Bone tissue, cellular, and molecular responses to titanium implants treated by anodic spark deposition

A myriad of titanium (Ti) surface modifications has been proposed to hasten the osseointegration. In this context, the aim of this study was to perform histomorphometric, cellular, and molecular analyses of the bone tissue grown in close contact with Ti implants treated by anodic spark deposition (ASD-AK). Acid-etched (AE) Ti implants either untreated or submitted to ASD-AK were placed into dog mandibles and retrieved at 3 and 8 weeks. It was noticed that both implants, AE and ASD-AK, were osseointegrated at 3 and 8 weeks. Histomorphometric analysis showed differences between treatments only for bone-to-implant contact, being higher on AE implants. Although not backed by histomorphometric results, gene expression of key bone markers was higher for bone grown in close contact with ASD-AK and for cells harvested from these fragments and cultured until subconfluence. Cell proliferation at days 7 and 10 and alkaline phosphatase activity at day 10 was higher on AE surfaces. No statistical significant difference was noticed for extracellular matrix mineralization at 17 days. Our results have shown that the Ti fixtures treated by ASD-AK allowed in vivo osseointegration and induced higher expression of key markers of osteoblast phenotype, suggesting that this surface treatment could be considered to produce implants for clinical applications. (c) 2012 Wiley Periodicals, Inc. J Biomed Mater Res Part A: 100A:30923098, 2012.

Microtensile bond strength of composite resin to glass-infiltrated alumina composite conditioned with Er,Cr:YSGG laser

Tribochemical silica-coating is the recommended conditioning method for improving glass-infiltrated alumina composite adhesion to resin cement. High-intensity lasers have been considered as an alternative for this purpose. This study evaluated the morphological effects of Er,Cr:YSGG laser irradiation on aluminous ceramic, and verified the microtensile bond strength of composite resin to ceramic following silica coating or laser irradiation. In-Ceram Alumina ceramic blocks were polished, submitted to airborne particle abrasion (110 mu m Al(2)O(3)), and conditioned with: (CG) tribochemical silica coating (110 mu m SiO(2)) + silanization (control group); (L1-L10) Er,Cr:YSGG laser (2.78 mu m, 20 Hz, 0.5 to 5.0 W) + silanization. Composite resin blocks were cemented to the ceramic blocks with resin cement. These sets were stored in 37A degrees C distilled water (24 h), embedded in acrylic resin, and sectioned to produce bar specimens that were submitted to microtensile testing. Bond strength values (MPa) were statistically analyzed (alpha a parts per thousand currency sign0.05), and failure modes were determined. Additional ceramic blocks were conditioned for qualitative analysis of the topography under SEM. There were no significant differences among silicatization and laser treatments (p > 0.05). Microtensile bond strength ranged from 19.2 to 27.9 MPa, and coefficients of variation ranged from 30 to 55%. Mixed failure of adhesive interface was predominant in all groups (75-96%). No chromatic alteration, cracks or melting were observed after laser irradiation with all parameters tested. Surface conditioning of glass-infiltrated alumina composite with Er,Cr:YSGG laser should be considered an innovative alternative for promoting adhesion of ceramics to resin cement, since it resulted in similar bond strength values compared to the tribochemical treatment.

Ultra-low friction coefficient in alumina-silicon nitride pair lubricated with water

In a ball-on-disc wear test, an alumina ceramic body sliding against a silicon nitride ceramic body in water achieved an ultra-low friction coefficient (ULFC) of 0.004. The profilometer and EDX measurements indicated that the ULFC regime in this unmated Al2O3-Si3N4 pair was achieved because of the formation of a flat and smooth interface of nanometric roughness, which favored the hydrodynamic lubrication. The triboreactions formed silicon and aluminum hydroxides which contributed to decrease roughness and shear stress at the contact interface. This behavior enables the development of low energy loss water-based tribological systems using oxide ceramics. 13 2012 Elsevier B.V. All rights reserved.

BEM modeling of saturated porous media susceptible to damage

This paper deals with the numerical analysis of saturated porous media, taking into account the damage phenomena on the solid skeleton. The porous media is taken into poro-elastic framework, in full-saturated condition, based on Biot's Theory. A scalar damage model is assumed for this analysis. An implicit boundary element method (BEM) formulation, based on time-independent fundamental solutions, is developed and implemented to couple the fluid flow and two-dimensional elastostatic problems. The integration over boundary elements is evaluated using a numerical Gauss procedure. A semi-analytical scheme for the case of triangular domain cells is followed to carry out the relevant domain integrals. The non-linear problem is solved by a Newton-Raphson procedure. Numerical examples are presented, in order to validate the implemented formulation and to illustrate its efficacy. (C) 2011 Elsevier Ltd. All rights reserved.

An EQCM-D study of the influence of chloride on the lead anodic oxidation

The influence of chloride on the electrodeposition of lead films and their dissolution in anodic stripping voltammetric experiments was examined. Gold substrates were plated with lead films, and mass changes were monitored by using the electrochemical quartz crystal microbalance with dissipation factor (EQCM-D). The results showed that the amount of electrodeposited lead is slightly dependent on the chloride concentration. The charge/mass ratio data indicated the presence of Pb(I) and Pb(II) as a result of film dissolution, and the precipitation and deposition of PbCl2 onto the electrode surface. Scanning electron microscopy images revealed that the morphology of the lead film was strongly influenced by chloride present in the plating solution and that much rougher films were obtained in comparison with those obtained in the absence of chloride. The rate of the anodic dissolution was higher for lead films with higher surface areas, which lead to an increase in their stripping voltammetric currents. (C) 2012 Elsevier Ltd. All rights reserved.

An electrochemical gas sensor based on paper supported room temperature ionic liquids

A sensitive and fast-responding membrane-free amperometric gas sensor is described, consisting of a small filter paper foil soaked with a room temperature ionic liquid (RTIL), upon which three electrodes are screen printed with carbon ink, using a suitable mask. It takes advantage of the high electrical conductivity and negligible vapour pressure of RTILs as well as their easy immobilization into a porous and inexpensive supporting material such as paper. Moreover, thanks to a careful control of the preparation procedure, a very close contact between the RTIL and electrode material can be achieved so as to allow gaseous analytes to undergo charge transfer just as soon as they reach the three-phase sites where the electrode material, paper supported RTIL and gas phase meet. Thus, the adverse effect on recorded currents of slow steps such as analyte diffusion and dissolution in a solvent is avoided. To evaluate the performance of this device, it was used as a wall-jet amperometric detector for flow injection analysis of 1-butanethiol vapours, adopted as the model gaseous analyte, present in headspace samples in equilibrium with aqueous solutions at controlled concentrations. With this purpose, the RTIL soaked paper electrochemical detector (RTIL-PED) was assembled by using 1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl) imide as the wicking RTIL and printing the working electrode with carbon ink doped with cobalt(II) phthalocyanine, to profit from its ability to electrocatalyze thiol oxidation. The results obtained were quite satisfactory (detection limit: 0.5 mu M; dynamic range: 2-200 mu M, both referring to solution concentrations; correlation coefficient: 0.998; repeatability: +/- 7% RSD; long-term stability: 9%), thus suggesting the possible use of this device for manifold applications.

Gold ion implantation into alumina using an “inverted ion source” configuration.

We describe an approach to ion implantation in which the plasma and its electronics are held at ground potential and the ion beam is injected into a space held at high negative potential, allowing considerable savings both economically and technologically. We used an “inverted ion implanter” of this kind to carry out implantation of gold into alumina, with Au ion energy 40 keV and dose (3–9) × 1016 cm−2. Resistivity was measured in situ as a function of dose and compared with predictions of a model based on percolation theory, in which electron transport in the composite is explained by conduction through a random resistor network formed by Au nanoparticles. Excellent agreement is found between the experimental results and the theory.

Photoluminescence of core-shell nanoparticles made from yttrium stabilized zirconia powder grain coated with alumina

A YSZ@Al2O3 nanocomposite was obtained by Al2O3 coating on the surface of yttrium stabilized zirconia via a polymeric precursor method. The resulting core–shell structures were characterized by X-ray diffraction, scanning electron microscopy, transmission electronic microscopy and PL spectra. The TEM micrographs clearly show a homogeneous Al2O3 shell around the ZrO2 core. The observed PL is related to surface–interface defects. Such novel technologies can, in principle, explore materials which are not available in the bulk single crystal form but their figure-of-merit is dramatically dependent on the surface–interface defect states.

Preparation and characterisation of refractory whiskers and selected alumina composites

A whisker is a common name of single crystalline inorganic fibre of small dimensions, typically 0.5-1 μm in diameter and 20-50 μm in length. Whiskers are mainly used as reinforcement of ceramics. This work describes the synthesis and characterisation of new whisker types. Ti0.33Ta0.33Nb0.33CxN1-x, TiB2, B4C, and LaxCe1-xB6 have been prepared by carbothermal vapour–liquid–solid (CTR-VLS) growth mechanisms in the temperature range 900-1800°C, in argon or nitrogen. Generally, carbon and different suitable oxides were used as whisker precursors. The oxides reacted via a carbothermal reduction process. A halogenide salt was added to form gaseous metal halogenides or oxohalogenides and small amount of a transition metal was added to catalyse the whisker growth. In this mechanism, the whisker constituents are dissolved into the catalyst, in liquid phase, which becomes supersaturated. Then a whisker could nucleate and grow out under continuous feed of constituents. The syntheses of TiC, TiB2, and B4C were followed at ordinary synthesis conditions by means of mass spectrometry (MS), thermogravimetry (TG), differential thermal analysis (DTA) and quenching. The main reaction starting temperatures and reaction time for the different mixtures was revealed, and it was found that the temperature inside the crucible during the reactions was up to 100°C below the furnace set-point, due to endothermic nature of the reactions. Quench experiments showed that whiskers were formed already when reaching the temperature plateau, but the yield increased fast with the holding time and reached a maximum after about 20-30 minutes. Growth models for whisker formation have been proposed. Alumina based composites reinforced by (2-5 vol.%) TiCnano and TiNnano and 25 vol.% of carbide, and boride phases (whiskers and particulates of TiC, TiN, TaC, NbC, (Ti,Ta)C, (Ti,Ta,Nb)C, SiC, TiB2 and B4C) have been prepared by a developed aqueous colloidal processing route followed by hot pressing for 90 min at 1700°C, 28 MPa or SPS sintering for 5 minutes at 1200-1600°C and 75 MPa. Vickers indentation measurements showed that the lowest possible sintering temperature is to prefer from mechanical properties point of view. In the TiNnano composites the fracture mode was typically intergranular, while it was transgranular in the SiCnano composites. The whisker and particulate composites have been compared in terms of e.g. microstructure and mechanical properties. Generally, additions of whiskers yielded higher fracture toughness compared to particulates. Composites of commercially available SiC whiskers showed best mechanical properties with a low spread but all the other whisker phases, especially TiB2, exhibited a great potential as reinforcement materials.

Numerical and analytical vibro-acoustic modelling of porous materials: the Cell Method for poroelasticity and the case of inclusions

Porous materials are widely used in many fields of industrial applications, to achieve the requirements of noise reduction, that nowadays derive from strict regulations. The modeling of porous materials is still a problematic issue. Numerical simulations are often problematic in case of real complex geometries, especially in terms of computational times and convergence. At the same time, analytical models, even if partly limited by restrictive simplificative hypotheses, represent a powerful instrument to capture quickly the physics of the problem and general trends. In this context, a recently developed numerical method, called the Cell Method, is described, is presented in the case of the Biot's theory and applied for representative cases. The peculiarity of the Cell Method is that it allows for a direct algebraic and geometrical discretization of the field equations, without any reduction to a weak integral form. Then, the second part of the thesis presents the case of interaction between two poroelastic materials under the context of double porosity. The idea of using periodically repeated inclusions of a second porous material into a layer composed by an original material is described. In particular, the problem is addressed considering the efficiency of the analytical method. A analytical procedure for the simulation of heterogeneous layers based is described and validated considering both conditions of absorption and transmission; a comparison with the available numerical methods is performed. ---------------- I materiali porosi sono ampiamente utilizzati per diverse applicazioni industriali, al fine di raggiungere gli obiettivi di riduzione del rumore, che sono resi impegnativi da norme al giorno d'oggi sempre più stringenti. La modellazione dei materiali porori per applicazioni vibro-acustiche rapprensenta un aspetto di una certa complessità. Le simulazioni numeriche sono spesso problematiche quando siano coinvolte geometrie di pezzi reali, in particolare riguardo i tempi computazionali e la convergenza. Allo stesso tempo, i modelli analitici, anche se parzialmente limitati a causa di ipotesi semplificative che ne restringono l'ambito di utilizzo, rappresentano uno strumento molto utile per comprendere rapidamente la fisica del problema e individuare tendenze generali. In questo contesto, un metodo numerico recentemente sviluppato, il Metodo delle Celle, viene descritto, implementato nel caso della teoria di Biot per la poroelasticità e applicato a casi rappresentativi. La peculiarità del Metodo delle Celle consiste nella discretizzazione diretta algebrica e geometrica delle equazioni di campo, senza alcuna riduzione a forme integrali deboli. Successivamente, nella seconda parte della tesi viene presentato il caso delle interazioni tra due materiali poroelastici a contatto, nel contesto dei materiali a doppia porosità. Viene descritta l'idea di utilizzare inclusioni periodicamente ripetute di un secondo materiale poroso all'interno di un layer a sua volta poroso. In particolare, il problema è studiando il metodo analitico e la sua efficienza. Una procedura analitica per il calcolo di strati eterogenei di materiale viene descritta e validata considerando sia condizioni di assorbimento, sia di trasmissione; viene effettuata una comparazione con i metodi numerici a disposizione.

Caratterizzazione di membrane metalliche e ionomeriche per applicazioni energetiche

The work of this thesis has been focused on the characterization of metallic membranes for the hydrogen purification from steam reforming process and also of perfluorosulphonic acid ionomeric (PFSI) membranes suitable as electrolytes in fuel cell applications. The experimental study of metallic membranes was divided in three sections: synthesis of palladium and silver palladium coatings on porous ceramic support via electroless deposition (ELD), solubility and diffusivity analysis of hydrogen in palladium based alloys (temperature range between 200 and 400 °C up to 12 bar of pressure) and permeation experiments of pure hydrogen and mixtures containing, besides hydrogen, also nitrogen and methane at high temperatures (up to 600 °C) and pressures (up to 10 bar). Sequential deposition of palladium and silver on to porous alumina tubes by ELD technique was carried out using two different procedures: a stirred batch and a continuous flux method. Pure palladium as well as Pd-Ag membranes were produced: the Pd-Ag membranes’ composition is calculated to be close to 77% Pd and 23% Ag by weight which was the target value that correspond to the best performance of the palladium-based alloys. One of the membranes produced showed an infinite selectivity through hydrogen and relatively high permeability value and is suitable for the potential use as a hydrogen separator. The hydrogen sorption in silver palladium alloys was carried out in a gravimetric system on films produced by ELD technique. In the temperature range inspected, up to 400°C, there is still a lack in literature. The experimental data were analyzed with rigorous equations allowing to calculate the enthalpy and entropy values of the Sieverts’ constant; the results were in very good agreement with the extrapolation made with literature data obtained a lower temperature (up to 150 °C). The information obtained in this study would be directly usable in the modeling of hydrogen permeation in Pd-based systems. Pure and mixed gas permeation tests were performed on Pd-based hydrogen selective membranes at operative conditions close to steam-reforming ones. Two membranes (one produced in this work and another produced by NGK Insulators Japan) showed a virtually infinite selectivity and good permeability. Mixture data revealed the existence of non negligible resistances to hydrogen transport in the gas phase. Even if the decrease of the driving force due to polarization concentration phenomena occurs, in principle, in all membrane-based separation systems endowed with high perm-selectivity, an extensive experimental analysis lack, at the moment, in the palladium-based membrane process in literature. Moreover a new procedure has been introduced for the proper comparison of the mass transport resistance in the gas phase and in the membrane. Another object of study was the water vapor sorption and permeation in PFSI membranes with short and long side chains was also studied; moreover the permeation of gases (i.e. He, N2 and O2) in dry and humid conditions was considered. The water vapor sorption showed strong interactions between the hydrophilic groups and the water as revealed from the hysteresis in the sorption-desorption isotherms and thermo gravimetric analysis. The data obtained were used in the modeling of water vapor permeation, that was described as diffusion-reaction of water molecules, and in the humid gases permeation experiments. In the dry gas experiments the permeability and diffusivity was found to increase with temperature and with the equivalent weight (EW) of the membrane. A linear correlation was drawn between the dry gas permeability and the opposite of the equivalent weight of PFSI membranes, based on which the permeability of pure PTFE is retrieved in the limit of high EW. In the other hand O2 ,N2 and He permeability values was found to increase significantly, and in a similar fashion, with water activity. A model that considers the PFSI membrane as a composite matrix with a hydrophilic and a hydrophobic phase was considered allowing to estimate the variation of gas permeability with relative humidity on the basis of the permeability in the dry PFSI membrane and in pure liquid water.

Stability, viscous dissipation and local thermal non-equilibrium in fluid saturated porous media

In this thesis, the field of study related to the stability analysis of fluid saturated porous media is investigated. In particular the contribution of the viscous heating to the onset of convective instability in the flow through ducts is analysed. In order to evaluate the contribution of the viscous dissipation, different geometries, different models describing the balance equations and different boundary conditions are used. Moreover, the local thermal non-equilibrium model is used to study the evolution of the temperature differences between the fluid and the solid matrix in a thermal boundary layer problem. On studying the onset of instability, different techniques for eigenvalue problems has been used. Analytical solutions, asymptotic analyses and numerical solutions by means of original and commercial codes are carried out.

Porous Polymeric Bioresorbable Scaffolds for Tissue Engineering

Tissue engineering is a discipline that aims at regenerating damaged biological tissues by using a cell-construct engineered in vitro made of cells grown into a porous 3D scaffold. The role of the scaffold is to guide cell growth and differentiation by acting as a bioresorbable temporary substrate that will be eventually replaced by new tissue produced by cells. As a matter or fact, the obtainment of a successful engineered tissue requires a multidisciplinary approach that must integrate the basic principles of biology, engineering and material science. The present Ph.D. thesis aimed at developing and characterizing innovative polymeric bioresorbable scaffolds made of hydrolysable polyesters. The potentialities of both commercial polyesters (i.e. poly-e-caprolactone, polylactide and some lactide copolymers) and of non-commercial polyesters (i.e. poly-w-pentadecalactone and some of its copolymers) were explored and discussed. Two techniques were employed to fabricate scaffolds: supercritical carbon dioxide (scCO2) foaming and electrospinning (ES). The former is a powerful technology that enables to produce 3D microporous foams by avoiding the use of solvents that can be toxic to mammalian cells. The scCO2 process, which is commonly applied to amorphous polymers, was successfully modified to foam a highly crystalline poly(w-pentadecalactone-co-e-caprolactone) copolymer and the effect of process parameters on scaffold morphology and thermo-mechanical properties was investigated. In the course of the present research activity, sub-micrometric fibrous non-woven meshes were produced using ES technology. Electrospun materials are considered highly promising scaffolds because they resemble the 3D organization of native extra cellular matrix. A careful control of process parameters allowed to fabricate defect-free fibres with diameters ranging from hundreds of nanometers to several microns, having either smooth or porous surface. Moreover, versatility of ES technology enabled to produce electrospun scaffolds from different polyesters as well as “composite” non-woven meshes by concomitantly electrospinning different fibres in terms of both fibre morphology and polymer material. The 3D-architecture of the electrospun scaffolds fabricated in this research was controlled in terms of mutual fibre orientation by properly modifying the instrumental apparatus. This aspect is particularly interesting since the micro/nano-architecture of the scaffold is known to affect cell behaviour. Since last generation scaffolds are expected to induce specific cell response, the present research activity also explored the possibility to produce electrospun scaffolds bioactive towards cells. Bio-functionalized substrates were obtained by loading polymer fibres with growth factors (i.e. biomolecules that elicit specific cell behaviour) and it was demonstrated that, despite the high voltages applied during electrospinning, the growth factor retains its biological activity once released from the fibres upon contact with cell culture medium. A second fuctionalization approach aiming, at a final stage, at controlling cell adhesion on electrospun scaffolds, consisted in covering fibre surface with highly hydrophilic polymer brushes of glycerol monomethacrylate synthesized by Atom Transfer Radical Polymerization. Future investigations are going to exploit the hydroxyl groups of the polymer brushes for functionalizing the fibre surface with desired biomolecules. Electrospun scaffolds were employed in cell culture experiments performed in collaboration with biochemical laboratories aimed at evaluating the biocompatibility of new electrospun polymers and at investigating the effect of fibre orientation on cell behaviour. Moreover, at a preliminary stage, electrospun scaffolds were also cultured with tumour mammalian cells for developing in vitro tumour models aimed at better understanding the role of natural ECM on tumour malignity in vivo.

Mechanische Eigenschaften von freitragenden artifiziellen und nativen Membranen

This thesis presents a new method to explore the local mechanical properties such as bending modulus or surface tension of artificial and native pore-spanning membranes. Therefore the elastic response of a free-standing membrane to a local indentation by the means of atomic force microscopy is measured. Starting point are highly hexagonal ordered pores in alumina produced by electrochemical anodization of planar aluminium. The homogeneous pore radius can by tailored in the range of 10 nm up to 200 nm, but radius of 33 nm, 90 nm and 200 nm turned out to be best suited for investigation of the mechanical properties of pore-spanning native or artificial membranes. In this work artificial membrane systems consisting of DODAB as a bilayer in gel phase or DOTAP as a fluide membrane are spreaded by vesicle absorption on hexagonal structured pores after chemisorption of a 3-mercaptopropionic acid monolayer. Centrally indenting these nanodrums with an atomic force microscope tip yields force-indentation curves, which are quantitatively analyzed by solving the corresponding shape equations of continuum curvature elasticity. Since the measured response depends in a known way on the system geometry (pore size, tip radius) and on material parameters (bending modulus, lateral tension, adhesion), this opens the possibility to monitor local elastic properties of lipid membranes in a well-controlled setting. Additionally the locally distributed mechanical properties of pore-spanning artificial membranes are compared to those of native pore-spanning membranes. Therefore the basal membrane of MDCK II cells was prepared on porous alumina assays and their mechanical properties were analyzed by means of atomic force microscopy. Finally the elastic behavior such as the Young modulus of living MDCK II cells under various osmotic pressures is investigated. By changing the osmolarity in the extracellular region of MDCK II cells a volume change is induced according to hydration and dehydration of the cells, respectively. This volume change induces also a change in the elastic behavior of the cell, which is quantified by the means of force spectroscopy.