阅读说明：本技术 一种载Sr和Ag的提高生物相容性的医用钛材制备方法 (Preparation method of medical titanium material loaded with Sr and Ag and capable of improving biocompatibility ) 是由 潘长江 贡志昊 权莉 柳森 叶玮 于 2020-05-12 设计创作，主要内容包括：本发明公开了一种载Sr和Ag的提高生物相容性的医用钛材制备方法,属于植入性生物材料表面改性技术领域,首先以医用钛材作为阳极,采用电化学氧化的方法在钛材表面制备规整的纳米管涂层,然后将获得的材料在含锶离子的溶液中进行水热处理获得载锶元素的材料,进一步将材料浸没到含银离子的溶液中充分吸附一定时间,最后采用水银高压汞灯进行照射,将吸附的银离子还原为银纳米颗粒,获得载锶和银的纳米管涂层材料。采用本发明的方法制备载Sr和Ag的纳米管材料,可以缓慢释放Sr<Sup>2+</Sup>和Ag<Sup>+</Sup>,从而协同提高材料的成骨性能、提高骨整合性并赋予材料优异的抗菌性能。(The invention discloses a preparation method of medical titanium material loaded with Sr and Ag and capable of improving biocompatibility, belonging to the technical field of surface modification of implantable biological materialsPreparing a regular nanotube coating, carrying out hydrothermal treatment on the obtained material in a solution containing strontium ions to obtain a strontium-loaded material, further immersing the material in the solution containing the silver ions for sufficient adsorption for a certain time, and finally irradiating by adopting a mercury high-pressure mercury lamp to reduce the adsorbed silver ions into silver nanoparticles to obtain the strontium-and silver-loaded nanotube coating material. The Sr and Ag loaded nanotube material prepared by the method can slowly release Sr 2+ And Ag + Thereby synergistically improving the osteogenic property of the material, improving the osseointegration property and endowing the material with excellent antibacterial property.)

1. A preparation method of medical titanium material loaded with Sr and Ag and capable of improving biocompatibility is characterized by comprising the following steps:

1) the medical titanium material is used as an anode, a regular nanotube array coating is prepared on the surface of the titanium material by adopting an electrochemical oxidation method, and then heat treatment is carried out in an air environment;

2) the material obtained in the step 1) is added with Sr²⁺Carrying out hydrothermal treatment on the solution;

3) immersing the material obtained in the step 2) into a solution containing silver ions for sufficient adsorption, and finally carrying out ultraviolet irradiation by using a high-pressure mercury lamp to reduce the adsorbed silver ions into silver nano particles so as to obtain the strontium and silver nano particle loaded nanotube coating material.

2. The preparation method of the medical titanium material loaded with Sr and Ag and capable of improving biocompatibility according to claim 1, is characterized in that: in the step 1), the voltage of the electrochemical oxidation is 30-70V, the treatment time is 1-4 hours, and the electrolyte of the electrochemical oxidation contains 0.1-1 wt% of NH₄F and deionized water; the heat treatment temperature is 400-550 ℃, and the heat treatment time is 1-4 hours.

3. The preparation method of the medical titanium material loaded with Sr and Ag and capable of improving biocompatibility according to claim 1, is characterized in that: in the step 2), the hydrothermal treatment temperature is 200-400 ℃, and the time is 0.5-2 hours.

4. The preparation method of the medical titanium material loaded with Sr and Ag and capable of improving biocompatibility according to claim 1, is characterized in that: in step 2), contains Sr²⁺The solution of (A) is Sr (OH)₂The aqueous solution of (1) has a concentration of 0.01M to 0.05M.

5. The preparation method of the medical titanium material loaded with Sr and Ag and capable of improving biocompatibility according to claim 1, is characterized in that: in step 3), the solution containing silver ions is AgNO₃The solution has a concentration of 0.01M-0.1M and an adsorption time of 5-30 minutes.

6. The preparation method of the medical titanium material loaded with Sr and Ag and capable of improving biocompatibility according to claim 1, is characterized in that: in the step 3), the ultraviolet irradiation time is 10-60 minutes, and the wavelength is 365 nm.

Technical Field

The invention belongs to the technical field of surface modification of implantable biomaterials, and particularly relates to a preparation method of a medical titanium material loaded with Sr and Ag and capable of improving biocompatibility.

Background

Titanium and its alloys have excellent mechanical properties and physiological corrosion resistance, and thus have wide applications in the field of hard tissue materials, however, they have poor integration with bone tissue after being implanted into the body and cannot promote bone tissue regeneration due to poor surface biocompatibility. At present, a large number of surface modification technologies are used for improving the biocompatibility of medical titanium materials, and include plasma spraying, ion implantation, acid-base treatment, Ca-P coating deposition, polymer coating preparation, in-situ biomolecule immobilization and the like. However, these methods are complicated, some require special equipment, and are not biocompatible enough.

The porous nano structure is constructed on the surface of the titanium material by a physical and chemical method, so that the growth and proliferation of bone cells can be promoted, the growth of bone tissues can be promoted, and the osseointegration performance of the material can be improved. The electrochemical oxidation is an important method for preparing the nano structure on the titanium surface in situ, which is economical and simple, the nano tube array structure can be formed on the titanium surface in situ by controlling proper process conditions, and the diameter and the length of the nano tube can be controlled by adjusting process parameters. Therefore, the nanotube array coating prepared by electrochemical oxidation can promote the regeneration of bone tissues and improve the osseointegration. The biocompatibility and other properties of the nano-tube can be further improved by loading bioactive molecules, drugs or nano-particles in the nano-tube.

Medical titanium materials are used as bone substitute materials, and need to have excellent antibacterial properties to prevent infection caused by implantation in addition to good bone regeneration capacity, and although the nanotube structure on the surface of the titanium material can promote the growth of osteoblasts, the antibacterial properties are poor. Recent studies have found that metal ions play a very important role in the biocompatibility of biomaterials, e.g., Cu²⁺Has good antibacterial property, endothelial cell growth promoting property and good blood compatibility. Sr is a trace element widely existing in human bone tissues and plays an important role in the growth and development of the bone tissues, and Sr²⁺Can promote the growth, proliferation and differentiation of bone cells. Silver is an important inorganic antimicrobial agent, has broad-spectrum antimicrobial properties, and does not produce drug resistance. Therefore, Sr and Ag are loaded in the nanotube array structure on the surface of the titanium material at the same time, so that the material can be endowed with excellent bone-promoting performance and antibacterial performance at the same time.

Disclosure of Invention

The purpose of the invention is as follows: the invention aims to provide a preparation method of medical titanium material loaded with Sr and Ag and used for improving biocompatibility, wherein Sr is carried on the surface of the titanium material²⁺And Ag⁺The sustained release of the implant material can promote the regeneration of bone tissues, improve the osseointegration performance of the implant material, endow the material with excellent antibacterial performance, and effectively prevent the infection after the implant.

The technical scheme is as follows: in order to achieve the purpose, the invention adopts the following technical scheme:

a preparation method of medical titanium material loaded with Sr and Ag and capable of improving biocompatibility comprises the following steps:

1) the medical titanium material is used as an anode, a regular nanotube array coating is prepared on the surface of the titanium material by adopting an electrochemical oxidation method, and then heat treatment is carried out in the air;

2) the material obtained in the step 1) is added with Sr²⁺Carrying out hydrothermal treatment on the solution;

3) immersing the material obtained in the step 2) into a solution containing silver ions for sufficient adsorption, and finally carrying out ultraviolet irradiation by using a high-pressure mercury lamp to reduce the adsorbed silver ions into silver nano particles so as to obtain the strontium and silver nano particle loaded nanotube coating material.

Further, in the step 1), the voltage of the electrochemical oxidation is 30-70V, the treatment time is 1-4 hours, and the electrolyte of the electrochemical oxidation contains 0.1-1 wt% of NH₄F and deionized water; the heat treatment temperature is 400-550 ℃, and the heat treatment time is 1-4 hours.

Further, in the step 2), the hydrothermal treatment temperature is 200-.

Further, in step 2), Sr is contained²⁺The solution of (A) is Sr (OH)₂The aqueous solution of (1) has a concentration of 0.01M to 0.05M.

Further, in the step 3), the solution containing silver ions is AgNO₃The solution has a concentration of 0.01M-0.1M and an adsorption time of 5-30 minutes.

Further, in the step 3), the ultraviolet irradiation time is 10-60 minutes, and the wavelength is 365 nm.

Has the advantages that: compared with the prior art, the medical titanium material carrying Sr and Ag and improving biocompatibility disclosed by the invention has the following advantages that the surface modification is carried out on the bone implant material by the method:

1) sr to promote bone cell growth²⁺The Ag nano particles with good antibacterial property are loaded in the titanium oxide nano tube, so that the material is endowed with excellent osteogenesis performance and antibacterial property, the osseointegration performance of the material is improved, and the occurrence of infection after implantation is prevented;

2) active metal ion (Sr)²⁺And Ag⁺) The release time of the material exceeds 14 days, the material can play a role for a longer time, and the biocompatibility of the material is continuously improved;

3) the unique porous nanotube structure is beneficial to the rapid tissue ingrowth and improves the whole bone capacity.

Drawings

FIG. 1 shows the surface loading of Sr on the medical titanium material²⁺And a schematic step diagram of silver nanoparticles;

FIG. 2 shows a titanium surface nanotube array (TNT) loaded with Sr²⁺Of (2) a nanotubeThe surface appearance of the array (TNT-Sr) and the Sr/Ag-loaded nanotube array (TNT-Sr/Ag);

FIG. 3 is a schematic diagram showing the release behavior of Sr/Ag ions;

fig. 4 is a schematic illustration of the proliferation behavior of osteoblasts;

FIG. 5 is a schematic diagram showing the adhesion and antibacterial properties of bacteria on the surface of a titanium material.

Detailed Description

In order to further explain the invention, the following embodiments are combined to provide a method for preparing a medical titanium material loaded with Sr and Ag and having improved biocompatibility. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined by the appended claims.

As shown in fig. 1, a method for preparing a medical titanium material loaded with Sr and Ag for improving biocompatibility includes the following steps:

1) preparing a regular nanotube array coating on the surface of a medical titanium material serving as an anode by adopting an electrochemical oxidation method, and carrying out heat treatment in air;

2) the material obtained in the step 1) is added with Sr²⁺Carrying out hydrothermal treatment on the solution;

3) immersing the material obtained in the step 2) into a solution containing silver ions for sufficient adsorption, and finally carrying out ultraviolet irradiation by using a high-pressure mercury lamp to reduce the adsorbed silver ions into silver nano particles so as to obtain the strontium and silver nano particle loaded nanotube coating material.

In the step 1), the voltage of electrochemical oxidation is 30-70V, the treatment time is 1-4 hours, and the electrolyte of electrochemical oxidation contains 0.1-1 wt% of NH₄F and deionized water; the heat treatment temperature is 400-550 ℃, and the heat treatment time is 1-4 hours.

In the step 2), the hydrothermal treatment temperature is 200-400 ℃ and the time is 0.5-2 hours.

In step 2), contains Sr²⁺Solution of (2)Is, Sr (OH)₂The aqueous solution of (1) has a concentration of 0.01M to 0.05M.

In step 3), the solution containing silver ions is AgNO₃The solution has a concentration of 0.01M-0.1M and an adsorption time of 5-30 minutes.

In step 3), the solution containing silver ions is AgNO₃The solution has a concentration of 0.01M-0.1M and an adsorption time of 5-30 minutes.

In the step 3), the ultraviolet irradiation time is 10-60 minutes, and the wavelength is 365 nm.