Key Engineering Materials Vols. 529-530

Abstract: The aim of the study was to investigate the reaction of phosphate bonded investment to zirconia during for the heat-pressing technique. Two kinds of dental zirconia were used in this study (inCoris ZI and P-NANOZR). Zirconia was invested into the three kinds of phosphate-bonded investment (Ceravety, PC-15 and Norivest). The investments were fired at several different temperatures. The X-ray diffraction peaks due to monoclinic ZrO₂ were not detected on the waxed-up side of zirconia discs. It demonstrates that no low temperature degradation occurred during the heating of the investment. X-ray diffractometry revealed that the peak assigned to ZrP₂O₇ was detected on the contact side of zirconia discs fired with phosphate-bonded investment at 850 and 950°C. It also revealed that diffraction peak assigned to YPO₄ and the monoclinic ZrO₂ were detected in the same side of zirconia discs contacted with phosphate-bonded investment fired at 1100 °C. It can be concluded that the reduction of Y caused the transformation from tetragonal to monoclinic phase and the reduction of strength.

Abstract: Direct pulp capping involves the application of dental materials to the exposed pulp in an attempt to act as a barrier, protect the dental pulp complex and preserve its vitality. The materials for direct pulp capping should ideally adhere to dental pulp tissue as soft tissue and dentin as hard tissue with tight sealing. We therefore developed visible light-induced crosslinkable gelatin which is capable of adhesive to soft tissue and hard tissue.

Abstract: Preparation of bioactive titanium (Ti) metal able to release Zn²⁺ ions was attempted by chemical and heat treatments of Ti metal. Ti metal was soaked in 5M NaOH solution at 60 °C to form sodium hydrogen titanate (SHT) on its surface. Then, it was soaked in a mixed solution of 100 mM Ca(CH₃COO)₂ and 0.01 - 1 mM Zn (CH₃COO)₂ at 40 °C for 24 h to replace Na⁺ ions in SHT with Ca²⁺ and Zn²⁺ ions at given range of 0.15 to 2.95 in Zn/Ca ratio. When it was heat-treated at 600 °C for 1 h, zinc-incorporated calcium titanate (ZCT) and rutile were formed on the surface of Ti metal. The ZCT partially replaced its Ca²⁺ and Zn²⁺ ions with H₃O⁺ ions by subsequent soaking in 1 mM acetic acid solution at 80 °C. Thus treated Ti metal formed apatite on its surface in a simulated body fluid (SBF) within 3 days, and slowly released Zn²⁺ ions into phosphate-buffered solution (PBS) up to 0.03 ppm. The Ti metal formed with this kind of bioactive ZCT layer on its surface is expected to be useful as orthopedic and dental implants, since it could bond to living bone sooner, by promoting formation of the surrounding bone.

Abstract: Micropores were formed on the surface of Ti metal, Ti-15Mo-5Zr-3Al alloy, Ti-12Ta-9Nb-3V-6Zr-O alloy plate by doubled sandblasting process using silicon carbide particles with 14.0 μm for average particle size as first process, then using the particles with 3.0 μm for average particle size as second process. Apatite Nuclei (AN) were precipitated in the pores. By these treatments, bioactive AN-precipitated Ti alloys were fabricated. Bioactivity of the AN-precipitated Ti alloys was examined by soaking in SBF and it was observed that hydroxyapatite was induced on the surface of the Ti alloys within 1 d. High adhesive strength of hydroxyapatite layer was achieved due to a mechanical interlocking effect between hydroxyapatite formed in the micropores and the plate.

Abstract: At the neck area of dental implant surface, machined surface (Ms) has been employed to avoid surface contamination. Recently, implants which have roughened surface texture (Rs) at their neck are also available. However, from the viewpoint of soft tissue integration, it remains to be elucidated whether or not surface topography affects the soft tissue attachment around implants. The aim of the present study was to clarify the influence of surface topography on peri-implant soft tissue integration. First, surface roughness of both surfaces was measured. Second, protein adsorption capability on both surfaces was examined. Then, as the rat implant model, titanium implants with each surface were inserted into the maxillae. Horseradish peroxidase (HRP) tracer was applied 4 weeks post implantation to the gingival sulci of implants or natural teeth (NT) to investigate the sealing capability of periodontal/peri-implant soft tissue. Collagen density was also observed by fluorescent staining. As a result, surface roughness (Sa) of Ms and Rs was 0.16 µm and 0.25 µm, respectively. Protein adsorption capability on both surface showed no significant differences. In the NT group of the rat implant model, presence of HRP was restricted only in the coronal portion of epithelium. In both implant groups, in contrast, more invasion of HRP was observed in the soft tissue around implants. Especially in the Ms group, more HRP was observed in the deeper area compared with Rs group. Stronger expression of collagen was observed around Rs compared to Ms at the connective tissue-implant interface. It could be speculated that, with dense collagen, Rs implants showed stronger soft tissue integration compared with Ms implants, but the integration is not as strong as NT’s.

Abstract: Electrochemical surface treatments of micro-arc oxidation (MAO) and following cathodic polarization were performed on zirconium (Zr) disks in this study to enhance the bioactivity of Zr. The surface oxide layers formed with electrochemical treatments on Zr disks were characterized using surface analyses; the calcium phosphate formation on the specimens after immersion in Hanks’ solution was evaluated. As a result, thick calcium phosphate layers formed on only Zr specimens that underwent both MAO treatment with a mixture of calcium glycerophosphate and magnesium acetate and subsequent cathodic polarization treatment with sodium sulfate solution, while no precipitate was observed without treatment. Thus, this technique was confirmed to be a promising method to improve the bioactivity of Zr.

Abstract: Sodium hydroxide (NaOH)-, heat- and autoclave-treated Ti metal did not form apatite in simulated body fluid (SBF) within 7 days although certain amounts of sodium (Na) still remained on the Ti metal surface even after the autoclave treatment. When hot water treatment was applied between NaOH and heat treatment, the Ti metal formed apatite within 7 days in SBF. Anatase-type TiO₂ was partially precipitated by the NaOH and heat treatment but it was disappeared by the subsequent autoclave treatment. When the hot water treatment was applied between the NaOH and heat treatment, considerable amount of anatase-type TiO₂ was formed and it still remained even after the autoclave treatment. The zeta potential of the Ti metal with the hot water treatment was almost zero in SBF. These results indicate that Ti metal can show apatite-forming ability in SBF even after autoclave treatment, when hot water treatment is applied between the NaOH and heat treatment, and that anatase-type TiO₂ might play an important role in the apatite formation rather than the amount of Na and/or the zeta potential.

Abstract: Titanium and its alloys are the main metals studied as porous metallic implants by their excellent mechanical properties and biological interactions. Production methods of porous metallic materials are based on powder metallurgy (PM), because it allows the manufacturing of parts with complex shapes and dimensions close to the finals (near-net shape), and the addition of alloying elements reaching a satisfactory structural homogeneity, and porosity. The pore production by space-holder technique constitutes of mixing organic compounds with metal powder, which when removed by thermal treatment prior structures are kept in place. The objective of this study is to obtain porous implants of commercially pure titanium (cpTi) and Ti-13Nb-13Zr alloy by PM with space-holder technique and albumin as an additive. For the processing of the samples were used hydride titanium powder (TiH₂) to obtain cpTi samples, and metal powders of Ti, Nb and Zr in the stoichiometric proportions for obtaining the alloy samples. The samples were prepared by mixing the metallic powder to the albumin (30wt%) and filling a silicone model that was pressed isostatically (140 MPa). The thermal treatment was performed in an oxidizing atmosphere (350°C/1h) for the decomposition of organic material. The sintering was performed at a temperature of 1300°C (1h/cpTi, 3h/Alloy) in high vacuum furnace (10^-5 mBar) to all samples. The calculated porosity showed a significant difference between the samples cpTi (40%) and alloy (60%). The samples surface characterization showed very rough with high specific surface area. Samples of cpTi presented formation of necks arising from sintering. In the alloy samples were observed homogenous microstructure with the presence of α and β phases composing the Widmanstätten structure. It is possible to conclude that the same amount albumin allowed the formation of pores in the microstructure of cpTi and alloy although in different proportions, without harming the sintering of both and allowing diffusion of the alloy elements.

Abstract: Electron beam melting (EBM) method is one of the free-form fabrication techniques that enable near-net-shape manufacturing of complex three-dimensional, porous, and graded products, and is expected to facilitate the development of new methods for manufacturing biomaterials that could be used for hard-tissue substitutes. Titanium and its alloys have been used widely as biomaterials for hard-tissue substitutes because of their excellent mechanical properties and biocompatibility. However, the osteointegration of these materials is less than that of bioactive ceramics. Therefore, various surface-modification techniques have been developed to improve the osteointegration. The simplest way is to synthesize bioactive ceramic films on the surface of titanium or its alloys. The purpose of the present work was to synthesize a bioactive TiO₂ film on Ti-6Al-4V (hereafter, abbreviated as Ti-64) substrates fabricated from powders using the EBM method and treated by a combination of chemical and hydrothermal treatment. Ti-64 plates fabricated by the EBM method were chemically treated with a H₂O₂/HNO₃ aqueous solution under appropriate conditions. The plates were then hydrothermally treated with a NH₃ aqueous solution. TiO₂-gel films were produced by chemical treatment with a H₂O₂/HNO₃ aqueous solution on the surface of a Ti-64 substrate. Anatase-type TiO₂ films with high crystallinity were synthesized by the hydrothermal treatment of the TiO₂-gel films.

Abstract: The objective of this study was to evaluate the corrosion behavior of Ti-29Nb-13Ta-4.6Zr alloy (TNTZ) with immersion in an acidic saline solution containing fluoride by investigating change in color and the surface structure of the oxide film. With immersion in fluoride-containing solution, TNTZ showed a less marked change in color than commercially pure titanium (TI), and a smaller decrease in glossiness. The outermost surface was covered with oxides from its constituent elements at before and after immersion in solution with or without fluoride. When immersed in fluoride-containing solution, the film consisted of larger niobium and tantalum oxides than that before or after immersion in solution without fluoride. In summary, TNTZ showed superior resistance to discoloration to TI after immersion in fluoride-containing solution. The results suggest that the subsequent increase in niobium and tantalum fractions in the oxide film in TNTZ improves resistance to corrosion.