Key Engineering Materials Vols. 361-363

Abstract: Scanning (SEM) and cross-sectional transmission (TEM) electron microscopy analyses have been performed to study the transformations induced on the surface of titanium implants by a sequence of chemical treatments having as goal to induce the nucleation and growth of hydroxycarbonated apatite (HCA). In the first step, an acid etching forms a rough titanium hydride layer, which remains unchanged after subsequent treatments. In a second step, soaking in a NaOH solution induces the growth of nanobelt tangles of nanocrystallized, monoclinic sodium titanate. In a third step, soaking in a simulated body fluid transforms sodium titanate into calcium and phosphorus titanate, by ion exchange in the monoclinic structure. Then, HCA grows and embodies the tangled structure. The interfaces between the different layers are shown to be strong enough to prevent from interfacial decohesion. The role of the titanate structure in the nucleation of HCA is finally discussed.

Abstract: Bioactive ceramics such as hydroxypatite (HA) promote and enhance biological fixation. There is still a discussion on the desired longevity of the coating. Stable coatings require an optimum between resorption rate, flexural strength and adhesive strength of the coating. Ceramic coatings containing fluorapatite (FA, Ca5(PO4)3F) and calcium zirconium phosphate (CZP, CaZr4(PO4)6) promise lower resorption rates than conventional HA coatings in the biological milieu. It is hoped that they can improve the long-term stability of implants by eliminating the detrimental resorption of coating material. For the in vivo studies plasma sprayed coatings were generated. The materials were implanted into the distal femur epiphysis of rabbits and investigated after 2, 4, 6, 12, and 24 weeks postoperatively. Histological analysis was preformed on the areas surrounding the implant. The amount of osseointegration was determined by using the automatically image analysis. The bonding strengths were compared with HA coating and uncoated titanium alloy. According to available data, there is inhibition of mineralization of bone at the interface of calcium zirconium phosphate ceramics of the described composition.

Abstract: In the present work two different hydroxyapatite nanofilms (50 and 100 nm thick) have been successfully deposited on titanium implants that were previously laser macrostructured in order to assess the influence of the thickness of nanometric calcium phosphate coatings on the osseointegration. Cylindrical implants were tested in a sheep tibia model together with titanium alloy controls achieving very good osseointegration results. Laser macrostructured titanium alloy implants have shown improved bone regeneration when coated with nanometric films of carbonated HA. The pulsed laser deposited nanofilm has promoted bone in-growth deep into the laser ablated craters. There were no significant differences between the two coating thicknesses, neither when assessed with electron microscopy or classical optical methods. This result suggests that the 50 nm coating is as effective as the 100 nm one, therefore implying that the thickness limit for such a bioactive layer to stimulate bone growth may be even further below.

Abstract: Objective: This series of laboratorial and in-vivo studies describe the characterization, evolution, and in-vivo performance of various Ca- and P-based nanothicknesses and microstructures ion beam assisted depositions (IBAD) onto Ti-6Al-4V implants. Materials and Methods: Characterization- The 4 mm in diameter and 10 mm in length implant rods (Ti-6Al-4V) with IBAD I, IBAD II, and control (alumina-blasted/acid-etched, AB/AE) surfaces were provided by an implant manufacturer. The in-vitro characterization comprised the following techniques: (1) SEM/EDS, (2) XPS/Depth Profiling (3) Thin-film XRD (4) AFM + ToF-SIMS for coating thickness determination (5) AFM- Ra determination. In-vivo- Three animal experiments were carried out for evaluation of the nanothickness bioceramic coatings. All experiments comprised a proximal tibia model with 4-6 implants placed along the bones. Times in-vivo ranged from 2-5 weeks. Static (bioactivity, bone to implant contact) and dynamic (mineral apposition rates- MAR) histomorphometric measurements were recorded. Biomechanical testing was performed by pullout and torque to interfacial failure testing. Results: Combination of the characterization techniques showed that all bioceramic coatings were Ca- and P-based bioceramics of amorphous microstructure. AFM +ToF-SIMS showed that IBAD II coatings were thicker (300-500 nm) compared to IBAD I coatings (30-50 nm). Surface roughness did not change significantly for the IBAD implant groups compared to control. The in-vivo results showed higher degrees of osseoactivity, torque to failure, and MAR for the coated implants at different times in-vivo. IBAD II had higher biomechanical fixation at early implantation times compared to other groups. Conclusions: The results obtained in the in-vitro part this study support that both IBAD I and IBAD II coatings are Ca- and P- based amorphous bioceramics in the nanothickness range with theoretical high dissolution rates. The increased osseoactivity observed for IBAD coated and the high MAR values observed for IBAD coated compared to AB/AE implants support the effect of the bioceramic coating presence in the overall bone healing. A thickness effect was reveled through biomechanical testing where IBAD II (300-500nm thickness) presented higher performance.

Abstract: Two different techniques were used to promote a bioactive surface on a cobalt base alloy: i) the cobalt alloy melt was cast into wollastonite-coated cavities of an investment mold, or ii) wollasonite-encapsulated as-cast samples were heat treated at 1220°C for 1 h, this is the typical treatment performed to this alloy for improving its mechanical behavior. In vitro bioactivity was assessed by immersing samples in a simulated body fluid for 21 days. Potentially bioactive layers were obtained in both of the cases. A thicker apatite layer was formed on the samples obtained by investment casting. However, since the heat treatment needs to be performed, the heat treatment method is also a promising technique for promoting the bone-bonding ability of this Co alloy.

Abstract: Discs of TiAl6V4 were cleaned and stored in calcium containing salt melt. The characterization of the reaction layer was realized by TF-XRD, SEM, SIMS, AES, and eddy current. The release of Ca ions was determined after storing the samples in TRIS-HCl buffer solution under physiological conditions for at least 16 weeks. The thickness of the generated calcium titanate layer varied in dependence on salt melt composition, temperature, and storing time in the range of 0.4-0.9.m. The Ca content of the layer depends on melt composition, temperature and storing time and was in the range from 5-42.g●cm-2 in correlation with the thickness. The morphology of the layers also changed in dependence on the salt melt composition and the storing time and temperature.

Abstract: We have developed a new Ti alloy, Ti-15%Zr-4%Nb-4%Ta alloy (Ti-15-4-4) that showed higher biological safety and mechanical properties than the currently used Ti-6%Al-4%V alloy. The purpose of this study is to determine the biological performance of the new alloy. Ti-15-4-4 implants (machined or blasted) were placed in surgically created defects in rabbit femurs. The rabbits were sacrificed after 4, 8, 16, 24 and 48 weeks. Bone mineral density (BMD) and area of newly formed bone around the implants were measured using micro-CT. Results showed that the Ti-15-4-4 alloy is biocompatible and forms new bone around the Ti-15-4-4 implant, regardless of the surface treatment. The BMD and area of newly formed bone around the blasted implant surfaces were significantly greater than those around the machined surfaces. These results indicate that the new Ti-15-4-4 alloy has a potential for use as implants and has the advantage of improved mechanical properties described in earlier studies.

Abstract: In this work, a solution able to precipitate calcium phosphate in titanium samples was studied. At first, a thermodynamic analysis of the proposed solution was conducted using a computational simulator that considers most of chemical reactions and evaluates parameters such as activity of species. After this procedure, experimental tests were performed in order to confirm this precipitation. With the use of TRIS at concentration of 50mM, the deposits were basically composed of octacalcium phosphate, as confirmed in some characterization techniques. The deposit presents a thickness of approximately 15μm after a 7-day exposure in the designed solution.

Abstract: Two different Ti oxide films produced by anodic oxidation were submitted to in vitro bioactivity and cell culture tests. The oxide films were produced in 1.0M H2SO4/150V and 1.0M Na2SO4/100V. Surfaces were found to be homogeneous and rough, with the presence of pores. Both oxide films presented anatase and rutile phases. Ti oxide film produced in Na2SO4 was rougher than the film grown with H2SO4 and composed of a rutile-rich phase. Both films were constituted by TiO2 and Ti2O3 oxides. Despite the differences observed, after 7 days, a calcium phosphate layer was precipitated on both surfaces. Indeed, these two treatment conditions seem to be efficient to spread and attach osteoblast-like cells within 4h.

Abstract: Plasma immersion ion implantation (PIII) is a very attractive method for the surface treatment of titanium hard tissue replacements such as hip joints and enhancement of the mechanical, chemical and biological properties of titanium. It has been considered as an alternative to form protective and hard oxide films on titanium and titanium-based implants. In this study, titanium oxide (TiO2) thin films were formed on titanium using PIII, which produces films with adhesion superior to those prepared with conventional techniques. The films were analysed by atomic force microscopy (AFM), X-ray diffraction (XRD) and pull test.