A nitrogen doped TiO<Subscript>2</Subscript> layer on Ti metal for the enhanced formation of apatite

Biomedical titanium metals subjected to gas under precisely regulated oxygen partial pressures (P_O2) from 10⁻¹⁸ to 10⁵ Pa at 973 K for 1 h were soaked in a simulated body fluid (SBF), whose ion concentrations were nearly equal to those of human blood plasma, at 36.5°C for up to 7 days. The effect of oxygen partial pressures on apatite formation was assessed using X-ray diffraction (XRD), scanning electron microscopy (SEM) and X-ray photoelectron spectroscopy (XPS) measurements. After heating, the weight of the oxide layer (mainly TiO₂) formed on the titanium metal was found to increase with increased oxygen partial pressure. Nitrogen (N)-doped TiO₂ (Interstitial N) was formed under a P_O2 of 10⁻¹⁴ Pa. At lower P_O2 (10⁻¹⁸ Pa), only a titanium nitride layer (TiN and Ti₂N) was formed. After soaking in SBF, apatite was detected on heat-treated titanium metal samples. The most apatite was formed, based on the growth rate calculated from the apatite coverage ratio, on the titanium metal heated under a P_O2 of 10⁻¹⁴ Pa, followed by the sample heated under a P_O2 of 10 and 10⁴ Pa (in N₂). The titanium metal heated under a P_O2 of 10⁵ Pa (in O₂) experienced far less apatite formation than the former three titanium samples. Similarly, very little weight change was observed for the titanium metal heated under a P_O2 of 10⁻¹⁸ Pa (in N₂). During the experimental observation period (5 days, 36.5°C, SBF), the following relationship held: The growth rate of apatite decreased in the order P_O2 of 10⁻¹⁴ Pa > P_O2 of 10 Pa ≥ P_O2 of 10⁴ Pa > P_O2 of 10⁵ Pa > > P_O2 of 10⁻¹⁸ Pa. These results suggest that N-doped TiO₂ (Interstitial N) strongly induces apatite formation but samples coated only with titanium nitride do not. Thus, controlling the formation of N-doped TiO₂ is expected to improve the bioactivity of biomedical titanium metal.     

Effect of Ca contamination on apatite formation in a Ti metal subjected to NaOH and heat treatments

It has long been known that titanium (Ti) metal bonds to living bone through an apatite layer formed on its surface in the living body after it had previously been subjected to NaOH and heat treatments and as a result had formed sodium titanate on its surface. These treatments were applied to a porous Ti metal layer on a total hip joint and the resultant joint has been in clinical use since 2007. It has been also demonstrated that the apatite formation on the treated Ti metal in the living body also occurred in an acelullar simulated body fluid (SBF) with ion concentrations nearly equal to those of the human blood plasma, and hence bone-bonding ability of the treated Ti metal can be evaluated using SBF in vitro. However, it was recently found that certain Ti metals subjected to the same NaOH and heat treatments display apatite formation in SBF which is decreased with the increasing volume of the NaOH solution used in some cases. This indicates that bone-bonding ability of the treated Ti metal varies with the volume of the NaOH solution used. In the present study, this phenomenon was systematically investigated using commercial NaOH reagents and is considered in terms of the structure and composition of the surface layers of the treated Ti metals. It was found that a larger amount of the calcium contamination in the NaOH reagent is concentrated on the surface of the Ti metal during the NaOH treatment with an increasing volume of the NaOH solution, and that this inhibited apatite formation on the Ti metal in SBF by suppressing Na ion release from the sodium titanate into the surrounding fluid. Even a Ca contamination level of 0.0005 % of the NaOH reagent was sufficient to inhibit apatite formation. On the other hand, another NaOH reagent with a nominal purity of just 97 % did not exhibit any such inhibition, since it contained almost no Ca contamination. This indicates that NaOH reagent must be carefully selected for obtaining reliable bone-bonding implants of Ti metal by the NaOH and heat treatments.     

Bonelike apatite formation on niobium metal treated in aqueous NaOH

The essential condition for a biomaterial to bond to the living bone is the formation of a biologically active bonelike apatite on its surface. In the present work, it has been demonstrated that chemical treatment can be used to create a calcium phosphate (CaP) surface layer, which might provide the alkali treated Nb metal with bone-bonding capability. Soaking Nb samples in 0.5 M NaOH, at 25 degrees C for 24 h produced a nano-porous approximately 40 nm thick amorphous sodium niobate hydrogel layer on their surface. Immersion in a simulated body fluid (SBF) lead to the deposition of an amorphous calcium phosphate layer on the alkali treated Nb. The formation of calcium phosphate is assumed to be a result of the local pH increase caused by the cathodic reaction of oxygen reduction on the finely porous surface of the alkali-treated metal. The local rise in pH increased the ionic activity product of hydroxyapatite and lead to the precipitation of CaP from SBF that was already supersaturated with respect to the apatite. The formation of a similar CaP layer upon implantation of alkali treated Nb into the human body should promote the bonding of the implant to the surrounding bone. This bone bonding capability could make Nb metal an attractive material for hard tissue replacements.     

Structure formation mechanisms of titanium inflammation in a nitrogen atmosphere

Experimental results on the structure- and phase-formation dynamics in rapid pulse heating of titanium powder in a nitrogen atmosphere are presented. A relation between the main macrokinetic ignition parameters and the microstructure formation process in the system studied is found.Institute for Structural Macrokinetics, Russian Academy of Sciences, Chernogolovka. Translated from Inzhenerno-Fizicheskii Zhurnal, Vol. 64, No. 2, pp. 186–194, February, 1993.     

Thermal behaviours of mechanically alloyed Ti50Al50 in a nitrogen atmosphere

Thermal behaviours of mechanical alloyed Ti₅₀Al₅₀ powders in a nitrogen atmosphere are investigated in this paper. X-ray diffraction and differential thermal analysis were used to determine their characteristics. At the initial milling stage, large amounts of defects were introduced and the grain sizes were gradually refined. The enthalpy changes of formation of -TiAl and ₂-Ti₃Al were decreased with increasing milling times. No obvious dissolution of nitrogen into the powder particles occurred at this stage. With increasing milling time, an amorphous phase containing nitrogen gradually occurred. The amorphous phase and small amounts of Ti solid solution were obtained after milling for 30 h in a N₂ atmosphere. The thermal process included two stages. Firstly, the amorphous phase crystallized at low temperature and resulted in the formation of a nanophase; secondly, the grain growth of this nanocrystalline phase occurred at high temperature. The annealing products are different for the milling products obtained at the initial stage (-TiAl + ₂-Ti₃Al) and final stage (-TiAl + Ti₂AlN), which is attributed to the different nitrogen contents in the milled products. The activation energies for the crystallization and grain growth are 251.9 and 296.9 kJ mol^–1, respectively.     

In-vitro apatite formation on phosphorylated bamboo

Natural self-reinforced composite, bamboo, was surface modified by phosphorylation with urea–H3PO4 and NaOH–H3PO4 methods; then precalcification was performed by immersing samples in saturated Ca(OH)2 solution. After that, calcium phosphate can be formed on the surface of bamboo samples in calcification media: simulated body fluid (1.5 SBF) and accelerated calcification solution (ACS). Experimental results reveal that pre-calcification is an inevitable step for the formation of calcium phosphate. The calcium phosphate formed in 1.5 SBF was identified by thin-film X-ray diffraction as apatite which was not well crystallized. Compared with the urea–H3PO4 method, the NaOH–H3PO4 method has the advantages of quicker and continuous apatite formation and stronger adhesive between apatite and bamboo.     

Bonelike apatite formation on carbon microspheres

Carbon microspheres with a diameter of 2 μm were prepared by hydrothermal process. The apatite-formation ability of the carbon microspheres was evaluated by soaking them in a simulated body fluid (SBF) for 5 and 10 d and apatite-formation mechanism was also analyzed. The result showed that bonelike apatite was formed on the surface of carbon microspheres. Our study indicates that the carbon microspheres synthesized by this method possess apatite-formation ability and may be used as a bioactive injectable filler for bone tissue regeneration.     

Mechanism of surface hardened layer formation on titanium alloys in a rarified nitrogen atmosphere

Translated from Fiziko-Khimicheskaya Mekhanika MaterLalov, Vol. 27, No. 2, pp. 38–42, March–April, 1991.     

Liquid phase deposited titania coating to enable in vitro apatite formation on Ti6Al4V alloy

A recently developed “GRAPE^® technology” provides titanium or titanium alloy implants with spontaneous apatite-forming ability in vitro, which requires properly designed gaps and optimum heat treatment in air. In this study, titanium alloy and commercially pure (cp) titanium substrates were thermally oxidized in air before aligning pairs of specimens in the GRAPE^® set-up, i.e., titanium alloy and cp titanium substrates were aligned parallel to each other with optimum gap width (spatial design). A liquid phase deposition (LPD) technique was employed for titania coatings on titanium alloy substrate. Then, they were soaked in Kokubo’s simulated body fluid (SBF, pH 7.4, 36.5 °C) for 7 days to confirm the in vitro apatite formation on the substrates under the specific spatial design. Anatase-type titania coatings fabricated by using LPD technique led to the deposition of apatite particles within 7 days and showed apatite X-ray diffraction. On the other hand, thermally oxidized titanium alloy substrate in air and non-treated specimens did not show any apatite X-ray diffraction. These results indicated that the heterogeneous nucleation of apatite induced on anatase-type titania coating prepared by LPD technique when it was aligned parallel to thermally oxidized cp titanium substrate with optimum gap width.     

Pores in p-type GaN by annealing under nitrogen atmosphere: formation and photodetector

Journal of Materials Science - Mg-doped p-GaN, which cannot be etched and porosified by wet etching, is annealed in a N2 environment to fabricate porous p-GaN for the first time. In the annealing...     

Reactions in the formation of Na3Zr2Si2PO12

Nasicon ceramics of formula Na₃Zr₂Si₂PO₁₂ were prepared from two systems, namely NH₄H₂PO₄-Na₂CO₃-SiO₂-ZrO₂ and Na₃PO₄-SiO₂-ZrO₂. The partial reactions and sequence of reactions was studied using differential thermal analysis and X-ray diffraction analysis. Kinetic restraints to completeness of reaction are indicated and sodium oxide volatilization is shown to occur. The rate-determining partial reaction involves zirconia and a sodium phosphosilicate intermediate.     

Morphological and chemical characterisation of biomimetic bone like apatite formation on alkali treated Ti6Al4V titanium alloy

The present study is an attempt to enhance the apatite-forming ability of titanium metal induced by the alkaline (NaOH) treatment. A cell free culture medium, acellular DMEM solution was utilised to develop bone-like apatite on alkali-treated titanium alloy surface. The main advantage of this process is the development of bone like apatite with essential trace elements on the metallic substrate by using the DMEM culture medium as a soaking medium. The formed apatite deposits were investigated by scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDXS). The obtained results suggest that the method utilized in this work can be successfully applied to obtain deposition of uniform coatings of crystalline hydroxyapatite on alkali treated titanium substrates.     

Low thermal expansion materials: a comparison of the structural behaviour of La0.33Ti2(PO4)3, Sr0.5Ti2(PO4)3 and NaTi2(PO4)3

Variable temperature neutron powder diffraction data have been used to examine the structural mechanism of unusual thermal expansion behaviour in La_0.33Ti₂(PO₄)₃ (LaTP). These data are compared to those we have recently reported for the related systems NaTi₂(PO₄)₃ (NaTP) and Sr_0.5Ti₂(PO₄)₃ (SrTP), which differ in the extent of occupation of the extra-framework MI (La, Sr, Na) cation sites. The root cause of the unusual behaviour is ascribed to the differing expansivities of the occupied and vacant MI sites. This leads to cooperative rotations of TiO₆ and PO₄ polyhedra, which can be used to quantify and rationalise the overall anisotropic thermal expansion behaviour.     

Ti合金表面沉积羟基磷灰石-牛血清蛋白生物活性涂层

通过仿生生长方法,将预处理后的钛片浸入到添加有牛血清蛋白的模拟体液中,使钙磷盐和牛血清蛋白(BSA)共沉积到钛合金的表面,制备生物活性涂层.利用SEM、XRD、红外光谱等对涂层进行了表征,结果表明:BSA通过化学作用和钙磷盐共沉积到基体的表面,并且BSA具有细化涂层晶粒的作用.     

Influence of surface modification on the apatite formation and corrosion behavior of Ti and Ti-15Mo alloy for biomedical applications

Commercially pure Ti and Ti-15Mo specimens were subjected to alkali-hydrogen peroxide and subsequent heat treatment to produce a nanoporous titanate gel layer with anatase phase. The surface morphology of the untreated, alkali-hydrogen peroxide treated and alkali-hydrogen peroxide heat treated specimens before and after 7 days of immersion in simulated body fluid was characterized using X-ray Diffractometer (XRD), Atomic Force Microscopy (AFM), Scanning Electron Microscopy (SEM) and Fourier Transform Infrared Spectroscopy (FT-IR). The formation of nanoporous titanate gel layer and the growth of apatite layer over the surface modified specimens after 7 days of immersion in simulated body fluid were confirmed. Further, the electrochemical corrosion behavior of all the specimens was examined using potentiodynamic polarization and electrochemical impedance spectroscopic techniques.     

Process of formation of bone-like apatite layer on silica gel

It has been proposed that a hydrated silica plays an important role in forming a biologically active apatite layer on the surfaces of bioactive glasses and glass-ceramics in the body. Recent experiments have shown that a silica hydrogel actually induces apatite formation on its surface in a simulated body fluid (SBF). In the present study the process of apatite formation on silica gel was investigated by means of thin-film X-ray diffraction, Fourier-transformed infrared reflection spectroscopy and scanning electron microscopic observation of the surface of the silica gel, as well as the measurement of changes in the ion concentration of the fluid. It was found that the induction period for the apatite nucleation on the surface of the silica gel was about 6 days. Once the apatite nuclei were formed they grew, taking a spherulitic form by consuming the calcium and phosphate ions from the surrounding fluid. Each spherulite consisted of a lot of flake that clustered into a petal-like morphology. The flake was carbonate-containing hydroxyapatite of small-crystallites and/or defective structure. The Ca/P ratio of the apatite was estimated as 1.5–1.6. Thus, the apatite formed was able to induce secondary nucleation of the apatite.     

Studies of hydride formation in Ti1−xZrxMn2

Hydriding characteristics are presented for compounds in Ti_1?xZr_xMn₂ such as amount of hydrogen take up, equilibrium pressures as a function of temperature and derived thermodynamic parameters (ΔH, ΔS, ΔG). Large reversible hydrogen uptake at ambient conditions is observed in a certain region of composition.     

Corrosion properties of plasma-sprayed Al2O3-TiO2 coatings on Ti metal

Three different oxides of CrO₂-TiO₂, Al₂O₃ and Al₂O₃-TiO₂ were plasma-sprayed on Ti substrate to evaluate the crystal structure and the corrosion properties of the coatings. No phase change of the coatings after corrosion test in 0.5 M H₂SO₄ solution at 25°C was found regardless of the presence of the NiCoCrAlY bond layer. Electrochemical measurements and SEM results revealed that the single coatings without the bond layer were always effective against corrosion resistance due to lower current density within the passive region. Pitting corrosion of the surface was observed for the Al₂O₃ coating. It can be concluded that the Al₂O₃-TiO₂ coating without the bond layer may be the best oxide among the oxides investigated due to low porosity (5.4%), smooth surface roughness (4.5 μm), low current density (6.3 × 10^‒8 A/cm²) in the passive region, low corrosion potential (E_corr, ‒0.55 V) and no pitting corrosion.     

Bone-like apatite layer formation on the new resin-modified glass-ionomer cement

In this study, the apatite-forming ability of the new resin-modified glass-ionomer cement was evaluated by soaking the cement in the simulated body fluid. The Fourier Transform Infrared (FTIR) spectrometer and X-Ray Diffraction (XRD) patterns of the soaked cement pointed to the creation of poorly crystalline carbonated apatite. It was found that the releasing of calcium ions from the soaked cement will dominate the undesirable effect of polyacrylic acid on apatite formation. Consequently, the ionic activity products (IAPs) of the apatite in the surrounding medium increased which accelerated apatite nucleation induced by the presence of the Si–OH and COOH groups. Accordingly, the apatite nuclei started to form via primary heterogeneous nucleation and continued by secondary nucleation. Therefore, nucleation and growth occurs as in the layer-by-layer mode so that finite numbers of monolayers are produced. Subsequent formation of film occurs by formation of discrete nuclei (layer-plus-island or SK growth).