The influence of titania-zirconia-zirconium titanate nanotube characteristics on osteoblast cell adhesion

Studies of biomaterial surfaces and their influence on cell behavior provide insights concerning the design of surface physicochemical and topography properties of implant materials. Fabrication of biocompatible metal oxide nanotubes on metallic biomaterials, especially titanium alloys such as Ti50Zr via anodization, alters the surface chemistry as well as surface topography of the alloy. In this study, four groups of TiO2-ZrO2-ZrTiO4 nanotubes that exhibit diverse nanoscale dimensional characteristics (i.e. inner diameter Di, outer diameter Do and wall thicknesses Wt) were fabricated via anodization. The nanotubes were annealed and characterized using scanning electron microscopy and 3-D profilometry. The potential applied during anodization influenced the oxidation rate of titanium and zirconium, thereby resulting in different nanoscale characteristics for the nanotubes. The different oxidation and dissolution rates both led to changes in the surface roughness parameters. The in vitro cell response to the nanotubes with different nanoscale dimensional characteristics was assessed using osteoblast cells (SaOS2). The results of the MTS assay indicated that the nanotubes with inner diameter (Di)≈40nm exhibited the highest percentage of cell adhesion of 41.0%. This result can be compared to (i) 25.9% cell adhesion at Di≈59nm, (ii) 33.1% at Di≈64nm, and (iii) 33.5% at Di≈82nm. The nanotubes with Di≈59nm exhibited the greatest roughness parameter of Sa (mean roughness), leading to the lowest ability to interlock with SaOS2 cells.

Hydroxyapatite/titania sol-gel coatings on titanium-zirconium alloy for biomedical applications

A simple sol–gel method was developed for hydroxyapatite/titania (HA/TiO2) coatings on non-toxic titanium–zirconium (TiZr) alloy for biomedical applications. The HA/TiO2-coated TiZr alloy displayed excellent bioactivity when soaked in a simulated body fluid (SBF) for an appropriate period. Differential scanning calorimetry, thermogravimetric analysis, X-ray diffraction and scanning electron microscopy-energy dispersive spectrometry were used to characterize the phase transformations and the surface structures and to assess the in vitro tests. The HA/TiO2 layers were spin-coated on the surface of TiZr alloy at a speed of 3000 rpm for 15 s, followed by a heat treatment at 600 °C for 20 min in an argon atmosphere sequentially. The TiO2 layer exhibited a cracked surface and an anatase structure and the HA layer displayed a uniform dense structure. Both the TiO2 and HA layers were 25 μm thick, and the total thickness of the HA/TiO2 coatings was 50 μm. The TiZr alloy after the above HA/TiO2 coatings displayed excellent bone-like apatite-forming ability when soaked in SBF and can be anticipated to be a promising load-bearing implant material.

Biomimetic processing of nanocrystallite bioactive apatite coating on titanium-zirconium alloy

In this paper nanocrystallite apatite coating on TiZr substrate was prepared by a biomimetic process. Surface morphology, thickness, crystalline phases a~nd bond strength of the coating were investigated by SEM, XRD and tensIle test, respectively. Results show that the apatite coating exhibIts a nanocrystalIite structure with similar stoichiometry to that of natural bone. The apatite layer becomes thicker with the increasing of the SBF immersion time and is firmly adhered to the substrate with the highest average bond strength of 15.5 MPa. This nanocrystallite apatite coating is expected to bond to surrounding bone tissue directly in vivo after implantation.

Nature of new order rights to minerals : a rubikian exercise since passing the mayday rubicon with a cubic zirconium?

The Mineral and Petroleum Resources Development Act 28 of 2002 has created new categories of rights to "minerals" that may be granted to applicants by the Minister of Minerals and Energy. In this article the nature of these rights will be examined. The legislature has labelled prospecting rights and mining rights to minerals as limited real rights in the MPRD Act. The remaining rights to minerals are not labelled. Provision is made for registration or recording rights in the revived Mining Titles Registration Act 16 of 1967 (as amended). Registered rights are claimed to constitute a limited real right binding against third parties. Discrepancies and contradictions regarding the nature of rights to minerals are created by the two statutes. It is concluded that only upon clarification of the provisions of the two sister statutes, would the nature of rights to minerals be more evident. The proposed amendment of section 5(1) of the MPRD Act would be in line with property doctrine based upon the common law and is to be welcomed.

Cell biological responses of osteoblasts on anodized nanotubular surface of a titanium-zirconium alloy

Anodization of titanium and its alloys, under controlled conditions, generates a nanotubular architecture on the material surface. The biological consequences of such changes are poorly understood, and therefore, we have analyzed the cellular and molecular responses of osteoblasts that were plated on nanotubular anodized surface of a titanium-zirconium (TiZr) alloy. Upon comparing these results with those obtained on acid etched and polished surfaces of the same alloy, we observed a significant increase in adhesion and proliferation of cells on anodized surfaces as compared to acid etched or polished surface. The expression of genes related to cell adhesion was high only on anodized TiZr, but that of genes related to osteoblast differentiation and osteocalcin protein and extracellular matrix secretion were higher on both anodized and acid etched surfaces. Examination of surface morphology, topography, roughness, surface area and wettability using scanning electron microscopy, atomic force microscopy, and contact angle goniometry, showed that higher surface area, hydrophilicity, and nanoscale roughness of nanotubular TiZr surfaces, which were generated specifically by the anodization process, could strongly enhance the adhesion and proliferation of osteoblasts. We propose that biological properties of known bioactive titanium alloys can be further enhanced by generating nanotubular surfaces using anodization.

Zirconium, calcium, and strontium contents in magnesium based biodegradable alloys modulate the efficiency of implant-induced osseointegration

Development of new biodegradable implants and devices is necessary to meet the increasing needs of regenerative orthopedic procedures. An important consideration while formulating new implant materials is that they should physicochemically and biologically mimic bone-like properties. In earlier studies, we have developed and characterized magnesium based biodegradable alloys, in particular magnesium-zirconium (Mg-Zr) alloys. Here we have reported the biological properties of four Mg-Zr alloys containing different quantities of strontium or calcium. The alloys were implanted in small cavities made in femur bones of New Zealand White rabbits, and the quantitative and qualitative assessments of newly induced bone tissue were carried out. A total of 30 experimental animals, three for each implant type, were studied, and bone induction was assessed by histological, immunohistochemical and radiological methods; cavities in the femurs with no implants and observed for the same period of time were kept as controls. Our results showed that Mg-Zr alloys containing appropriate quantities of strontium were more efficient in inducing good quality mineralized bone than other alloys. Our results have been discussed in the context of physicochemical and biological properties of the alloys, and they could be very useful in determining the nature of future generations of biodegradable orthopedic implants.

Effects of zirconium and strontium on the biocorrosion of Mg-Zr-Sr alloys for biodegradable implant applications

The successful applications of magnesium (Mg) alloys as biodegradable orthopedic implants are mainly restricted due to their rapid degradation rate in the physiological environment, leading to a loss of mechanical integrity. This study systematically investigated the degradation behaviors of novel Mg-Zr-Sr alloys using electrochemical techniques, hydrogen evolution, and weight loss in simulated body fluid (SBF). The microstructure and degradation behaviors of the alloys were characterized using optical microscopy, XRD, SEM, and EDX. The results indicate that Zr and Sr concentrations in Mg alloys strongly affected the degradation rate of the alloys in SBF. A high concentration of 5 wt% Zr led to acceleration of anodic dissolution, which significantly decreased the biocorrosion resistance of the alloys and their biocompatibility. A high volume fraction of Mg17Sr2 phases due to the addition of excessive Sr (over 5 wt%) resulted in enhanced galvanic effects between the Mg matrix and Mg17Sr2 phases, which reduced the biocorrosion resistance. The average Sr release rate is approximately 0.15 mg L^-1 day^-1, which is much lower than the body burden and proves its good biocompatibility. A new biocorrosion model has been established to illustrate the degradation of alloys and the formation of degradation products on the surface of the alloys. It can be concluded that the optimal concentration of Zr and Sr is less than 2 wt% for as-cast Mg-Zr-Sr alloys used as biodegradable orthopedic implants.

Grain refinement of pure magnesium using rolled Zirmax® master alloy (MG-33.3ZR)

Owing to the limited solubility of zirconium in molten magnesium, almost all of the zirconium contained in the Zirmax® master alloy (Mg-33.3Zr) is present in the form of nearly pure zirconium particles. Of them, zirconium particle clusters and individual zirconium particles greater than 5

Effect of surface roughness of Ti, Zr, and TiZr on apatite precipitation from simulated body fluid

Some of the critical properties for a successful orthopedic or dental implant material are its biocompatibility and bioactivity. Pure titanium (Ti) and zirconium (Zr) are widely accepted as biocompatible metals, due to their non-toxicity. While the bioactivity of Ti and some Ti alloys has been extensively investigated, there is still insufficient data for Zr and titanium-zirconium (TiZr) alloys. In the present study, the bioactivity, that is, the apatite forming ability on the alkali and heat treated surfaces of Ti, Zr, and TiZr alloy in simulated body fluid (SBF), was studied. In particular, the effect of the surface roughness characteristics on the bioactivity was evaluated for the first time. The results indicate that the pretreated Ti, Zr and TiZr alloy could form apatite coating on their surfaces. It should be noted that the surface roughness also critically affected the bioactivity of these pretreated metallic samples. A surface morphology with an average roughness of approximately 0.6 microm led to the fastest apatite formation on the metal surfaces. This apatite layer on the metal surface is expected to bond to the surrounding bones directly after implantation.

Effect of heat-treatment atmosphere on the bond strength of apatite layer on Ti substrate

Objectives
The purpose of this study was to investigate the bond strength of apatite layer on titanium (Ti) substrate coated by biomimetic method and to improve the bonding of apatite layer to Ti substrate by optimizing the alkali heat-treatment process.

Methods
Ti plates pre-treated with an alkali solution of 10 M sodium hydroxide (NaOH) were heat-treated at 600 °C for 1 h at different atmospheres: in air and in vacuum. A dense apatite layer formed on top of the sodium titanate layer after soaking the alkali and heat-treated Ti samples in simulated body fluid (SBF) for up to 3 weeks. The bond strengths of the sodium titanate layer on Ti substrate, and apatite layer on the sodium titanate layer, were measured, respectively, by applying a tensile load. The fracture sites were observed with a scanning electron microscope (SEM).

Results
The apatite layer on the substrate after alkali heat-treatment in air achieved higher bond strength than that on the substrate after alkali heat-treatment in vacuum. It was found that the interfacial structure between the sodium titanate and Ti substrate has a significant influence on the bond strength of the apatite layer.

Significance
It is advised that titanium implants can achieve better osseointegration under load-bearing conditions by depositing an apatite layer in vivo on a Ti surface subjected to alkali and heat-treated in air.

Nanocrystalline zirconia powders synthesised by mechanochemical processing

Mechanochemical processing of zirconium and yttrium chloride precursors with lithium hydroxide has been used to synthesise ultrafine powders of yttria-stabilised zirconia. The precursors reacted during milling to form a composite consisting of nanocrystalline oxide grains embedded within a matrix of lithium chloride. The ultrafine powder was recovered subsequently by removing the lithium chloride through washing with deionised water and methanol. The powders were characterised using X-ray diffraction (XRD), transmission electron microscopy (TEM), and BET gas adsorption. The sintering behaviour of cold pressed pellets was examined by dilatometry.

Influence of calcium ion deposition on apatite-inducing ability of porous titanium for biomedical applications

In the present study, the influence of calcium ion deposition on the apatite-inducing ability of porous titanium(Ti) was investigated in a modified simulated body fluid (m-SBF). Calcium hydroxide (Ca(OH)₂) solutions with five degrees of saturation were used to hydrothermally deposit Ca ions on porous Ti with a porosity of 80%. Apatite-inducing ability of the Ca-ion-deposited porous Ti was evaluated by soaking them in m-SBF for up to 14 days. Scanning electron microscopy (SEM) and X-ray diffractometry (XRD) confirmed that a thin layer of calcium titanate (CaTiO₃)/calcium oxide (CaO) mixture with a nanostructured porous network was produced on porous Ti substrates after hydrothermal treatment at 200 °C for 8 h. X-ray photoelectron spectroscopy results demonstrated that the content of the Ca ions deposited on Ti and the thickness of the CaTiO₃/CaO layer increased with increasing saturation degree of the Ca(OH)₂ solution. The thickest (over 10 nm) CaTiO₃/CaO layer with the highest Ca content was achieved on the Ti treated in an oversaturated Ca(OH)₂ solution (0.2 M). SEM, XRD, transmission electron microscopy and Fourier transformed infrared spectroscopy analysis indicated that the porous Ti samples deposited with the highest content of Ca ions exhibited the best apatite-inducing ability, producing a dense and complete carbonated apatite coating after a 14 day soaking in m-SBF. The present study illustrated the validity of using Ca ion deposition as a pre-treatment to endow desirable apatite-inducing ability of porous Ti for bone tissue engineering applications.