Niobium treated by Plasma Electrolytic Oxidation with calcium and phosphorus electrolytes.

Niobium plates were electrochemically treated by Plasma Electrolytic Oxidation (PEO) with electrolytes containing phosphorous and/or calcium. Three different electrolyte and experimental parameters were used forming three different surfaces. Film morphology, thickness, and chemical composition were analyzed by scanning electron microscopy (SEM), and energy dispersive spectroscopy (EDS). A profilometer and the sessile drop technique measured the average surfaces roughness (Ra) and contact angles respectively. X-ray diffraction technique (XRD) analyzed the oxide crystallinity, and scratch tests evaluated the film adhesion. All oxidized surfaces presented pores, without observed cracks. Comparing the different experimental conditions, films obtained with phosphoric acid (P100) show superficial pores, phosphorus incorporation, high hydrophilicity, non-crystalline oxide formation, and good scratch resistance. Films treated with calcium acetate electrolyte (Ca100), compared to P100 exhibit smaller size pores and film thickness, smaller hydrophilicity, and lower scratch resistance. They also demonstrated higher oxide crystallinity, calcium incorporation, and pores interconnections. When the PEO was executed with a blended electrolyte containing calcium acetate and phosphoric acid (Ca50P50) the formed films presented the highest thickness, high phosphorus incorporation, and the lowest contact angle compared with other films. In addition, the pores size, the scratch resistance, calcium incorporation, and oxide crystallinity present intermediate values compared to P100 and Ca100 films. Film crystallinity seems to be influenced by calcium incorporation, whereas, hydrophilicity is phosphorus amount dependent. The pores amount and their interconnections reduced the scratch resistance. Surface features obtained in this work are largely mentioned as positive characteristics for osseointegration processes.

Apatite grown in niobium by two-step plasma electrolytic oxidation.

Plasma electrolytic oxidation (PEO) of niobium plates were done electrochemically in two steps with electrolytes containing phosphorous and calcium being observed the formation of crystalline apatite. All samples were submitted to a first step of PEO using an electrolyte containing phosphate ions. The second oxidization step was made using three different electrolytes. Some samples were oxidized by PEO in electrolyte containing calcium, while in other samples it was used two mixtures of phosphoric acid and calcium acetate monohydrate solutions. Three different surface layers were obtained. The morphology and chemical composition of the films were analyzed by scanning electronic microscopy (SEM), and energy dispersive spectroscopy (EDS) respectively. It was observed that all samples submitted to two-step oxidation shown porous surface and a calcium and phosphorus rich layer. Average surface roughness (Ra) was measured by a profilometer remaining in the sub-micrometric range. The contact angle by sessile drop technique, using 1µL of distilled water was performed with an optical goniometer. It was verified a higher hydrophilicity in all surfaces compared to the polished niobium. Orthorhombic Nb2O5 was identified by XRD in the oxide layer. Crystalline apatite was identified by XRD in surfaces after the second oxidation made with the Ca-rich electrolyte and a mixture of an electrolyte richer in Ca compared to P. These results indicate that a two-step oxidized niobium surface present great features for applications in the osseointegration processes: favorable chemical composition that increase the biocompatibility, the formation of crystalline niobium pentoxide (orthorhombic), high hydrophilicity and formation of crystalline calcium phosphate (apatite) under adequate electrolyte composition.

Nanomechanical and nanotribological properties of bioactive titanium surfaces prepared by alkali treatment.

Alkali-heat treatment (AHT) is a simple and practical method to make titanium surfaces bioactive. Hydroxyapatite nucleates on Ti when in contact with body fluids due to the presence of a thin sodium titanate film produced by the AHT. This method was proposed more than a decade ago and it has been widely investigated at varied scopes. However, there is still little information about the mechanical properties of this film. In this work, the tribo-mechanical behavior of films produced by alkali treatment (AT) and AHT on Ti is investigated using instrumented indentation technique. The films were also characterized by TF-XRD, SEM, EDS and in vitro bioactivity tests. Analytical methods were employed to obtain the mechanical properties of the film from instrumented indentation data. The heat treatment subsequent to the alkaline processing increased the film elastic modulus from 1.7 GPa to 2.8 GPa, the hardness from 12 MPa to 20 MPa and the critical load for scratch test from 1.5 mN to 5.5 mN. Despite the overall improvement in the film bioactivity and tribo-mechanical behavior, the AHT elastic modulus is only 2% of the pristine Ti whereas hardness is less than 1%. This information must be considered for implant design purposes.