrees C). The role of the sputtering conditions on ZnO thin films nanostructuring, optical properties and morphology is investigated by Xray diffraction (XRD), X-ray reflectometry (XRR) and Spectroscopic ellipsometry (SE). XRD investigations revealed that ZnO films show a (0 0 l) texture with nanosized crystallites. Right-angle asymmetry of the (0 0 2) diffraction peak is observed. The peak profile analysis using pseudo-Voigt functions unveils a double overlapped peak structure with different coherent zone size values. A double layer structure is evidenced by analyzing the XRR data. Samples prepared at 0.3 Pa at a temperature of 400 degrees C have a similar to 4 nm bottom layer consisting of highly depleted in oxygen ZnO1-x structure, continued by a 53 nm top layer of textured ZnO. Electrical measurements show that the temperature dependence of the conductivity is well described by the Mott variable range hopping (VRH) law. The samples obtained at 400 degrees C have a significantly lower resistivity. (C) 2012 Elsevier B. V. All rights reserved.

We report on the coating with ZnO adherent thin films of cotton woven fabrics by Pulsed laser deposition technique in order to obtain innovative textile materials, presenting protective effects against UV radiations and antifungal action.

Smooth and adherent bioactive coatings with similar to 0.5 mu m thickness were deposited onto Si substrates by the radiofrequency-magnetron sputtering method at 150 degrees C under 0.4 Pa of Ar atmosphere using a bioglass powder as target with a composition in the SiO2-CaO-MgO-P2O5-CaF2-B2O3-Na2O system. The bioactivity of the as-prepared bioglass samples was assessed by immersion in simulated body fluid for different periods of time up to 30 days. Grazing incidence X-ray diffraction, Fourier transform infra-red spectrometry and energy dispersive spectroscopy revealed that important structural and compositional changes took place upon immersing the samples in SBF. Whilst the excellent biomineralisation capability of the BG thin films was demonstrated by the in vitro induction of extensive and homogenous crystalline hydroxyapatite in-growths on their surfaces, a series of bioactivity process kinetics peculiarities (derogations from the classical model) were emphasised and thoroughly discussed. (C) 2012 Elsevier B. V. All rights reserved.

The growth of La5Ca9Cu24O41 thin films on SrLaAlO4 (1 0 0) and Gd3Ga5O12 (1 0 0) substrates by pulsed laser deposition is reported in this paper. The influence of deposition process parameters, such as oxygen pressure, substrate temperature, and laser repetition rate, on the crystallinity, orientation and microstructure of the films has been investigated. X-ray diffraction and atomic force microscopy studies showed a clear dependence of the film crystallographic orientation and morphology (grain size) on the substrate temperature and the oxygen pressure used in the deposition process. (c) 2012 Elsevier B.V. All rights reserved.

The search of new alternative materials for bone reconstruction is a major objective in biomaterials engineering and reconstructive medicine. In this study the compact bone derived materials are proposed, their structure and composition being modified by thermal treatments performed in 200-1200 degrees C range, using 200 degrees C temperature steps. The monitoring of the bone modifications under heat-treatment was carried out using thermal analysis (TGA-DSC), microstructural (SEM), compositional (EDS) and structural (FTIR, XRD) methods. Tailoring the bone material's morphological, chemical and structural properties by heat-treatments, expressed by the HA/beta-TCP compositional ratio, degree of crystallinity and porosity control, could lead to the obtaining of good quality bone substitute materials suitable for the bone regeneration of large osseous defects.

Spectroscopic ellipsometry, X-ray diffraction and transmission electron microscopy experiments are employed to characterize aluminum nitride (AlN) thin films obtained by radio-frequency magnetron sputtering at low temperature (approximate to 50 degrees C). To understand the growth mechanism and to get in depth information of such films by using ex situ characterization techniques, the AlN thin film sample series were prepared for different sputtering times, while keeping constant all the other deposition conditions. The diffraction studies reveal a [002] oriented growth of the AlN thin films. The misorientation of this crystallographic axis to the normal to the surface reduces progressively with film growth. A nonmonotonic behavior of the AlN pseudo-refractive index versus deposition time indicates a complex depth profile of the AlN thin films optical properties. The difference in orientation dispersion of the [002] crystallite axis, the variation of defects concentration and each constituent atom density influence the refractive index evolution. Our interpretation validity was verified by producing and characterizing samples obtained at intermediate deposition time. The AlN thin films show also very good pull-out adherence values. (C) 2012 Elsevier B. V. All rights reserved.

Transmission electron microscopy and X-ray photoelectron spectroscopy analyses are performed to investigate Ge nanoparticles embedded in an amorphous SiO2 matrix. GeSiO thin films are prepared by two methods, sol-gel and radio frequency magnetron sputtering. After the deposition, the sol-gel films are annealed in either N-2 (at 1 atm and 800 A degrees C) or H-2 (at 2 atm and 500 A degrees C), and the sputtered films in H-2 (at 2 atm and 500 A degrees C), to allow Ge segregation. Amorphous Ge-rich nanoparticles (3-7 nm size) are observed in sol-gel films. Crystalline Ge nanoparticles in the high pressure tetragonal phase (10-50 nm size) are identified in the sputtered films. The size of the nanoparticles increases with Ge concentration in the volume of the film. At the film surface, the Ge concentration is much larger that in the volume for both sol-gel and sputtered films. At the same time, at the film surface, only oxidized Ge is observed.

Cotton/polyester woven fabrics were functionalized with ZnO thin films or nanoparticles by pulsed laser deposition, using a KrF* excimer laser source. Depending on the number of applied laser pulses, well-separated nanoparticles (for 10 pulses) or compact thin films (for 100 pulses) were deposited. The synthesized nanostructures were evaluated morphologically by scanning electron microscopy and atomic force microscopy, physico-chemically by x-ray diffraction and functionally by the contact angle method. By modifying the ambient gas nature and pressure in the deposition chamber, hydrophilic or hydrophobic surfaces were obtained. When using an oxygen flux, both the deposited thin films and nanoparticles were hydrophilic. After deposition in vacuum, the nanoparticles were hydrophobic, but the thin films were super-hydrophobic. This radical modification of wetting behavior was assigned to the differences in microstructure features and surface electrical charging in the two cases. (C) 2011 American Institute of Physics. [doi:10.1063/1.3639297]

Smooth, transparent and highly oriented nanostructured ZnO films were synthesized by RF-magnetron sputtering onto Si(100) substrates. A mild-pressed zinc oxide powder target was used for all depositions. The sputtering parameters were varied in order to obtain structures with good adherence and crystallinity. The depositions were carried out in inert argon atmosphere at four sputtering pressures (0.2 Pa, 0.25 Pa, 0.3 Pa and 0.45 Pa). ZnO films were deposited at 150 degrees C. The films were characterized from structural (XRD) and morphological (AFM) point of view. The influence of each sputtering parameter on the morphological and structural properties is discussed.

Thin (380-510 nm) films of a low silica content bioglass with MgO, B2O3, and CaF2 as additives were deposited at low-temperature (150A degrees C) by radio-frequency magnetron sputtering onto titanium substrates. The influence of sputtering conditions on morphology, structure, composition, bonding strength and in vitro bioactivity of sputtered bioglass films was investigated. Excellent pull-out adherence (similar to 73 MPa) was obtained when using a 0.3 Pa argon sputtering pressure (BG-a). The adherence declined (similar to 46 MPa) upon increasing the working pressure to 0.4 Pa (BG-b) or when using a reactive gas mixture (similar to 50 MPa). The SBF tests clearly demonstrated strong biomineralization features for all bioglass sputtered films. The biomineralization rate increased from BG-a to BG-b, and yet more for BG-c. A well-crystallized calcium hydrogen phosphate-like phase was observed after 3 and 15 days of immersion in SBF in all bioglass layers, which transformed monotonously into hydroxyapatite under prolonged SBF immersion. Alkali and alkali-earth salts (NaCl, KCl and CaCO3) were also found at the surface of samples soaked in SBF for 30 days. The study indicated that features such as composition, structure, adherence and bioactivity of bioglass films can be tailored simply by altering the magnetron sputtering working conditions, proving that this less explored technique is a promising alternative for preparing implant-type coatings.

Functionalized implants represent an advanced approaching in implantology, aiming to improve the biointegration and the long-term success of surgical procedures. We report on the synthesis of hydroxyapatite (HA) thin films on polymethylmetacrylate (PMMA) substrates - used as cranio-spinal implant-type structures - by two alternative methods: pulsed laser deposition (PLD) and radio-frequency magnetron sputtering (MS). The deposition parameters were optimized in order to avoid the substrate overheating. Stoichiometric HA structures were obtained by PLD with incident laser fluences of 1.4-2.75 J/cm(2), pressures of 30-46.66 Pa and 10 Hz pulses repetition rate. The MS depositions were performed at constant pressure of 0.3 Pa in inert and reactive atmospheres. SEM-EDS, XRD, FTIR and pull-out measurements were performed assessing the apatitic-type structure of the prepared films along with their satisfactory mechanical adhesion. Cell viability, proliferation and adhesion tests in osteosarcoma SaOs2 cell cultures were performed to validate the bioactive behaviour of the structures and to select the most favourable deposition regimes. For PLD, this requires a low thence of 1.4 J/cm2, reduced pressure of water vapours and a 100 degrees C/4 h thermal treatment. For MS, the best results were obtained for 80% Ar + 20% O-2 reactive atmosphere at low RF power (similar to 75 W). Cells grown on these coatings exhibit behaviour similar to those grown on the standard borosilicate glass control: increased viability, good proliferation, and optimal cell adhesion. In vitro tests proved that HA/PMMA neurosurgical structures prepared by PLD and MS are compatible for the interaction with human bone cells. (C) 2010 Elsevier B.V. All rights reserved.

Bioglass coatings were prepared by radio frequency magnetron sputtering deposition at low temperature (150 degrees C) onto silicon substrates. The influence of argon pressure values used during deposition (0.2 Pa, 0.3 Pa and 0.4 Pa) on the short-range structure and biomineralization potential of the bioglass coatings was studied. The biomineralization capability was evaluated after 30 days of immersion in simulated body fluid. SEM-EDS, XRD and FTIR measurements were performed. The tests clearly showed strong biomineralization features for the bioglass films. The thickness of the chemically grown hydroxyapatite layers was more than twice greater for the BG films deposited at the highest working pressure, in comparison to those grown on the films obtained at lower working pressures. The paper attempts to explain this experimental fact based on structural and compositional considerations. (C) 2010 Elsevier B.V. All rights reserved.

Implant type coatings were prepared by magnetron sputtering (MS) technique onto medical grade Ti6Al4V alloy substrates starting from biological 45S5 glass system powders. The as-deposited thin layers were annealed 2 h at 700 degrees C in ambient air, followed by a slow cooling (2 degrees C/min) in order to induce crystallization. The behavior of the coatings was investigated by soaking the samples in simulated body fluids (SBF) and extracting them after 24 and 72 h. The changes in the films' structure were investigated by scanning electron microscopy (SEM), X-ray diffraction (XRD), energy dispersive spectroscopy (EDS) analysis and by Fourier transform infrared spectroscopy (FTIR). A pitched, pore free microstructure with 6 mu m agglomerates of submicron grains in a continuous matrix was revealed by the SEM images of the annealed samples. Complex silicates as Na(4)Ca(4)Si(6)O(18)-combeite and phosphates NaCaPO(4) as crystalline phases were identified in the XRD diffraction patterns. In-growths after 24 h show the enrichment in Si-O (s) non-bonding oxygen (NBO). The polymerization reaction in the surface layer appears for the sample immersed 72 h in SBF. No crystalline hydroxyapatite (HA) was evidenced for those samples. Subsequent dissolution processes of the surface layers were noticed from XRD patterns and SEM images. (c) 2010 Elsevier B.V. All rights reserved.

A growing need for eco-friendly energy sources have led recently to a frantic search of new compositional systems for photovoltaic applications. The nanocomposite titania-germanium (TiO2-Ge) systems represent a new viable family of optoelectronic materials. Their structural, optical and electronic properties can be easily tailored by customizing the density and size of Ge dots in the TiO2 matrix. Early studies on TiO2-Ge nanocomposites have shown promises for their use as an alternative in photovoltaic applications. In this study we report the TiO2-Ge films synthesis by reactive magnetron co-sputtering. Their properties were evaluated by compositional (EDS), structural (XRD, FTIR) and optical (UV-Vis) characterizations.

In this work, an improved version of the radio frequency magnetron sputtering (RF-MS) technique was used to prepare highly adherent B-type carbonated hydroxylapatite (B-CHA) thin films. Fourier transform infrared spectroscopy (FTIR) and grazing incidence X-ray diffraction studies proved that the coatings maintained the composition and revealed the polycrystalline structure of HA. Scanning electron microscopy analysis showed that the CHA films are rough and exhibit a homogeneous microstructure. Energy-dispersive Xray spectroscopy (EDX) mapping demonstrated a uniform distribution of the Ca and P cations while a Ca/P ratio of 1.8 was found. In addition, the FTIR experiments showed a remarkable reproducibility of the nanostructures. Human mesenchymal stem cells (hMSCs), in vitro differentiated osteoblasts, and explanted bone cells were grown over the surface of CHA coatings for periods between a few hours and 21 days. Osteoprogenitor cells maintained viability and characteristic morphology after adhesion on CHA coatings. Ki67-positive osteoblasts were the evidence of cell proliferation events. Cells showed positive staining for markers of osteoblast phenotype such as collagen type I, bone sialoprotein and osteonectin. Our data showed the formation of mineralized foci by differentiation of hMSCs to human primary osteoblasts after cultivation in osteogenic media on RF-sputtered films. The results demonstrate the capacity of B-type CHA coating to support MSCs adhesion and osteogenic differentiation ability. (C) 2010 Wiley Periodicals, Inc. J Biomed Mater Res Part A: 95A: 1203-1214,2010.

We report on the versatility of pulsed laser deposition and radio frequency magnetron sputtering deposition methods to synthesize highly adherent bioactive hydroxyapatite thin layers on cranio-spinal implants as appropriate biofixation alternatives.

Radiofrequency magnetron sputtering deposition at low temperature (150A degrees C) was used to deposit bioactive glass coatings onto titanium substrates. Three different working atmospheres were used: Ar 100%, Ar + 7%O(2), and Ar + 20%O(2). The preliminary adhesion tests (pull-out) produced excellent adhesion values (similar to 75 MPa) for the as-deposited bio-glass films. Bioactivity tests in simulated body fluid were carried out for 30 days. SEM-EDS, XRD and FTIR measurements were performed. The tests clearly showed strong bioactive features for all the prepared films. The best biomineralization capability, expressed by the thickest chemically grown carbonated hydroxyapatite layer, was obtained for the bio-glass coating sputtered in a reactive atmosphere with 7% O(2).

In this study, Fourier Transform Infrared Spectroscopy (FTIR) in Attenuated Total Reflectance mode was employed as main characterization technique to investigate the reaction mechanisms in vitro (SBF) of bioglass and glass-ceramic sputtered coatings. Two bioglass compositional systems are compared in order to gain more information regarding their in vitro bioreactivity. Important correlations between the concentration of non-bridging silicon-oxygen (Si-O-NBO) groups and the content of network modifiers were found. FTIR revealed that the high concentrations of Si-O-NBO groups are promoting the enhancing of coatings' reactivity. This information could be very useful for the development and tailoring of new bioactive glasses with an optimum biological behaviour. By varying the compositional features and the structural state, the sputtered glassy coatings exhibited different in vitro behaviour: inertness, resorbability and bioactivity.

We report on the synthesis of 700 nm thick bioglass thin films by magnetron sputtering from 45S5 bioglass targets in the argon atmosphere. The adhesion of films to Ti substrates increased 1 75 times when introducing an similar to 70 nm thick mixed glass-Ti buffer layer (BG(1-x)Ti(x) (x = 0-1)) with gradient of composition by co-sputtering. The morphological and structural properties of the films were studied by XRD, ETIR and microscopic techniques, showing an improvement after the two-hour thermal air treatment at 650 degrees C. We investigated in vitro the viability and proliferation of human osteoblast cells cultivated onto the surface of the films The osteoblasts spread over the surface adopting typical polyhedral shapes with numerous focal adhesion points and protrusions infiltrating deep into the films. We assigned this evolution to the improved mechanical properties and enhanced bioactivity due to the prevalent formation of combeite and wollastonite crystalline phases in the heat treated bioglass films (C) 2010 Elsevier B.V All rights reserved

Highly oriented (001) AlN (wurtzite type) thin films have been successfully deposited on silicon, platinized silicon and glass substrates by reactive radio-frequency magnetron sputtering at low temperature (150 degrees C). X-ray diffraction, spectroscopic ellipsometry and scanning electron microscopy techniques have been employed to asses the structural characteristics of the AlN films. We have investigated both the influence of AlN film's thickness and of the substrate nature on crystallinity. The thicker films present a better c axis alignment, a minimum orientation dispersion of 3.5. being reached for 1 mu m AlN on silicon. The micro-and macrostrain of the AlN lattice relaxes as the film thickness increases. The film deposited onto platinum has the maximum value of tensile strain along c axis. The film on glass exhibited the poorest texturing and the highest defect concentration. From an optical point of view the film deposited on Pt is the denser one and that deposited on glass is the most rarefied. One can conclude that when using a low deposition temperature and a base pressure of similar to 10(-4) Pa the increase of film thickness leads to improved AlN structure on Si or Pt supports.

GeSiO nanosystems were obtained using two different preparation methods, sol-gel and magnetron-sputtering. Transmission electron microscopy measurements were performed to investigate the films structure. Amorphous and crystalline Ge dots embedded in amorphous silicon dioxide were observed. The Ge concentration in the GeSiO films was by Energy-dispersive X-ray spectroscopy.

Hydrogenated amorphous carbon (a-C: H) films were grown by radio-frequency (1.78 MHz) plasma enhanced chemical vapour deposition technique onto medical grade Ti6Al4V substrates. By varying the deposition pressure (13.33 Pa and 53.33 Pa, respectively) and methane dilution (20% and 60%, respectively) several types of carbonic films were obtained, presenting different bonding structures, surface energies and morphological features reflected in their biological behaviour. FTIR, Raman, UV-Vis, XPS and AFM measurements were used for characterizing these structures. The surface energy was determined by contact angle measurements, and their thrombogenicity was tested by the activated partial thromboplastin time (aPTT) method. We have noticed that at the same values of methane in argon dilution but at different pressure values, the film structure was totally changed: soft polymer-like carbon (PLC) type at the higher pressure and hard diamond-like carbon (DLC) type at the lower pressure. Raman spectroscopy and XPS suggested that the highest sp(3) ratio (similar to 52%), was found for DLC films prepared in a 60% methane dilution in argon. It has been found that for both PLC and DLC structures the surface energy has a decreasing tendency with the methane concentration increase in the deposition atmosphere. Excellent aPTT results were obtained for the DLC-60 (18.6.+/- 0.3 min) and PLC-20 (17.4 +/- 0.5 min) structures, superior to those recorded for Ti6Al4V and PMMA commercial materials. These values recommend the prepared carbonic structures for medical applications: harder coatings (DLC) for metal prostheses (heart valves, acetabular cups etc.), while softer and flexible coatings (PLC) for the textile vessels or stents biofunctionalization.

The aim of this paper was to study the influence of crystallization heat treatments up to 750 degrees C, upon the integrity and structure of hydroxylapatite thin films. Two different types of hydroxylapatite coatings were investigated: abrupt structures prepared by magnetron sputtering and respectively functional graded structures deposited by a co-sputtering technique. A clear dependence was noticed between adherence values and annealing temperature and was correlated with the SEM, XRD and FTIR results. X-ray diffraction and FTIR measurements showed that the hydroxylapatite coatings annealed at 400 degrees C were less crystalline, similar to biological apatites. Over 550 degrees C, the apatite coatings obtained were well crystallized and preferentially oriented on (002) HA crystal plane. The adherence of HA coating increased with annealing the temperature up to 550 degrees C due to diffusion phenomena. At 550 degrees C the adhesion test results indicated better adhesion values in case of functional graded structures (> 85 MPa) in comparison with abrupt ones (similar to 70 MPa). At 750 degrees C an adherence decreasing occurred for both types of structures. This is mainly due to the effect of a significant thermal stress owed to the mismatch of the thermal expansion coefficients between the crystallized HA and Ti substrate. The presence of rutile lines in XRD spectrum suggests an increasing of the diffusion phenomena and a strong substrate oxidation at the HAM interface with annealing temperature.

The fabrication and characterisation of surface acoustic wave resonators operating in the gigahertz frequency range are presented. The devices were fabricated on thin AlN layers deposited by magnetron sputtering on high resistivity (100) oriented silicon substrates. Using direct writing e-beam lithography, well defined interdigital transducers with 300 nm finger width and spacing have been obtained. On-wafer microwave measurements have demonstrated a narrow bandstop frequency characteristic with high rejection at approximately 5 GHz and an electromechanical coupling coefficient of 0.53%.

Bio-glass films were deposited by radio-frequency magnetron sputtering technique onto medical grade Ti6Al7Nb alloy substrates from prepared silica based bio-glass target. A low deposition temperature was used (150 degrees C) and three different working pressures, followed by annealing in air at 550 and 750 degrees C. A quasi-stoichiometric target to substrate atomic transfer was found for Si, Ca and P, along with strong enrichment in Na and depletion in K and Mg, as evidenced by the energy dispersive microanalysis. The best results, taking into account stoichiometry and surface roughness, were obtained for the BG layers deposited at 0.3 Pa argon working pressure. The infrared spectroscopy of the as-sputtered and of the annealed films evidenced the characteristic molecular vibrations of silicate, phosphate and carbonate functional groups. The as-deposited films are amorphous and became partly crystalline after annealing at 750 degrees C, as evidenced by X-ray diffraction. The pull-out measurements, performed with a certified pull-test machine, gave very strong film-substrate adhesion strength values. For the non-crystalline layers, the pull-out strength is higher than 85 MPa, and decreases after annealing at 750 degrees C to 72.9 +/- 7.1 MPa. The main objective of this work was to establish the influence of the working pressure upon the composition and morphology of the as-deposited films, and of the annealing temperature upon structure and film substrate adhesion. (C) 2009 Elsevier B. V. All rights reserved.

The magnetron sputtering method was used to obtain layers of indium tin oxide or hydroxyapatite on glass fiber woven and on reference glass plates. The layers were characterized by scanning microscopy, UV-vis spectroscopy and conductivity measurements. Hydrophilic properties of the woven samples were investigated by optical microscopy following the behavior of a water droplet upon the each of the samples. The change of the drop profile in time due to wetting of the fabric leads to the wetting kinetics. The most efficient treatments to improve the hydrophilic/wetting properties of the glass fiber woven were found.

We studied the chemical growth of calcium phosphate nanostructured coatings onto silicon wafers pre-covered with carbonated polycrystalline hydroxyapatite films. Silicon wafers were covered with hydroxyapatite thin layers by radio frequency magnetron sputtering and then immersed in 370 degrees C simulated body fluids for up to 20 days. Immersed structures were extracted every 2 days for studies by Fourier transform IR spectrometry. The chemically grown layers were further analyzed by X-ray diffraction and scanning electron microscopy. The growth kinetics of calcium phosphate deposits was monitored by estimating the area of phosphate, carbonate and water stretching bands of the recorded infra-red vibrational spectra. Sequential annealing in vacuum up to 950 degrees C was applied to elucidate the nature of incorporated water. Our studies revealed that the layers growing in simulated body fluid are rougher than initial hydroxyapatite interlayers, contain carbonates, include water in interlayer's voids and have therefore an increased biological activity for promoting faster implants integration with human bone tissues.

Fluorinated hydroxyapatite [Ca-10(PO4)(6)(OH)(x)F1-x] implantologic structures could constitute an alternative to classic hydroxyapatite [Ca-10(PO4)6(OH)21 ones in medical applications due to their bioactivity and low solubility. Bioactive apatites are usually used as coatings onto surface of biocompatible metals, leading to implants which take advantage of the coating's bioactivity and good mechanical properties of metals. In this work, powders and apatite type films were prepared on Ti6Al4V medical grade alloy using three sol-gel chemical routes by mixing different calcium and phosphorous precursors Ca(NO3)2, P2O5 and C6H15PO3, and two fluoride reagents: HPF6 and NH4F. The resulting calcium phosphates and fluorapatite/hydroxyapatite solid solution (FHA) compounds were investigated by SEM, XRD and evaluated in vitro in SBF Kokubo solution. An efficient preparation algorithm was designed for the Ca(NO3)(2+) C6H15PO3+ NH4F chemical route which produced monophasic powders with a high crystallinity degree. This chemical route led to FHA sol-gel coatings with bioactive potential.

The structural role of V in 28Li(2)O-72SiO(2) (in mol%) lithium silicate glass doped with 0.5 mol% V2O5 was assessed using Si-29 and V-51 Nuclear Magnetic Resonance (NMR), Fourier-transform infrared (FTIR), and X-ray photoelectron (XPS) spectroscopy techniques. Despite the low amount of V2O5 used, the structural information obtained or deduced from the statistical analysis of the NMR data could explain the evolution of glass properties after V2O5 addition. The XPS results indicated that all vanadium exists in 5+ oxidation state. Both the Si-29 NMR and FTIR data point toward an increase in the polymerization of the silicate network, caused by the V2O5 acting as network former, capable to form various QVn tetrahedral units (for n = 0, 1, and 2) in the glasses. These QVn units, which are similar to phosphate units, scavenge the Li+ ions and cause the silicate network to polymerize. However, in an overall balance, the entire glass network is depolymerized due to the additional nonbridging oxygens contributed by the vanadium polyhedra. The addition of vanadium causes the network to expand and increases the ionic conductivity.