Electrodeposition of biphasic calcium phosphate coatings with improved dissolution properties

Biphasic calcium phosphate coatings (hydroxyapatite/β-tricalcium phosphate) on titanium substrate (Ti6Al4V) are synthetized by pulsed current electrodeposition coupled to a thermal treatment under controlled atmosphere. The experimental conditions of the process such as the hydrogen peroxide amount and the treatment temperature are optimized in order to obtain different coatings compositions. The physico-chemical and structural characterizations of the coatings are carried out respectively by scanning electron microscopy associated with energy dispersive X-ray spectroscopy (SEM-EDXS) and X-ray diffraction (XRD). The in vitro dissolution-precipitation properties of the coated substrates are investigated by immersions into Dulbecco's Modified Eagle Medium (DMEM) from 1 to 28 days. The calcium and phosphorus concentrations variations in the biological liquid are assessed by Induced Coupled Plasma - Atomic Emission Spectroscopy (ICP-AES) for each immersion time. Furthermore, the corrosion behavior of the coated substrates are investigated using potentiodynamic polarization tests in DMEM and in Ringer's solution. The results show that this innovative process is suitable to synthesize two coatings composed respectively of HAP (37%)/β-TCP (63%) and HAP (62%)/β-TCP (38%) with different morphologies. On the other hand, the in vitro studies reveal that the coatings composition greatly influences their behavior in physiological medium, i.e. their dissolution-precipitation and their corrosion protection properties

Sol-gel synthesis of 45S5 bioglass – Prosthetic coating by electrophoretic deposition

In this work, the 45S5 bioactive glass has been prepared by the sol-gel process using an organic acid catalyst instead of nitric acid usually used. The physico-chemical and structural characterizations confirmed and validated the elemental composition of the resulting glass. In addition, the 45S5 bioactive glass powder thus obtained was successfully used to elaborate by electrophoretic deposition a prosthetic coating on titanium alloy Ti6Al4V

Electrodeposition of Calcium Phosphate Coatings on Metallic Substrates for Bone Implant Applications: A Review

This review summaries more than three decades of scientific knowledge on electrodeposition of calcium phosphate coatings. This low-temperature process aims to make the surface of metallic bone implants bioactive within a physiological environment. The first part of the review describes the reaction mechanisms that lead to the synthesis of a bioactive coating. Electrodeposition occurs in three consecutive steps that involve electrochemical reactions, pH modification, and precipitation of the calcium phosphate coating. However, the process also produces undesired dihydrogen bubbles during the deposition because of the reduction of water, the solvent of the electrolyte solution. To prevent the production of large amounts of dihydrogen bubbles, the current density value is limited during deposition. To circumvent this issue, the use of pulsed current has been proposed in recent years to replace the traditional direct current. Thanks to breaking times, dihydrogen bubbles can regularly escape from the surface of the implant, and the deposition of the calcium phosphate coating is less disturbed by the accumulation of bubbles. In addition, the pulsed current has a positive impact on the chemical composition, morphology, roughness, and mechanical properties of the electrodeposited calcium phosphate coating. Finally, the review describes one of the most interesting properties of electrodeposition, i.e., the possibility of adding ionic substituents to the calcium phosphate crystal lattice to improve the biological performance of the bone implant. Several cations and anions are reviewed from the scientific literature with a description of their biological impact on the physiological environment

New prosthetic calcium phosphate coatings elaborated by electrodepositon : physico-chemical and structural characterization

Ce manuscrit présente un procédé innovant d’élaboration de revêtements prothétiques phosphocalciques : l’électrodéposition. Un protocole original est développé, qui associe l’électrodéposition en mode courant pulsé et l’incorporation de peroxyde d’hydrogène (H2O2)dans la solution électrolytique. Ce protocole permet d’obtenir des revêtements phosphocalciques homogènes et compacts dont la composition chimique est contrôlée. Ils peuvent être constitués d’une hydroxyapatite déficitaire en calcium avec un déficit variable ou d’une hydroxyapatite stoechiométrique. La morphologie des revêtements élaborés est observée par MEB et MEBT, et leur composition chimique est étudiée par microanalyse X et par une méthode normalisée basée sur la DRX, en déterminant le rapport atomique Ca/P caractéristique de ces revêtements. L’étude du comportement en température des échantillons élaborés est présentée afin de déterminer la température optimale de traitement nécessaire pour obtenir une valeur suffisante de l’adhérence du revêtement phosphocalcique sur le substrat métallique. Malgré une limitation de cette température à 550°C lorsque le traitement est réalisé à l’air, la mesure de l’adhérence conduit à une valeur de 16,5 MPa qui répond aux critères normalisés pour les implants chirurgicaux. Par ailleurs, la bioactivité des revêtements élaborés est évaluée en milieu physiologique en étudiant d’une part leur comportement vis-àvis de la corrosion par la représentation de Tafel des courbes de polarisation et par spectroscopie d’impédance électrochimique, et en étudiant d’autre part les réactions de dissolution-précipitation qui interviennent lors d’une immersion prolongée. La formation d’une couche d’apatite osseuse à la surface du revêtement électrodéposé est alors observée.Le protocole d’élaboration développé permet de moduler l’intensité de ces comportements en milieu physiologique. Enfin, la flexibilité de l’électrodéposition est utilisée pour incorporer uniformément dans les revêtements phosphocalciques élaborés du strontium qui est un agent actif dont la cinétique de relargage en milieu physiologique peut être modulée. Une étude structurale de ces nouveaux revêtements permet d’observer que l’incorporation de cet élément modifie la proportion des phases constituant le revêtement après un traitement en température adéquate. La proportion des phases et la répartition uniforme du strontium sont également observées à une échelle submicrométrique par EELS.This manuscript presents an innovative process to produce prosthetic calcium phosphate coatings: electrodeposition. An original protocol is developed, combining pulsed electrodeposition current mode and the incorporation of hydrogen peroxide (H2O2) into the electrolytic solution. This protocol leads to homogeneous and compact calcium phosphate coatings whose chemical composition is controlled. They may consist of a calcium-deficient hydroxyapatite with a variable deficit or of a stoichiometric hydroxyapatite. The morphology of the coatings is observed by SEM and STEM, and their chemical composition is studied by X-ray microanalysis and by a standardized method based on XRD, determining the characteristic Ca/P atomic ratio of these coatings. The study of the thermal behavior of the elaborated samples is performed in order to determine the optimal treatment temperature to obtain a sufficient value of the calcium phosphate coating adhesion onto the metallic substrate. Despite the limitation of this temperature to 550°C when the treatment is carried out in air, the measurement of the coating adhesion to the substrate leads to a value of 16.5 MPa that corresponds to the standardized criteria for the surgical implants. Furthermore, the bioactivity of the elaborated coatings is evaluated in a physiological environment by studying firstly their corrosion behavior using the Tafel representation of the polarization curves and the electrochemical impedance spectroscopy, and secondly by studying the dissolution precipitation reactions that occur during a prolonged immersion. The formation of a “bonelike” apatite layer on the surface of the electrodeposited coating is then observed. The elaboration protocol developed allows the modulation of these behaviors in physiological medium. Finally, the flexibility of the electrodeposition process is used to uniformly incorporate strontium in the calcium phosphate coating that is an active agent whose release in physiological medium can be modulated. A structural study is performed to observe that the incorporation of this element in the coating modifies the proportion of the phases that compose the coating after a suitable thermal treatment. The phase proportion and the uniform distribution of the strontium are also observed at the submicron scale by EELS

Le financement des missions catholiques au XIXème siècle, entre autonomie laïque et centralité romaine : L’Œuvre de la Propagation de la Foi (1822-1922)

Au XIXe siècle, l’intervention laïque est peu courante dans une Église catholique hiérarchisée où celui qui n’est pas clerc ne fait pas partie de l’Église enseignante ou même agissante. Il faut attendre le concile de Vatican II pour que l’activité des laïques soit envisagée du point de vue de la doctrine. Cependant le XIXe siècle assista à l’émergence de quelques formes variées d’apostolat laïque, de la Société de Saint-Vincent-de-Paul à la première Action catholique, mais rares sont celles q..

Le financement des missions catholiques au XIXème siècle, entre autonomie laïque et centralité romaine : L’Œuvre de la Propagation de la Foi (1822-1922)

Au XIXe siècle, l’intervention laïque est peu courante dans une Église catholique hiérarchisée où celui qui n’est pas clerc ne fait pas partie de l’Église enseignante ou même agissante. Il faut attendre le concile de Vatican II pour que l’activité des laïques soit envisagée du point de vue de la doctrine. Cependant le XIXe siècle assista à l’émergence de quelques formes variées d’apostolat laïque, de la Société de Saint-Vincent-de-Paul à la première Action catholique, mais rares sont celles q..

Effect of surface mechanical attrition treatment on the microstructure of cobalt–chromium–molybdenum biomedical alloy

International audienc

Multilayer thin films of aluminum oxide and tantalum oxide deposited by pulsed direct current magnetron sputtering for dielectric applications

This research describes the synthesis of multilayer thin films of aluminum oxide and tantalum oxide for dielectric applications. The multilayer thin films are made of two, four, or eight oxide layers produced by physical vapor deposition (PVD), specifically mid-frequency pulsed direct current magnetron sputtering. The oxide layers are stoichiometric Al2O3 and Ta2O5 with two specific morphologies observed from cross-section images obtained by scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The Al2O3 layers exhibit a columnar structure whereas the Ta2O5 layers are uniform and dense. However, the morphology of the Ta2O5 layers changes progressively in the four-layer and eight-layer systems under the influence of the morphology of the Al2O3 layer below. This behavior is induced by the morphological continuity of the interface between two oxide layers. X-ray diffraction (XRD) shows the low crystallinity of these oxide layers due to the experimental conditions used during the magnetron sputtering process, particularly the low deposition temperature. The dielectric behavior of the multilayer thin films is studied by dielectric strength measurements. The results are compared to the values obtained for single layers of Al2O3 and Ta2O5 produced under the same experimental conditions. The two-layer system shows an intermediate value compared to the single layers, higher than Al2O3 and lower than Ta2O5. The dielectric strengths of the four-layer and the eight-layer systems are higher than those measured for the single layers of Al2O3 and Ta2O5. Finally, the morphology and the crystallinity of the multilayer thin films are changed by thermal annealing of these samples at 850 °C under vacuum. The thermal annealing induces crystallization of the Ta2O5 layers and the loss of morphological continuity at the interface between the oxide layers. These modifications result however in a lower dielectric strength for all the multilayer thin films