CN109568655B - Preparation process of single/multi-element doped sodium titanate nanorod array coating - Google Patents
Preparation process of single/multi-element doped sodium titanate nanorod array coating Download PDFInfo
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Abstract
The invention discloses a preparation process of a single/multi-element doped sodium titanate nanorod array coating, which is characterized in that different sodium titanate nanorod array coatings are prepared on the surface of pure titanium by a Hydrothermal (HT) method, and the coatings are subjected to hydrothermal treatment again to realize the single/multi-element (Mg, Ca, Sr or Zn) doping of nano rod-shaped sodium titanate in the coatings. The coating is of a double-layer structure and is characterized in that: the inner layer (adjacent to the substrate) is a dense nanoparticle layer; the surface layer is a nano rod which is oriented approximately vertical to the compact nano particle layer. The coating and the substrate have no discontinuous interface and high bonding strength (21.0-30.2N). Can be quickly induced to form bone apatite in the simulated body fluid environment, and has good bioactivity. The invention uses human bone for reference, carries out bone-imitating surface modification on a pure titanium matrix from the structure and the components, endows the micro-nano structure and the trace elements on the surface of the implant, and improves the osseointegration effect through the synergistic effect of the micro-nano structure and the trace elements.
Description
Technical Field
The invention belongs to the technical field of medical metal surface biological activation modification, and relates to a preparation technology of a titanium-based medical implant surface bioactive coating, in particular to a hydrothermal preparation technology of a sodium titanate nanorod array coating doped with multiple elements.
Background
Although titanium and titanium alloy have good biocompatibility, the titanium and titanium alloy still belong to a biological inert material, are difficult to integrate with host bones after being implanted into a body, and are easy to induce fiber encapsulation to cause the implant to loosen or even fail. In order to improve the osseointegration capability of the titanium-based implant, the surface of the titanium-based implant needs to be biologically activated and modified. It is known that natural bone matrix is composed of fibrous collagen and nanoparticulate Hydroxyapatite (HA) doped with trace metal elements such as Mg, Sr and Zn. According to the structure bone-like matrix, a nanorod/fiber array coating can be constructed on the titanium-based surface; according to the component bone-imitating matrix, a certain amount of trace metal elements can be doped in the nanorod/fiber array, and the bone integration capacity of the titanium-based implant can be improved by constructing the three-dimensional configuration bone-imitating matrix coating.
The hydrothermal treatment can directly generate a three-dimensional Sodium Titanate (ST) nanorod array on the titanium-based surface in situ to simulate the configuration of a natural bone matrix, and element doping can be realized in the nanorods to simulate the components of the natural bone matrix by utilizing the ion exchange principle in the hydrothermal treatment process. In the previous research, although the sodium titanate nanorods are formed on the surface of titanium by utilizing hydrothermal treatment, the nanorod configuration parameters (such as rod spacing, diameter and orientation) are not accurately regulated, and the single-element or multi-element co-doping of the sodium titanate nanorods through ion exchange is not reported.
Firstly, preparing a sodium titanate nanorod array coating by a hydrothermal method, and regulating and controlling the distance between nanorods by regulating and controlling the concentration of a nucleation solution; meanwhile, in the hydrothermal process, single/co-doping of the four elements of Mg, Ca, Sr and Zn is realized through ion exchange, and the doping amount of each element is regulated and controlled through hydrothermal process parameters. The simple, convenient and feasible two-step hydrothermal method can be used for constructing a single/multi-component doped sodium titanate nanorod array of the bone-like matrix on the titanium-based surface so as to improve the osseointegration effect of the titanium-based implant and enable the titanium-based implant to have certain antibacterial property.
Disclosure of Invention
The invention aims to provide a preparation process for forming a single-element-doped or multi-element-co-doped Sodium titanate nanorod array biological coating on the surface of a titanium substrate by a hydrothermal technology which is convenient to operate, namely a preparation process for a single/multi-element-doped Sodium Titanate (ST) nanorod array coating, wherein an incontinuous interface does not exist between a double-layer structure coating and the substrate, and the coating has high bonding strength (21.0-30.2N). The sodium titanate nanorod array coating co-doped with multiple elements can quickly induce and form bone apatite in a simulated body fluid environment, and has good biological activity.
The technical scheme of the invention is as follows:
the preparation method of the single/multi-element doped sodium titanate nanorod array coating adopts hydrothermal treatment and HT technology, firstly, a pure titanium matrix is subjected to HT treatment by adopting a one-time hydrothermal technology to realize the construction of the sodium titanate nanorod array coating, and the diameter of the sodium titanate nanorods is controlled to be 65-67 nm, and the distance between the sodium titanate nanorods is controlled to be 45-244 nm by adjusting the concentration of NaOH in a hydrothermal solution to be 0.3-2M, the temperature of hydrothermal treatment to be 100-220 ℃ and the time to be 1-6 h; secondly, carrying out HT hydrothermal treatment on the sodium titanate nanorod array coating with the nanorod diameter of 67nm and the nanorod distance of 72nm again by utilizing the Ion exchange and IE principle to realize the doping of single or multiple elements Mg, Ca, Sr and Zn of the sodium titanate nanorods in the coating, wherein the undoped or single/multiple element doped sodium titanate nanorod array coating is a double-layer structure coating, and the inner layer is adjacent to the substrate to form a compact nanoparticle layer; the surface layer is a nano rod oriented nearly vertical to the compact nano particle layer, and the components of the double-layer structure coating are sodium titanate which is not doped or doped with magnesium, calcium, strontium, zinc or co-doped with four elements.
Carrying out HT treatment on a pure titanium substrate, and specifically comprising the following steps:
and (3) placing the pure titanium sheet sample in a high-pressure reaction kettle, adding 0.3-2M NaOH solution with the concentration of mol per liter, wherein the solution filling degree is 20%, and performing hydrothermal treatment at the temperature of 100-220 ℃ for 1-6 hours to obtain different sodium titanate nanorod array coatings.
Carrying out HT treatment on the sodium titanate nanorod array coating with the diameter of 67nm and the nanorod spacing of 72nm by using the ion exchange principle, and specifically operating as follows:
placing a sodium titanate nanorod array coating with nanorod diameter of 67nm and nanorod spacing of 72nm into a high-pressure reaction kettle, and adding 0.01-10 mM Mg (CH) with millimole concentration per liter3COO)2Solution, or 0.01-1000 mM Ca (CH)3COO)2Solution, or 0.1 to 1000mM Sr (CH)3COO)2Solution, or 0.1-10 mM Zn (CH)3COO)2And carrying out hydrothermal treatment on the solution at the temperature of 100 ℃ for 4-24 hours to obtain the sodium titanate nanorod array coating with single element gradient doping amount.
Carrying out HT treatment on the sodium titanate nanorod array coating with the nanorod diameter of 67nm and the nanorod spacing of 72nm again by using the ion exchange principle, and specifically operating as follows:
placing a sodium titanate nanorod array coating with nanorod diameter of 67nm and nanorod spacing of 72nm into a high-pressure reaction kettle, and adding 5-100 mM Mg (CH) with millimole concentration per liter3COO)2+0.5～1000mM Ca(CH3COO)2+0.5～20mM Sr(CH3COO)2+0.001～1mM Zn(CH3COO)2The mixed solution is subjected to hydrothermal treatment at the temperature of 100 ℃ for 24 hours to obtain the sodium titanate nanorod array coating co-doped with various elements.
The single/multi-element doped sodium titanate nanorod array coating is a double-layer structure coating, the inner layer and the matrix are adjacent to form a compact nanoparticle layer, and the thickness of the compact nanoparticle layer is 350-390 nm; the surface layer is nanorods oriented approximately perpendicular to the compact nanoparticle layer, the diameter of the nanorods is 67nm, the distance between the nanorods is 45-244 nm, the length of the nanorods is 1130-2105 nm, the components of the double-layer structure coating are sodium titanate doped with magnesium, calcium, strontium, zinc or four elements, an incontinuous interface is not formed between the double-layer structure coating and the matrix, the coating after doping has high bonding strength (21.0-30.2N), compared with the coating before element doping (20.8N), the bonding strength of the coating is improved, the sodium titanate nanorod array coating co-doped with multiple elements can rapidly induce to form bone apatite in a simulated body fluid environment, and the sodium titanate nanorod array coating has good bioactivity.
The invention has the following beneficial effects:
1) the hydrothermal solution (the alkali-heat solution and the ion exchange solution) prepared by the method is simple in components, easy to control, free of easily decomposed components and stable in process;
2) the invention overcomes the problem of simultaneous doping of elements in the sodium titanate nanorods, and realizes single element doping and common doping of four elements of magnesium, calcium, strontium and zinc in the sodium titanate nanorods through simple and easy ion exchange, so that the sodium titanate nanorods are closer to the bionic components of natural bones;
3) the single-element doped or four-element co-doped sodium titanate nanorod array biological coating is a double-layer structure coating without an discontinuous interface with a matrix, and has high bonding strength; the nano-rod array design of the coating is close to the nano-fiber form presented on the surface of a natural bone, so that the coating has a more bionic effect; and the doping element enables the coating to have good biological activity, and hydroxyapatite can be rapidly induced in simulated body fluid.
Drawings
FIG. 1 is a surface morphology and a TEM photograph of S72 nanorods of different (same rod diameter, different rod spacing (S45, S72, S140, and S244)) sodium titanate nanorod array coatings (example 1 coatings) prepared by a hydrothermal treatment process using the present invention;
FIG. 2 is a graph showing the scratch test acoustic emission signal and scratch morphology of the sodium titanate nanorod array coating (the S72 coating of example 1) prepared by the hydrothermal treatment process according to the present invention;
FIG. 3 is SEM surface morphology of sodium titanate nanorod array coating (S72 coating of example 1) after soaking in SBF for different periods of time;
FIG. 4 SEM photographs of the surface morphology and the cross-sectional morphology of the magnesium-doped sodium titanate nanorod array coating (example 2 coating) prepared by the hydrothermal treatment process of the invention and TEM photographs of nanorods;
FIG. 5 is SEM photograph of surface morphology and cross-sectional morphology of the calcium-doped sodium titanate nanorod array coating (example 3 coating) and TEM photograph of nanorods prepared by the hydrothermal treatment process of the invention;
FIG. 6 SEM photographs of the surface morphology and the cross-sectional morphology of the strontium-doped sodium titanate nanorod array coating (example 4 coating) prepared by the hydrothermal treatment process of the invention and TEM photographs of nanorods;
FIG. 7 SEM photographs of the surface morphology and the cross-sectional morphology of the zinc-doped sodium titanate nanorod array coating (example 5 coating) prepared by the hydrothermal treatment process of the invention and TEM photographs of nanorods;
SEM photos of the surface appearance and the section appearance of the magnesium, calcium, strontium and zinc co-doped sodium titanate nanorod array coating (the coating of example 6) prepared by the hydrothermal treatment process and TEM photos of nanorods;
FIG. 8 is a graph showing scratch test acoustic emission signals and scratch morphology of a magnesium, calcium, strontium, and zinc co-doped sodium titanate nanorod array coating (example 6 coating) prepared by a hydrothermal treatment process according to the present invention;
FIG. 9 surface SEM topography of magnesium, calcium, strontium and zinc co-doped sodium titanate nanorod array coating (example 6 coating) after soaking in SBF for different times.
Detailed Description
The invention is described in further detail below with reference to the accompanying drawings:
referring to fig. 1, by controlling the concentration of the nucleation solution, sodium titanate nanorod array coatings of different sizes (same rod diameter, different rod spacing (S45, S72, S140, and S244)) can be prepared (fig. 1 a). TEM analysis (FIGS. 1b-1e) of S72 coated sodium titanate nanorods in FIG. 1a, and electron diffraction (FIG. 1c), high resolution (FIG. 1d) and energy spectrum (FIG. 1e) thereof were analyzed by taking the nanorod portion in the dotted circle in FIG. 1b as an example, and the phase of the nanorod was Na2TiO3。
Referring to fig. 2, the scratch morphology, the critical load of the scratch test acoustic emission signal vs, the magnified image of the spalling position and the corresponding energy spectrum of the coating of S72 are shown, and the critical load of the coating is 20.8 +/-0.1N. The coating spalling point and the corresponding energy spectrum show that the spalling point is positioned in the coating, and the measured critical load is the cohesive strength of the coating.
Referring to fig. 3, when the coating of S72 is soaked in Simulated Body Fluid (SBF) for 15d, spherical Hydroxyapatite (HA) is deposited on the surface of the coating; when soaked in SBF to 21d, the spherical HA on the coating surface had been deposited and interconnected to form a HA-spread layer. The sodium titanate coating subjected to hydrothermal surface modification HAs good HA induction capability.
Example 1
Putting a pure titanium sheet sample into a high-pressure reaction kettle, adding a NaOH solution with the concentration of 0.3-2M, wherein the solution filling degree is 20%, carrying out hydrothermal treatment at the temperature of 100 ℃ for 0-1.5 hours, discarding the liquid in the reaction kettle, adding the NaOH with the concentration of 0.5M again, wherein the solution filling degree is 20%, carrying out hydrothermal treatment at the temperature of 220 ℃ for 3.5-6 hours to obtain the sodium titanate nanorod array coating, wherein the nanorods are approximately perpendicular to the titanium substrate, the diameter of the nanorods is about 67nm, the distance between the nanorods is about 72nm, and the length of the nanorods is about 2 mu M. The microscopic surface and section morphologies SEM and the nanorod TEM of the coating are respectively shown in figures 1(a), (b) and (c), the acoustic emission signals and the scratch morphologies of the scratch test are respectively shown in figure 2, the bonding strength of the coating and a titanium matrix is 20.8 +/-0.1N, the surface SEM of the sodium titanate nanorod array coating after SBF soaking for different time is shown in figure 3, the coating has good biological activity in a simulated body fluid environment, spherical apatite appears in 15 days, and the induced apatite completely covers the surface of the nanorod coating in 21 days.
Referring to FIG. 4, the surface morphology of the magnesium-doped sodium titanate nanorod array coating (FIG. 4a) is the same as that of the coating before doping, and it can be seen from the cross-sectional morphology and the line scan energy spectrum (FIG. 4b) that magnesium has been incorporated into the coating. TEM (FIG. 4c1), electron diffraction (FIG. 4c2), high resolution (FIG. 4c3) and energy spectrum (FIG. 4c4) analysis of the Mg-doped sodium titanate nanorods, the Mg-doped sodium titanate still maintains the phase structure of the undoped sodium titanate, which indicates that Mg is incorporated into the crystal lattice of sodium titanate in the form of ions to replace part of sodium ions due to the radius of Mg and sodium ions (r (Mg)2+)＝0.065nm<r(Na+) 0.095nm), distortion of the crystal lattice of sodium titanate is caused, so that the interplanar spacing becomes small.
Example 2
Putting a pure titanium sheet sample into a high-pressure reaction kettle, adding a NaOH solution with the concentration of 1M, wherein the solution filling degree is 20%, carrying out hydrothermal treatment at the temperature of 100 ℃ for 1.5 hours, discarding the liquid in the reaction kettle, adding the NaOH solution with the concentration of 0.5M again, wherein the solution filling degree is 20%, and carrying out hydrothermal treatment at the temperature of 220 ℃ for 3.5 hours to obtain the sodium titanate nanorod array coating (S72). The sodium titanate nanorod array coating (S72) was placed in an autoclave, and Mg (CH) was added at a concentration of 0.01mM3COO)2Solution of water at a temperature of 100 ℃And performing heat treatment for 24 hours to obtain the magnesium-doped sodium titanate nanorod array coating, wherein the nanorods are approximately vertical to the titanium matrix, the diameter of the nanorods is about 67nm, the distance between the nanorods is about 72nm, the length of the nanorods is about 2 mu m, and the shapes of the nanorods are basically unchanged before and after doping. Surface and cross-sectional micro-topography SEM and nanorod TEM are shown in FIGS. 4(a), (b), and (c), respectively.
Referring to FIG. 5, the surface morphology of the calcium-doped sodium titanate nanorod array coating (FIG. 5a) is the same as that of the coating before doping, and it can be seen from the cross-sectional morphology and the line scan energy spectrum (FIG. 5b) that calcium has been doped into the coating. TEM (FIG. 5c1), electron diffraction (FIG. 5c2), high resolution (FIG. 5c3) and energy spectrum (FIG. 5c4) analysis of the calcium-doped sodium titanate nanorods, the calcium-doped sodium titanate still maintains the phase structure of the undoped sodium titanate, indicating that calcium is incorporated into the sodium titanate crystal lattice in the form of ions to replace part of sodium ions due to the calcium and sodium ion radius (r (Ca) of the sodium titanate lattice)2+)＝0.099nm>r(Na+) 0.095nm), distortion of the crystal lattice of sodium titanate is caused, so that the interplanar spacing becomes large.
Example 3
Putting a pure titanium sheet sample into a high-pressure reaction kettle, adding a NaOH solution with the concentration of 1M, wherein the solution filling degree is 20%, carrying out hydrothermal treatment at the temperature of 100 ℃ for 1.5 hours, discarding the liquid in the reaction kettle, adding the NaOH solution with the concentration of 0.5M again, wherein the solution filling degree is 20%, and carrying out hydrothermal treatment at the temperature of 220 ℃ for 3.5 hours to obtain the sodium titanate nanorod array coating (S72). The sodium titanate nanorod array coating (S72) was placed in an autoclave, and Ca (CH) was added at a concentration of 0.01mM3COO)2And carrying out hydrothermal treatment on the solution at the temperature of 100 ℃ for 24 hours to obtain the calcium-doped sodium titanate nanorod array coating, wherein the nanorods are approximately vertical to the titanium matrix, the diameter of the nanorods is about 67nm, the spacing is about 72nm, the length is about 2 mu m, and the shapes of the nanorods are basically not changed before and after doping. The surface and cross-sectional micro-topography SEM and nanorod TEM of the coating are shown in FIGS. 5(a), (b), and (c), respectively.
Referring to FIG. 6, the surface morphology of the strontium-doped sodium titanate nanorod array coating (FIG. 6a) is the same as that of the coating before doping, and the strontium-doped sodium titanate nanorod array coating can be seen from the cross-sectional morphology and the linear scanning energy spectrum (FIG. 6b)Into the coating. TEM (FIG. 6c1), electron diffraction (FIG. 6c2), high resolution (FIG. 6c3) and energy spectrum (FIG. 6c4) analysis of the strontium-doped sodium titanate nanorods, the strontium-doped sodium titanate still maintains the phase structure of the undoped sodium titanate, indicating that strontium is incorporated into the sodium titanate crystal lattice in the form of ions to replace part of sodium ions due to the strontium and sodium ion radius (r (Sr) of the sodium titanate nanorods2+)＝0.113nm>r(Na+) 0.095nm), distortion of the crystal lattice of sodium titanate is caused, so that the interplanar spacing becomes large.
Example 4
Putting a pure titanium sheet sample into a high-pressure reaction kettle, adding a NaOH solution with the concentration of 1M, wherein the solution filling degree is 20%, carrying out hydrothermal treatment at the temperature of 100 ℃ for 1.5 hours, discarding the liquid in the reaction kettle, adding the NaOH solution with the concentration of 0.5M again, wherein the solution filling degree is 20%, and carrying out hydrothermal treatment at the temperature of 220 ℃ for 3.5 hours to obtain the sodium titanate nanorod array coating (S72). The sodium titanate nanorod array coating (S72) is placed in a high-pressure reaction kettle, and Sr (CH) with the concentration of 0.1mM is added3COO)2And carrying out hydrothermal treatment on the solution at the temperature of 100 ℃ for 4 hours to obtain the strontium-doped sodium titanate nanorod array coating, wherein the nanorods are approximately vertical to the titanium matrix, the diameter of the nanorods is about 67nm, the spacing is about 72nm, the length is about 2 mu m, and the shapes of the nanorods are basically unchanged before and after doping. Surface and cross-sectional micro-topography SEM and nanorod TEM are shown in FIGS. 6(a), (b), and (c), respectively.
Referring to FIG. 7, the surface morphology of the zinc-doped sodium titanate nanorod array coating (FIG. 7a) is the same as that of the coating before doping, and it can be seen from the cross-sectional morphology and the line scan energy spectrum (FIG. 7b) that zinc has been incorporated into the coating. TEM (FIG. 7c1), electron diffraction (FIG. 7c2), high resolution (FIG. 7c3) and energy spectrum (FIG. 7c4) analysis of the zinc-doped sodium titanate nanorods, the zinc-doped sodium titanate still maintains the phase structure of the undoped sodium titanate, indicating that zinc is incorporated into the sodium titanate crystal lattice in the form of ions to replace part of sodium ions due to the zinc and sodium ion radii (r (Zn) of the zinc and sodium ions2+)＝0.074nm<The difference in r (Na +) ═ 0.095nm) causes distortion of the crystal lattice of sodium titanate, so that the interplanar spacing becomes small.
Example 5
Putting a pure titanium sheet sample into a high-pressure reaction kettle, adding a NaOH solution with the concentration of 1M, wherein the solution filling degree is 20%, carrying out hydrothermal treatment at the temperature of 100 ℃ for 1.5 hours, discarding the liquid in the reaction kettle, adding the NaOH solution with the concentration of 0.5M again, wherein the solution filling degree is 20%, and carrying out hydrothermal treatment at the temperature of 220 ℃ for 3.5 hours to obtain the sodium titanate nanorod array coating (S72). The sodium titanate nanorod array coating (S72) was placed in an autoclave, and Zn (CH) was added at a concentration of 0.001mM3COO)2And carrying out hydrothermal treatment on the solution at the temperature of 100 ℃ for 20 hours to obtain the zinc-doped sodium titanate nanorod array coating, wherein the nanorods are approximately vertical to the titanium matrix, the diameter of the nanorods is about 67nm, the spacing is about 72nm, the length is about 2 mu m, and the shapes of the nanorods are basically not changed before and after doping. Surface and cross-sectional micro-topography SEM and nanorod TEM are shown in FIGS. 7(a), (b), and (c), respectively.
Referring to fig. 8, the surface morphology of the magnesium calcium strontium zinc co-doped sodium titanate nanorod array coating (fig. 8a) is the same as that of the coating before doping, and it can be seen from the cross-sectional morphology and the line scan energy spectrum (fig. 8b) that magnesium, calcium, strontium and zinc have been doped into the coating. TEM (FIG. 8c1), electron diffraction (FIG. 8c2), high resolution (FIG. 8c3) and energy spectrum (FIG. 8c4) analysis of the MgCaSrZn co-doped sodium titanate nanorods, the MgCaZnTe co-doped sodium titanate still maintains the phase structure of the undoped sodium titanate, which shows that Mg, Ca, Sr and Zn are incorporated into the crystal lattice of the sodium titanate in ion form to replace part of sodium ions due to the ionic radius (r (Mg) of Mg, Ca, Sr, Zn and Na2+)＝0.065nm<r(Zn2+)＝0.074nm<r(Na+)＝0.095nm<r(Ca2+)＝0.099nm<r(Sr2+) 0.113nm) and the amount of each ion doped, distortion of the crystal lattice of sodium titanate is caused, so that the interplanar spacing becomes small.
Referring to fig. 9, the scratch morphology, the critical load of a scratch test acoustic emission signal vs, an enlarged image of a spalling position and a corresponding energy spectrum of the magnesium-calcium-strontium-zinc co-doped sodium titanate nanorod array coating are shown, and the critical load of the coating is 28.1 +/-0.1N. The coating spalling point and the corresponding energy spectrum show that the spalling point is positioned in the coating, and the measured critical load is the cohesive strength of the coating. The bonding strength of the coating after doping magnesium calcium strontium zinc ions is improved relative to that before doping (20.8 +/-0.1N), the mechanism is that magnesium, calcium, strontium and zinc replace partial sodium ions in a sodium titanate crystal lattice, and the bonding energy of magnesium, calcium, strontium and zinc in oxygen is larger than that of sodium and oxygen.
Referring to fig. 10, when the magnesium-calcium-strontium-zinc co-doped sodium titanate nanorod array coating is soaked in Simulated Body Fluid (SBF) for 9d, spherical Hydroxyapatite (HA) is deposited and formed on the surface of the coating; when the coating was soaked in SBF for 17d, the HA was completely deposited on the surface of the coating and formed a HA layer. Indicating that the doping ions contribute to the HA-inducing ability of the sodium titanate coating.
Example 6
Putting a pure titanium sheet sample into a high-pressure reaction kettle, adding a NaOH solution with the concentration of 1M, wherein the solution filling degree is 20%, carrying out hydrothermal treatment at the temperature of 100 ℃ for 1.5 hours, discarding the liquid in the reaction kettle, adding the NaOH solution with the concentration of 0.5M again, wherein the solution filling degree is 20%, and carrying out hydrothermal treatment at the temperature of 220 ℃ for 3.5 hours to obtain the sodium titanate nanorod array coating (S72). The sodium titanate nanorod array coating (S72) is placed in a high-pressure reaction kettle, and 10mM Mgg (CH) is added3COO)2+1mM Ca(CH3COO)2+1mM Sr(CH3COO)2+0.01mM Zn(CH3COO)2The mixed solution is subjected to hydrothermal treatment at the temperature of 100 ℃ for 24 hours to obtain the magnesium, strontium and zinc co-doped sodium titanate nanorod array coating, the nanorods are approximately vertical to the titanium matrix, the diameter of the nanorods is about 67nm, the distance between the nanorods is about 72nm, the length of the nanorods is about 2 mu m, and the shapes of the nanorods before and after doping are basically unchanged. Surface and cross-sectional micro-topography SEM and nanorod TEM are shown in FIGS. 8(a), 8(b), and 8(c), respectively. According to the acoustic emission signals and scratch morphology of the scratch test, referring to fig. 9, the bonding strength of the coating and the titanium matrix is 28.1 +/-0.1N, the surface SEM of the sodium titanate nanorod array coating after the SBF is soaked for different time is referring to fig. 10, the coating has good bioactivity in a simulated body fluid environment, spherical apatite appears in 9 days, and the induced apatite completely covers the surface of the nanorod coating in 17 days.
The examples are given by way of illustration and not by way of limitation, and in summary, it is within the scope of the present invention to provide a bioactive coating having good bioactivity and bonding strength on the surface of a pure titanium substrate using hydrothermal treatment techniques.
The double-layer structure coating prepared by the preparation process has no discontinuous interface with the substrate, and has high bonding strength. Can be quickly induced to form bone apatite in a body fluid-like environment, and has good biological activity. The biological coating of the sodium titanate nanorod array doped with single element or multiple elements is a double-layer structure coating, and the surface layer is a sodium titanate nanorod doped with magnesium, strontium, zinc or co-doping of four elements, so that the adhesion and growth of cells can be remarkably promoted.
Claims (5)
1. The preparation process of the single/multi-element doped sodium titanate nanorod array coating is characterized in that a hydrothermal treatment is adopted for preparing the coating, namely an HT technology, firstly, a pure titanium matrix is subjected to HT treatment by adopting a one-time hydrothermal process to realize the construction of the sodium titanate nanorod array coating, and the diameter of the sodium titanate nanorods is controlled to be 65-67 nm, and the distance between the sodium titanate nanorods is controlled to be 45-244 nm by adjusting the concentration of NaOH in a hydrothermal solution to be 0.3-2M, the temperature of the hydrothermal treatment to be 100-220 ℃ and the time to be 1-6 h; secondly, carrying out HT hydrothermal treatment on the sodium titanate nanorod array coating with the nanorod diameter of 67nm and the nanorod distance of 72nm again by utilizing the Ion exchange and IE principle to realize the doping of single or multiple elements Mg, Ca, Sr and Zn of the sodium titanate nanorods in the coating, wherein the undoped or single/multiple element doped sodium titanate nanorod array coating is a double-layer structure coating, and the inner layer is adjacent to the substrate to form a compact nanoparticle layer; the surface layer is a nano rod oriented nearly vertical to the compact nano particle layer, and the components of the double-layer structure coating are sodium titanate which is not doped or doped with magnesium, calcium, strontium, zinc or co-doped with four elements.
2. The preparation process of the single/multi-element doped sodium titanate nanorod array coating according to claim 1, wherein the pure titanium matrix is subjected to HT treatment, and the specific operations are as follows:
and (3) placing the pure titanium sheet sample in a high-pressure reaction kettle, adding 0.3-2M NaOH solution with the concentration of mol per liter, wherein the solution filling degree is 20%, and performing hydrothermal treatment at the temperature of 100-220 ℃ for 1-6 hours to obtain different sodium titanate nanorod array coatings.
3. The preparation process of the single/multi-element doped sodium titanate nanorod array coating according to claim 1, wherein the sodium titanate nanorod array coating with the sodium titanate nanorod diameter of 67nm and the nanorod spacing of 72nm is subjected to HT treatment again by using an ion exchange principle, and the specific operations are as follows:
placing a sodium titanate nanorod array coating with nanorod diameter of 67nm and nanorod spacing of 72nm into a high-pressure reaction kettle, and adding 0.01-10 mM Mg (CH) with millimole concentration per liter3COO)2Solution, or 0.01-1000 mM Ca (CH)3COO)2Solution, or 0.1 to 1000mM Sr (CH)3COO)2Solution, or 0.1-10 mM Zn (CH)3COO)2And carrying out hydrothermal treatment on the solution at the temperature of 100 ℃ for 4-24 hours to obtain the sodium titanate nanorod array coating with single element gradient doping amount.
4. The preparation process of the single/multi-element doped sodium titanate nanorod array coating according to claim 1, wherein the sodium titanate nanorod array coating with the nanorod diameter of 67nm and the nanorod spacing of 72nm is subjected to HT treatment again by using an ion exchange principle, and the specific operations are as follows:
placing a sodium titanate nanorod array coating with nanorod diameter of 67nm and nanorod spacing of 72nm into a high-pressure reaction kettle, and adding 5-100 mM Mg (CH) with millimole concentration per liter3COO)2+ 0.5～1000mM Ca(CH3COO)2+ 0.5～20mMSr(CH3COO)2+ 0.001～1 mM Zn(CH3COO)2The mixed solution is subjected to hydrothermal treatment at the temperature of 100 ℃ for 24 hours to obtain the sodium titanate nanorod array coating co-doped with various elements.
5. The preparation process of the single/multi-element doped sodium titanate nanorod array coating according to claim 1, characterized in that: the single/multi-element doped sodium titanate nanorod array coating is a double-layer structure coating, the inner layer and the matrix are adjacent to form a compact nanoparticle layer, and the thickness of the compact nanoparticle layer is 350-390 nm; the surface layer is nanorods oriented approximately perpendicular to the compact nanoparticle layer, the diameter of the nanorods is 67nm, the distance between the nanorods is 45-244 nm, the length of the nanorods is 1130-2105 nm, the components of the double-layer structure coating are sodium titanate doped with magnesium, calcium, strontium, zinc or four elements, an incontinuous interface is not formed between the double-layer structure coating and the matrix, the coating after doping has high bonding strength of 21.0-30.2N, compared with 20.8N before element doping, the bonding strength of the coating is improved, the sodium titanate nanorod array coating co-doped with various elements can rapidly induce to form bone apatite in a simulated body fluid environment, and the sodium titanate nanorod array coating has good bioactivity.
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