Development of Rapid Bioactivity-Expressed Zr-50Ti Alloys by Surface Treatment with Modified Simulated Body Fluid.

Zr-50Ti alloys are promising biomaterials due to their excellent mechanical properties and low magnetic susceptibility. However, Zr-50Ti alloys do not inherently bond well with bone. This study aims to enhance the bioactivity and bonding strength of Zr-50Ti alloys for orthopedic implant materials. Initially, the surface of Zr-50Ti alloys was treated with a sulfuric acid solution to create a microporous structure, increasing surface roughness and area. Subsequently, low crystalline calcium phosphate (L-CaP) precipitation was controlled by adding Mg2+ and/or CO32- ions in modified simulated body fluid (m-SBF). The treated Zr-50Ti alloys were then subjected to cold isostatic pressing to force m-SBF into the micropores, followed by incubation to allow L-CaP formation. The apatite-forming process was tested in simulated body fluid (SBF). The results demonstrated that the incorporation of Mg2+ and/or CO32- ions enabled the L-CaP to cover the entire surface of Zr-50Ti alloys within only one day. After short-term soaking in SBF, the L-CaP layer, modulated by Mg2+ and/or CO32- ions, formed a uniform hydroxyapatite (HA) coating on the surface of the Zr-50Ti alloys, showing potential for optimized bone integration. After soaking in SBF for 14 days, the bonding strength between the apatite layer and alloy has the potential to meet the orthopedic application requirement of 22 MPa. This study demonstrates an effective method to enhance the bioactivity and bonding strength of Zr-50Ti alloys for orthopedic applications.

Surface Modification of Carbon Fiber-Polyetheretherketone Composite to Impart Bioactivity by Using Apatite Nuclei.

The authors aimed to impart the apatite-forming ability to 50 wt% carbon fiber-polyetheretherketone composite (50C-PEEK), which has more suitable mechanical properties as artificial bone materials than pure PEEK. First, the 50C-PEEK was treated with sulfuric acid in a short time to form pores on the surface. Second, the surface of the 50C-PEEK was treated with oxygen plasma to improve the hydrophilicity. Finally, fine particles of calcium phosphate, which the authors refer to as "apatite nuclei", were precipitated on the surface of the 50C-PEEK by soaking in an aqueous solution containing multiple inorganic ions such as phosphate and calcium (modified-SBF) at pH 8.20, 25 °C. The 50C-PEEK without the modified-SBF treatment did not show the formation of apatitic phase even after immersion in simulated body fluid (SBF) for 7 days. The 50C-PEEK treated with the modified-SBF showed the formation of apatitic phase on the entire surface within 1 day in the SBF. The apatite nuclei-precipitated 50C-PEEK will be expected as a new artificial bone material with high bioactivity that is obtained without complicated fabrication processes.

Synthesis and Characterization of Lithium-Ion Conductive LATP-LaPO4 Composites Using La2O3 Nano-Powder.

LATP-based composite electrolytes were prepared by sintering the mixtures of LATP precursor and La2O3 nano-powder. Powder X-ray diffraction and scanning electron microscopy suggest that La2O3 can react with LATP during sintering to form fine LaPO4 particles that are dispersed in the LATP matrix. The room temperature conductivity initially increases with La2O3 nano-powder addition showing the maximum of 0.69 mS∙cm-1 at 6 wt.%, above which, conductivity decreases with the introduction of La2O3. The activation energy of conductivity is not largely varied with the La2O3 content, suggesting that the conduction mechanism is essentially preserved despite LaPO4 dispersion. In comparison with the previously reported LATP-LLTO system, although some unidentified impurity slightly reduces the conductivity maximum, the fine dispersion of LaPO4 particles can be achieved in the LATP-La2O3 system.

Impartation of apatite-forming ability to chitosan nanofibres by using apatite nuclei.

Chitosan nanofibre-apatite nuclei composites obtained by mixing apatite nuclei which possess high apatite-forming ability with chitosan nanofibre have been expected to be novel bone restorative materials with suitable properties such as light weight, low coefficient of thermal expansion, high mechanical strength, biocompatibility and bioactivity. In this study, the authors prepared three types of apatite nuclei by changing the reaction time aimed to optimise their crystallinity and fabricated their composites with chitosan nanofibre. In order to evaluate the bioactivity in vitro, the authors tested apatite-forming ability in simulated body fluid. As a result, the materials showed enough apatite-forming ability in a short time by mixing chitosan nanofibre and apatite nuclei with extremely low crystallinity and their high reactivity in simulated body fluid.

Impartation of hydroxyapatite formation ability to ultra-high molecular weight polyethylene by deposition of apatite nuclei.

The authors aimed to impart hydroxyapatite formation ability to ultra-high molecular weight polyethylene (UHMWPE) by deposition of apatite nuclei (ApN) by the following two methods. The first method was electrophoretic deposition (EPD). A porous UHMWPE was placed between electrodes in the ApN-dispersed ethanol and constant voltage was applied. By this treatment, the ApN were migrated from anode-side surface to the cathode one through the pores by an electric field in the pores of the UHMWPE and deposited inside the pores. The second method was direct precipitation (DP) of the ApN. A porous UHMWPE was soaked in a simulated body fluid (1.0SBF) with higher pH than the physiological one and subsequently, its temperature was raised. By this treatment, the ApN were precipitated in the pores of the UHMWPE directly in the reaction solution. For both methods, the ApN-deposited UHMWPE showed HAp formation ability not only on the top surface but also inside the pores near the surface of the porous UHMWPE in 1.0SBF although the adhesion strength of thus-formed HAp layer was higher in the case of the EPD in comparison with the DP, oxygen plasma treatment before the DP enabled to achieve a similar level of the HAp layer adhesion to the EPD.

Improvement of hydroxyapatite formation ability of titanium-based alloys by combination of acid etching and apatite nuclei precipitation.

The authors aimed to improve hydroxyapatite formation ability of Ti6Al4V, Ti-15Mo-5Zr-3Al alloy, Ti-12Ta-9Nb-6Zr-3V-O alloy (Gummetal®) and commercially pure Ti (cpTi) mesh by a combination of acid etching and apatite nuclei precipitation. Surfaces of specimens were etched with H2SO4 for pores formation on the specimens. Thus-etched specimens were soaked in an alkalinised simulated body fluid (SBF), which was adjusted at higher pH than that of conventional SBF and this solution was subsequently heated. By this treatment, apatite nuclei were precipitated in the pores of the specimens. By a soak in the conventional SBF to check hydroxyapatite formation ability, hydroxyapatite was covered the entire surfaces of the specimens within 1 day and high hydroxyapatite formation ability was successfully shown. The adhesion strength of the hydroxyapatite film formed in the above SBF test showed larger value as increasing the surface roughness of the specimens by adjusting the above acid etching condition depending on the kinds of Ti-based alloys. This is because the adhesion of the hydroxyapatite film occurred by the mechanical interlocking effect. In addition, this method showed shape selectivity of the materials because similar hydroxyapatite formation ability could be introduced to the cpTi mesh.

Development of bioactive zirconium-tin alloy by combination of micropores formation and apatite nuclei deposition.

In previous studies, Zr gained apatite-forming ability by various methods; however, it took more than 7 days in simulated body fluid (SBF) to gain apatite-forming ability. In this study, the authors developed the method to achieve apatite-forming ability in Zr alloy within 1 day in SBF by a combination with apatite nuclei that promote apatite formation in SBF. First, Zr-Sn alloy was soaked in concentrated sulphuric acid, and pores in micro-level were formed on the surface of Zr-Sn alloy. To attain apatite forming ability in Zr-Sn alloy, second, apatite nuclei were formed in the micropores. To evaluate apatite-forming ability, thus-obtained Zr-Sn alloy with apatite nuclei was soaked in SBF; hydroxyapatite formation was observed on the whole surface of the Zr-Sn alloy plates. From this result, it was clarified that higher apatite-forming ability was attained on the apatite nuclei-treated Zr-Sn alloy with micropores in comparison with that without micropores. When adhesive strength of formed hydroxyapatite film with respect to Zr-Sn alloy plates was measured, high-adhesive strength of the formed apatite film was attained by forming micropores and subsequently precipitating apatite nuclei in the fabrication process because of an interlocking effect caused by hydroxyapatite formed in the micropores.

Role of Magnesium and the Effect of Surface Roughness on the Hydroxyapatite-Forming Ability of Zirconia Induced by Biomimetic Aqueous Solution Treatment.

Zirconia is a well-known bioceramic for dental and orthopedic applications due to its mechanical and aesthetic properties. However, it lacks sufficient bioactivity to bond with the living bone. This study was aimed to induce bioactivity to tetragonal zirconia polycrystal (3Y-TZP) by simple biomimetic aqueous solution treatment. First, hydrofluoric acid (HF) etching was performed to enhance the surface roughness of the 3Y-TZP surface. Then, the samples were treated with two types of aqueous solutions containing calcium and phosphate ions (Ca-P solutions); one solution additionally contained magnesium (Mg) ions and the other without Mg ions. Finally, hydroxyapatite (HAp)-forming ability was evaluated by the conventional simulated body fluid (SBF) test, and the effect of Mg ions on the adhesive strength of the HAp layer to the roughened 3Y-TZP surface was also investigated. The results concluded that there were no noticeable differences in the effect of Mg ions on the HAp-forming ability, and both types of solution treatments resulted in dense HAp formation in 1 day SBF immersion. However, incorporation of Mg ions in one of the Ca-P solutions significantly improved the adhesive strength of the HAp layer to the HF-etched 3Y-TZP substrate compared to the Ca-P solution with no Mg ions.

Effect of Doubled Sandblasting Process and Basic Simulated Body Fluid Treatment on Fabrication of Bioactive Stainless Steels.

In our recent study, we aimed to impart hydroxyapatite (HA)-forming to bioinert stainless steels (SUS316L). The surfaces of SUS316L specimen were treated by a sandblasting process using alumina grinding particles with 14.0 or 3.0 µm for average particle size, respectively. In addition, a doubled sandblasting process (DSP) using the 14.0 µm particles and subsequently 3.0 µm ones were also conducted. Compared with the case of the 14.0 µm particles, the 3.0 µm particles were available to increase the surface roughness and the surface area of the specimen. Moreover, these values were further increased in the case of the DSP. These specimens were soaked in simulated body fluid (SBF) at pH = 8.4, 25 °C and were directly heated in the solution by electromagnetic induction. By this treatment, formation of CaP was induced on each specimen. These materials performed high HA-forming ability in SBF. Average bonding strength of the HA film formed on them in SBF was increased depending on the increase of surface roughness and surface area. These results indicated that sandblasting condition was an important factor to improve interlocking effect related to the increase of the surface roughness and the surface area.

Structural Relaxation of Lix(Ni0.874Co0.090Al0.036)O2 after Lithium Extraction down to x = 0.12.

A structural relaxation study has been carried out on Lix(Ni0.874Co0.090Al0.036)O2 after the electrochemical lithium was extraction down to x = 0.12. These relaxation analyses have been carried out using X-ray diffraction coupled with the Rietveld analysis, assuming two phases (H2 and H3) and co-existence with R3¯m symmetry. The mole fraction of the H3 phase seemed not to vary largely during the relaxation time. As for the lattice constants, both H2 and H3 phases gradually increased the a-axis with the relaxation time. On the other hand, H2 and H3 phases increased and decreased the c-axis, respectively. The results are compared with that of previously reported Ni-rich NCA.

Defect Structure and Oxide Ion Conduction of Potassium Ion Substituted CaWO4.

We have prepared Ca1−xKxWO4−x/2 solid solutions with the Scheelite-type structure to investigate high-temperature electrochemical properties. Room-temperature X-ray diffraction suggested the solid solution range was x ≤ 0.2, since the second phase presumably of K2WO4 was detected for x = 0.3. For all the substituted samples up to x = 0.4, a large jump in conductivity has been observed around 500 °C. At higher temperatures, oxide ion conduction is found to be predominant even for x = 0.4, exceeding the solution limit estimated from the room-temperature XRD. The conductivity at high temperature is essentially proportional to the amount of substituted potassium ions up to x = 0.4, indicating that oxide ion conduction is associated with the formed oxide ion vacancy. High-temperature X-ray diffraction detected no apparent change in lattice parameters around 500 °C for x = 0.1, and the remaining second phase seems to be incorporated into the Scheelite lattice at high temperatures.

Fabrication of Bioactive Fiber-reinforced PEEK and MXD6 by Incorporation of Precursor of Apatite.

We aimed to develop an effective process to provide bioactivity to carbon fiber-reinforced polyetheretherketone (PEEK), glass fiber-reinforced PEEK and glass fiber-reinforced poly(m-xylyleneadipamide)-6 (MXD6), possessing similar elastic modulus to cortical bone in this study. First, we formed fine pores on the surface of each substrate by a short-time sulfuric acid treatment. Second, in order to provide hydrophilic property, we treated the surfaces of each substrate with oxygen plasma. Finally, we deposited fine particles of amorphous calcium phosphate (PrAp) in the pores by soaking each substrate in SBF adjusted at pH 8.40, 25.0°C, and subsequently kept at 70.0°C for 24 h. By this treatment, we obtained the bioactive fiber-reinforced polymers. By soaking thus-obtained each material in SBF, apatite formation was induced on the whole surface of each substrate within 1 day by PrAp deposited in the pores and high apatite-forming ability was performed on each material. The adhesive strength between the apatite layer showed high value by mechanical anchoring effect generated by the apatite formed in the pores. © 2017 Wiley Periodicals, Inc. J Biomed Mater Res Part B: Appl Biomater, 106B: 2254-2265, 2018.

Effect of pores formation process and oxygen plasma treatment to hydroxyapatite formation on bioactive PEEK prepared by incorporation of precursor of apatite.

When bioinert substrates with fine-sized pores are immersed in a simulated body fluid (SBF) and the pH value or the temperature is increased, fine particles of calcium phosphate, which the authors denoted as 'precursor of apatite' (PrA), are formed in the pores. By this method, hydroxyapatite formation ability can be provided to various kinds of bioinert materials. In this study, the authors studied fabrication methods of bioactive PEEK by using the above-mentioned process. First, the fine-sized pores were formed on the surface of the PEEK substrate by H2SO4 treatment. Next, to provide hydrophilic property to the PEEK, the surfaces of the PEEK were treated with O2 plasma. Finally, PrA were formed in the pores by the above-mentioned process, which is denoted as 'Alkaline SBF' treatment, and the bioactive PEEK was obtained. By immersing in SBF with the physiological condition, hydroxyapatite formation was induced on the whole surface of the substrate within 1day. The formation of PrA directly contributed to hydroxyapatite formation ability. By applying the O2 plasma treatment, hydroxyapatite formation was uniformly performed on the whole surface of the substrate. The H2SO4 treatment contributed to a considerable enhancement of adhesive strength of the formed hydroxyapatite layer formed in SBF because of the increase of surface areas of the substrate. As a comparative study, the sandblasting method was applied as the pores formation process instead of the H2SO4 treatment. Although hydroxyapatite formation was provided also in this case, however, the adhesion of the formed hydroxyapatite layer to the substrate was not sufficient even if the O2 plasma treatment was conducted. This result indicates that the fine-sized pores should be formed on the whole surface of the substrate uniformly to achieve high adhesive strength of the hydroxyapatite layer. Therefore, it is considered that the H2SO4 treatment before the O2 plasma and the 'Alkaline SBF' treatment is an important factor to achieve high adhesive strength of hydroxyapatite layer to the PEEK substrate. This material is expected to be a candidate for next-generation implant materials with high bioactivity.

Increased enantioselectivity and remarkable acceleration of lipase-catalyzed transesterification by using an imidazolium PEG-alkyl sulfate ionic liquid.

Several types of imidazolium salt ionic liquids were prepared derived from poly(oxyethylene)alkyl sulfate and used as an additive or coating material for lipase-catalyzed transesterification in an organic solvent. A remarkably increased enantioselectivity was obtained when the salt was added at 3-10 mol % versus substrate in the Burkholderia cepacia lipase (lipase PS-C)-catalyzed transesterification of 1-phenylethanol by using vinyl acetate in diisopropyl ether or a hexane solvent system. In particular, a remarkable acceleration was accomplished by the ionic liquid coating with lipase PS in an iPr(2)O solvent system while maintaining excellent enantioselectivity; it reached approximately 500- to 1000-fold acceleration for some substrates with excellent enantioselectivity. A similar acceleration was also observed for IL 1-coated Candida rugosa lipase. MALDI-TOF mass spectrometry experiments of the ionic-liquid-coated lipase PS suggest that ionic liquid binds with lipase protein.