Cosmin Mihai Cotrut

A biodegradable AZ91 magnesium alloy coated with a thin nanostructured hydroxyapatite for improving the corrosion resistance

The main aim of this study was to investigate the properties of an AZ91 alloy coated with nanostructured hydroxyapatite (HA) prepared by radio frequency (RF) magnetron sputtering. The bioactivity and biomineralization of the AZ91 magnesium alloy coated with HA were investigated in simulated body fluid (SBF) via an in vitro test. Scanning electron microscopy (SEM), Fourier transform infrared (FTIR) spectroscopy, and X-ray diffraction (XRD) analyses were performed. The samples were immersed in SBF to study the ability of the surface to promote the formation of an apatite layer as well as corrosion resistance and mass change of the HA-coated AZ91 alloy. Electrochemical tests were performed to estimate the corrosion behaviour of HA-coated and uncoated samples. The results revealed the capability of the HA coating to significantly improve the corrosion resistance of the uncoated AZ91 alloy.

Characterization and In Vitro and In Vivo Assessment of a Novel Cellulose Acetate-Coated Mg-Based Alloy for Orthopedic Applications

Despite their good biocompatibility and adequate mechanical behavior, the main limitation of Mg alloys might be their high degradation rates in a physiological environment. In this study, a novel Mg-based alloy exhibiting an elastic modulus E = 42 GPa, Mg-1Ca-0.2Mn-0.6Zr, was synthesized and thermo-mechanically processed. In order to improve its performance as a temporary bone implant, a coating based on cellulose acetate (CA) was realized by using the dipping method. The formation of the polymer coating was demonstrated by FT-IR, XPS, SEM and corrosion behavior comparative analyses of both uncoated and CA-coated alloys. The potentiodynamic polarization test revealed that the CA coating significantly improved the corrosion resistance of the Mg alloy. Using a series of in vitro and in vivo experiments, the biocompatibility of both groups of biomaterials was assessed. In vitro experiments demonstrated that the media containing their extracts showed good cytocompatibility on MC3T3-E1 pre-osteoblasts in terms of cell adhesion and spreading, viability, proliferation and osteogenic differentiation. In vivo studies conducted in rats revealed that the intramedullary coated implant for fixation of femur fracture was more efficient in inducing bone regeneration than the uncoated one. In this manner, the present study suggests that the CA-coated Mg-based alloy holds promise for orthopedic aplications.

Study on a hydrophobic Ti-doped hydroxyapatite coating for corrosion protection of a titanium based alloy

In the paper, hydroxyapatite coatings enriched with Ti were prepared as a possible candidate for biomedical applications, especially for implantable devices that are in direct contact with bone. The hydroxyapatite coatings with different Ti contents were prepared by an RF magnetron sputtering method on a Ti6Al4V alloy using pure hydroxyapatite and TiO2 targets. The Ti content was modified by changing the RF power fed to the TiO2 target. The formation of the hydroxyapatite compound was not influenced by the addition of Ti. The Ca/P ratio of the Ti-doped hydroxyapatite coatings was found to be in the range between 1.64 and 1.68, which is close to the stoichiometric hydroxyapatite coating. The roughness of the doped hydroxyapatite coatings was augmented by increasing the RF power on the TiO2 cathode. The addition of Ti led to an increase in the contact angle of the hydroxyapatite coatings. The in vitro corrosion performance of the Ti6Al4 alloy was improved significantly by the hydrophobic hydroxyapatite coatings with and without the Ti addition. A surface with a higher Ti concentration and water contact angle exhibited a better corrosion resistance in simulated body fluid at 37 °C. Therefore, the deposition of a hydrophobic Ti-doped HA coating could be a promising surface treatment for the improvement of the electrochemical behaviour of metallic implants.

Development of Bioabsorbable Interference Screws: How Biomaterials Composition and Clinical and Retrieval Studies Influence the Innovative Screw Design and Manufacturing Processes

The current development of bioresorbable materials provided the support for improvement of the clinical performance of the interference screws used during knee-ligament reconstruction. In general, commercially available biodegradable interference screws used in clinical practice are chemically based on degradable, but now a trend to use biodegradable composite materials using the same synthetic biodegradable polymers as matrix reinforced with biodegradable ceramics could be observed. Hydroxyapatite or tricalcium phosphate are used as ceramics in order to reduce the foreign body reaction and increase osteoconduction and mechanical properties of the biodegradable composite materials. In our study several new design features of an innovative interference screw were proposed in order to ameliorate press-fit fixation without damaging the graft based on clinical experience, retrieval analysis of some failed screw, and finite element simulation. We proposed a self-tapping screw with conical shape and three cutting flutes at the distal end and cylindrical shape at the proximal end. The clinical performance of an interference screw is assured by the combination between the clinical technique, screw design, and biodegradable composite material properties, which guarantees the integrity of the screw during insertion, the tissue regrowth, and the stability of fixation.

Radio Frequency Magnetron Sputter Deposition as a Tool for Surface Modification of Medical Implants

The resent advances in radio frequency (RF)‐magnetron sputtering of hydroxyapatite films are reviewed and challenges posed. The principles underlying RF‐magnetron sput‐ tering used to prepare calcium phosphate‐based, mainly hydroxyapatite coatings, are discussed in this chapter. The fundamental characteristic of the RF‐magnetron sputtering is an energy input into the growing film. In order to tailor the film properties, one has to adjust the energy input into the substrate depending on the desired film properties. The effect of different deposition control parameters, such as deposition time, substrate tem‐ perature, and substrate biasing on the hydroxyapatite (HA) film properties is discussed.

Influence of the electrolyte’s pH on the properties of electrochemically deposited hydroxyapatite coating on additively manufactured Ti64 alloy

Properties of the hydroxyapatite obtained by electrochemical assisted deposition (ED) are dependent on several factors including deposition temperature, electrolyte pH and concentrations, applied potential. All of these factors directly influence the morphology, stoichiometry, crystallinity, electrochemical behaviour, and particularly the coating thickness. Coating structure together with surface micro- and nano-scale topography significantly influence early stages of the implant bio-integration. The aim of this study is to analyse the effect of pH modification on the morphology, corrosion behaviour and in vitro bioactivity and in vivo biocompatibility of hydroxyapatite prepared by ED on the additively manufactured Ti64 samples. The coatings prepared in the electrolytes with pH = 6 have predominantly needle like morphology with the dimensions in the nanometric scale (~30 nm). Samples coated at pH = 6 demonstrated higher protection efficiency against the corrosive attack as compared to the ones coated at pH = 5 (~93% against 89%). The in vitro bioactivity results indicated that both coatings have a greater capacity of biomineralization, compared to the uncoated Ti64. Somehow, the coating deposited at pH = 6 exhibited good corrosion behaviour and high biomineralization ability. In vivo subcutaneous implantation of the coated samples into the white rats for up to 21 days with following histological studies showed no serious inflammatory process.

Potential Controlled Co-Ni Nanowires with Compositional Gradient

Co-Ni nanowires with composition gradient were grown by template assisted electrochemical deposition. Using PCTE membrane to grow nanowires makes the deposition of an alloy inside the pores more challenging because the growth is affected by the transport of the electroactive ions into the pores. A novel step-wise deposition-stripping strategy was used to grow NWs with controlled composition along the length of nanowire while maintaining constant the electrolyte composition. A detailed electrochemical analysis was performed to understand and control the Co stripping process, and to demonstrate the applicability of the proposed method. Redox reactions allow us to create custom deposition-stripping programs that enable us to better select and control the potential used to grow the nanowires of controlled composition. Samples were analyzed using scanning electron microscopy (SEM) and EDS. Quantitative analysis performed on samples has revealed that the designed stripping technique and selected potentials resulted in Co-Ni nanowires with up to 3 times more Ni then the samples obtained from similar electrolyte.

Corrosion Behavior of TiSiN Coatings Deposited on Ni-Cr Alloy in Artificial Saliva with and without Fluoride

TiSiN thin films were deposited on NiCr dental alloy in order to enhance the corrosion resistance in artificial saliva with and without fluoride content. The TiSiN films were prepared using reactive cathodic arc method at two different substrate bias voltages (-50 V and-200 V). For the corrosion evaluation, artificial saliva with pH=5.2 was chosen, because this is a critical value for mineral dissolution of dental tissue which can affect the dental alloys. A content of 0.1 % NaF was added to the artificial saliva to simulate the effect of fluoride based hygiene products. The TiSiN coated NiCr alloys exhibited a higher corrosion resistance than the NiCr substrate, irrespective of the testing environment. The best corrosion resistance was found for the TiSiN deposited at-200 V.

TiSiN coatings for improved bond strength of CoCr alloy to dental ceramic

In this work, TiSiN coatings were selected to improve the adhesion between dental ceramic and CoCr substrate. The coatings were prepared by the cathodic arc technique in N2 reactive atmosphere, at different bias voltages, and analyzed for elemental composition, surface roughness, wettability and corrosion resistance in Fusayama Meyer artificial saliva. After the coating deposition, low-fusing dental ceramic film was fired on coated alloy, using a dental furnace. The bond strength of these specimens was tested using a 3-point bending test.