阅读说明：本技术 一种人工种植体 (Artificial implant ) 是由 吴连俊 刘崇星 刘劲松 姚李韬 刘传通 姚丽丽 杨颖� 于 2020-03-27 设计创作，主要内容包括：本发明公开了一种人工种植体,其技术方案是包括基体和涂层,所述基体为氧化锆陶瓷,所述涂层为表面形成纳米孔结构的钽涂层,所述钽涂层的纳米孔径在15～50nm,所述钽涂层的厚度在0.5～2μm,还包括一种人工种植体的制备方法,本发明提供一种人工种植体,该种植体的基体选为氧化锆,利用磁控溅射结合阳极氧化技术,在氧化锆表面上形成具有一定厚度且与氧化锆基体结合力良好的钽纳米结构涂层,增加种植体表面的粗糙度和亲水性,促进氧化锆种植体早期骨结合。(The invention discloses an artificial implant, which comprises a substrate and a coating, wherein the substrate is zirconia ceramic, the coating is a tantalum coating with a nano-pore structure formed on the surface, the nano-pore diameter of the tantalum coating is 15-50 nm, and the thickness of the tantalum coating is 0.5-2 mu m.)

1. An artificial implant, characterized in that: the coating is a tantalum coating with a nano-pore structure formed on the surface.

2. An artificial implant according to claim 1, wherein: the nano-aperture of the tantalum coating is 15-50 nm.

3. An artificial implant according to claim 1, wherein: the thickness of the tantalum coating is 0.5-2 mu m.

4. The method for preparing an artificial implant according to claim 1, 2 or 3, wherein: the preparation method comprises the following preparation steps:

step a: sintering the yttrium-stabilized zirconia ceramic at 1000-2000 ℃ for 1-5 h to obtain zirconia crystals; step b: washing and drying the zirconium oxide crystal;

step c, mounting the tantalum target material on a sputtering target of a magnetron sputtering device, and sputtering a tantalum coating on the surface of the zirconium oxide by using a magnetron sputtering technology, wherein magnetron sputtering parameters comprise sputtering power of 20-100 w, sputtering rate of 0.8-1.2 nm/s and reference air pressure of 1 × 10^-4～5×10^-4Pa; working air pressure: 0.4 Pa-0.6 Pa; sputtering time: 0.5-3 h: temperature: 25-30 ℃;

step d: by utilizing an electrochemical anodic oxidation technology, taking zirconium oxide deposited with a tantalum base layer as an anode and a platinum sheet as a cathode, soaking the cathode and the anode in an acid electrolyte at the same time, electrolyzing for 2-8 min under a constant voltage, and further forming a tantalum nano-pore structure on the surface of the tantalum base layer, wherein the electrolytic voltage is 12-18 v;

step e: and washing dirt on the surface of the tantalum nano-pore coating.

5. The method for preparing an artificial implant according to claim 4, wherein: in the step d, the acid electrolyte is selected from a mixed solution of concentrated sulfuric acid and hydrofluoric acid, and the mixed solution is prepared from 90-98 wt% of concentrated sulfuric acid solution and 5-40 wt% of hydrofluoric acid according to a volume ratio (90-99): (1-10) mixing.

6. The method for preparing an artificial implant according to claim 5, wherein: the concentration of the hydrofluoric acid is 5-10 wt%.

7. The method for preparing an artificial implant according to claim 4,5 or 6, wherein: in the step d, the temperature of the acid electrolyte is controlled at 0 ℃, and the electrolysis time is 5 min.

8. The method for preparing an artificial implant according to claim 4, wherein: in the step c, the sputtering power is selected to be 100-150 w, and the sputtering time is selected to be 2-3 h.

9. The method for preparing an artificial implant according to claim 4, wherein: in the step b, the washing method comprises the steps of ultrasonically cleaning the zirconium oxide crystal in acetone, ethanol and deionized water for 10-20 min in sequence, and drying.

10. The method for preparing an artificial implant according to claim 4, wherein: in the step e, the zirconium oxide deposited with the tantalum nano-pore coating is sequentially subjected to ultrasonic cleaning in ethanol and deionized water for 10-20 min, and then dried.

Technical Field

The invention relates to the field of medicine, in particular to an artificial implant.

Background

In recent years, zirconia implants have been increasingly used in the field of implant materials due to their superior aesthetic properties, good biocompatibility and stable chemical properties. However, since zirconia is a bio-inert material and has no groups chemically bonded to living bone tissues on the surface, when it is implanted into a human body as an implant, there is no good contact between the material and the bone tissues of the human body, which may cause some fibrous tissues to easily grow into the interface between the implant and the bone tissues, thereby breaking the osseointegration, loosening the implant, and finally causing implant failure.

Therefore, how to promote early osseointegration of the zirconia implant becomes a crucial issue. At present, there are many methods for surface modification, such as sand blasting, acid etching, laser treatment, and coating, however, these methods have some disadvantages, such as surface contamination of zirconia substrate, easy separation of coating, and undesirable osseointegration effect.

Research shows that tantalum and oxides thereof are widely applied to biological materials due to excellent biocompatibility, corrosion resistance and bone induction capacity, a coating with a nano structure prepared on the surface of an implant can obviously improve the bone bonding capacity of the implant, but for zirconia ceramics, the surface chemical property of zirconia is very stable, so that the coating prepared in the past has poor bonding force with a substrate and is easy to fall off in the implantation process.

Disclosure of Invention

Aiming at the defects in the prior art, the invention aims to provide an artificial implant, wherein a substrate of the implant is selected from zirconia, a tantalum nano-structure coating which has a certain thickness and good bonding force with a zirconia substrate is formed on the surface of the zirconia by utilizing magnetron sputtering combined with an anodic oxidation technology, so that the roughness and the hydrophilicity of the surface of the implant are increased, and the early osseointegration of the zirconia implant is promoted.

In order to achieve the purpose, the invention provides the following technical scheme: an artificial implant comprises a substrate and a coating, wherein the substrate is zirconia ceramic, and the coating is a tantalum coating with a nano-pore structure formed on the surface.

As a further improvement of the invention, the nano-aperture of the tantalum coating is 15-50 nm.

As a further improvement of the invention, the thickness of the tantalum coating is 0.5-2 μm.

A preparation method of an artificial implant comprises the following preparation steps:

step a: sintering the yttrium-stabilized zirconia ceramic at 1000-2000 ℃ for 1-5 h to obtain zirconia crystals;

step b: washing and drying the zirconium oxide crystal;

step c, mounting the tantalum target material on a sputtering target of a magnetron sputtering device, and sputtering a tantalum coating on the surface of the zirconium oxide by using a magnetron sputtering technology, wherein magnetron sputtering parameters comprise sputtering power of 20-100 w, sputtering rate of 0.8-1.2 nm/s and reference air pressure of 1 × 10^-4～5×10^-4Pa working air pressure: 0.4 Pa-0.6 Pa; sputtering time: 0.5-3 h: temperature: 25-30 ℃;

step d: by utilizing an electrochemical anodic oxidation technology, taking zirconium oxide deposited with a tantalum coating as an anode and a platinum sheet as a cathode, soaking the cathode and the anode in an acidic electrolyte at the same time, electrolyzing for 2-8 min under a constant voltage, and further forming a tantalum nano-pore structure on the surface of the tantalum coating, wherein the electrolytic voltage is 12-18 v;

step e: and washing dirt on the surface of the tantalum nano-pore coating.

As a further improvement of the present invention, in step d, the acidic electrolyte is selected from a mixed solution of concentrated sulfuric acid and hydrofluoric acid, and the mixed solution is prepared from 90-98 wt% of concentrated sulfuric acid solution and 5-40 wt% of hydrofluoric acid according to a volume ratio (90-99): (1-10) mixing.

As a further improvement of the invention, the concentration of the hydrofluoric acid is 5-10 wt%.

As a further improvement of the invention, in the step d, the temperature of the acid electrolyte is controlled at 0 ℃, and the electrolysis time is 5 min.

In the step c, the sputtering power is selected to be 100-150 w, and the sputtering time is selected to be 2-3 h.

As a further improvement of the invention, in the step b, the washing method comprises the steps of sequentially ultrasonically washing the zirconium oxide crystal in acetone, ethanol and deionized water for 10-20 min, and drying.

As a further improvement of the invention, in the step e, the washing method comprises the steps of sequentially ultrasonically washing the zirconium oxide deposited with the tantalum nano-pore coating in ethanol and deionized water for 10-20 min, and then drying.

The invention has the beneficial effects that:

(1) the method utilizes the magnetron sputtering and anodic oxidation technology to form the tantalum nano-structure coating with a certain thickness and good bonding force with the zirconia matrix on the surface of the zirconia, and compared with the method adopting the electron beam evaporation and anodic oxidation, the coating prepared by the method has better bonding force with the zirconia matrix, is not easy to separate, has no pollution and has high energy utilization rate;

(2) according to the invention, the tantalum coating with proper thickness prepared by the magnetron sputtering technology is not too thick, so that the tantalum coating has poor binding force and is easy to fall off, and the problem that the tantalum coating is too thin, so that a nano structure is difficult to form in the subsequent anodic oxidation electrolysis step, or the surface of the zirconia matrix is easy to be polluted is avoided, so that the thickness is controlled within the range of 0.5-2 μm.

(3) The tantalum nano-pore coating prepared by the invention can increase the roughness and the hydrophilicity of the surface of the zirconia implant, the pore diameter of the nano-pore is 15-50 nm, the size of the protein is about 10nm generally, and the cell adhesion and spreading are facilitated, so that the bone induction activity of osteoblasts is promoted, and the bone combination rate of the implant is improved.

Drawings

FIG. 1 is an SEM image of the surface topography of a coating prepared in example two;

FIG. 2 is an SEM image of a cross-section of a coating prepared in example two;

FIG. 3 is a graph showing the roughness of the coatings prepared in example two, comparative example one, and comparative example two;

FIG. 4 is a contact angle of the coatings prepared in example two, comparative example one, and comparative example two;

FIGS. 5-A, 5-B, and 5-C are graphs showing the adhesion of surface cells of the coatings prepared in example two, comparative example one, and comparative example two;

FIGS. 6-A, 6-B, and 6-C show the proliferation of surface cells of the coatings prepared in example two, comparative example one, and comparative example two.

Detailed Description