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.

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.

Generation of hydroxyapatite patterns by electrophoretic deposition.

Hydroxyapatite (HAp) patterns with distinct boundaries were generated by electrophoretic deposition (EPD) utilizing an insulating mask that partially blocks the electric field. For the EPD process, we selected two types of mask: a polytetrafluoroethylene (PTFE) board with holes and a resist pattern. A porous PTFE film, which differed from the mask PTFE, was employed as a substrate and attached to the mask. EPD was performed with a suspension of wollastonite particles in acetone, which were deposited on the substrate in the form of the patterned mask. The deposited wollastonite particles induced HAp patterns during a soak in simulated body fluid (SBF). As a result, minute HAp patterns, such as dots, lines, and corners were fabricated on the porous PTFE substrate with a minimum line width of about 100 microm.

Excitation energy dependence for the Li 1s X-ray photoelectron spectra of LiMn2O4.

The Li 1s XPS (X-ray Photoelectron Spectroscopy) spectra of LiMn2O4, which is one of the major positive-electrode materials in lithium-ion rechargeable batteries, and MnO2 as a reference material, were measured by a laboratory-type XPS spectrometer. The Li 1s peak was not observed in the spectra excited by the Mg Kalpha line (1253.6 eV), because the Li 1s peak overlapped the background of the Mn 3p peak of LiMn2O4. The photoionization cross section of Mn 3p was larger than that of Li 1s for Mg Kalpha excitation. Therefore, the XPS measurement of LiMn2O4 by soft X-ray synchrotron excitation was carried out at beamline BL-7B on NewSUBARU synchrotron facility. Excitation energies of 110, 120, 130, 140, 150 and 151.4 eV were selected. The Li 1s peak was clearly observed in these XPS spectra. In order to investigate the excitation energy dependence, the area ratio of the Li 1s and Mn 3p peaks in the XPS spectra was plotted against the excitation energy. As a result, when the excitation energy was 110 eV, the area ratio had the maximum value.

Preparation of ferrimagnetic magnetite microspheres for in situ hyperthermic treatment of cancer.

Ferrimagnetic microspheres 20-30 microm in diameter are useful as thermoseeds for inducing hyperthermia in cancers, especially for tumors located deep inside the body. The microspheres are entrapped in the capillary bed of the tumors when they are implanted through blood vessels and heat cancers locally by their hysteresis loss when placed under an alternating magnetic field. In the present study, preparation of magnetite (Fe(3)O(4)) microspheres 20-30 microm in diameter was attempted by melting powders in high-frequency induction thermal plasma, and by precipitation from aqueous solution. The microspheres prepared by melting powders in high-frequency induction thermal plasma were composed of a large amount of Fe(3)O(4) and a small amount of wustite (FeO), and those subsequently heat treated at 600 degrees C for 1 h under 5.1 x 10(3) Pa were fully composed of Fe(3)O(4) 1 microm in size. The saturation magnetization and coercive force of the heat-treated microspheres were 92 emu g(-1) and 50 Oe, respectively. The heat generation of the heat-treated microspheres was estimated to be 10 Wg(-1), under 300 Oe and 100 kHz. The microspheres prepared by precipitation from aqueous solution consisted of beta-FeOOH, and those subsequently heat treated at 400 degrees C for 1 h in a 70% CO(2) + 30% H(2) atmosphere consisted of Fe(3)O(4) crystals 50 nm in size. The saturation magnetization and coercive force of the heat-treated microspheres were 53 emu g(-1) and 156 Oe, respectively. The heat generation of the heat-treated microspheres was estimated to be 41 Wg(-1), under 300 Oe and 100 kHz. The latter microspheres are believed to be promising thermoseeds for hyperthermic treatment of cancer.

Micropattern formation of apatite by combination of a biomimetic process and transcription of resist pattern.

Two kinds of methods combining a biomimetic process and transcription of resist pattern were conducted to form an apatite micropattern. For method 1, apatite nuclei were formed on a resist pattern printed substrate by setting it in contact with CaO-SiO(2)-based glass in a simulated body fluid (SBF) with inorganic ion concentrations nearly equal to those of human blood plasma. Next, apatite was grown from the nuclei by soaking the substrate in an aqueous solution with ion concentrations 1.5 times those of SBF (1.5 SBF). Then, the resist material was dissolved off by organic solvent with the apatite just formed on it. Apatite micropattern transcribing the resist pattern was obtained. For method 2, apatite nuclei were formed on a resist pattern printed substrate by setting it in contact with CaO-SiO(2)-based glass in SBF. Next, the resist material was dissolved off with the apatite nuclei just formed on it. Then, the substrate was soaked in 1.5 SBF to grow the remaining nuclei and an apatite micropattern transcribing the resist pattern was obtained. For both methods, minute apatite patterns with various shapes as straight lines, bending lines, and blocks were clearly formed. The minimum line width of the obtained pattern was 2 microm. These methods are promising for producing multifunctional materials with bioaffinity.