阅读说明：本技术 一种医用钛合金表面含锰羟基磷灰石/二氧化钛生物陶瓷涂层及其制备方法 (Medical titanium alloy surface manganese-containing hydroxyapatite/titanium dioxide biological ceramic coating and preparation method thereof ) 是由 赵全明 董健 于 2018-11-01 设计创作，主要内容包括：一种医用钛合金表面含锰羟基磷灰石/二氧化钛生物陶瓷涂层及其制备方法,将锰盐、钙盐、磷盐、甘油和膜层稳定剂溶于水中,配制成电解液；以医用钛合金为阳极、不锈钢为阴极,将医用钛合金和不锈钢置于解液中,对医用钛合金进行微弧氧化处理,制备含锰羟基磷灰石/二氧化钛生物陶瓷涂层。本发明配制的电解液成分简单、易于控制、不含易分解成分、工艺稳定,有利于涂层的大规模批量化生产。本发明制备的涂层与基体之间无不连续界面,具有高的结合强度和结构稳定性,在植入使用过程中不易剥落,能够与基体结合构建出具有良好机械和生物学性能的人体硬组织修复或替换器件。该复合涂层具有良好的生物活性、生物相容性及成骨功能。(Manganese-containing hydroxyapatite/titanium dioxide biological ceramic coating on the surface of medical titanium alloy and a preparation method thereof, manganese salt, calcium salt, phosphorus salt, glycerol and film stabilizer are dissolved in water to prepare electrolyte; and (3) taking the medical titanium alloy as an anode and the stainless steel as a cathode, placing the medical titanium alloy and the stainless steel in the electrolyte, and performing micro-arc oxidation treatment on the medical titanium alloy to prepare the manganese-containing hydroxyapatite/titanium dioxide biological ceramic coating. The electrolyte prepared by the method has simple components, is easy to control, does not contain easily decomposed components, has stable process, and is beneficial to large-scale batch production of coatings. The coating prepared by the invention has no discontinuous interface with the substrate, has high bonding strength and structural stability, is not easy to peel off in the implantation use process, and can be combined with the substrate to construct a human hard tissue repair or replacement device with good mechanical and biological properties. The composite coating has good biological activity, biocompatibility and osteogenesis function.)

1. A preparation method of a medical titanium alloy surface manganese-containing hydroxyapatite/titanium dioxide biological ceramic coating is characterized by comprising the following steps:

1) preparing an electrolyte:

Dissolving manganese salt, calcium salt, phosphorus salt, glycerol and a film stabilizer in water, and uniformly mixing to prepare electrolyte;

2) Micro-arc oxidation:

The medical titanium alloy is taken as an anode, the stainless steel is taken as a cathode, the medical titanium alloy and the stainless steel are placed in the electrolyte prepared in the step 1), the medical titanium alloy is subjected to micro-arc oxidation treatment, and the manganese-containing hydroxyapatite/titanium dioxide biological ceramic coating is prepared on the surface of the medical titanium alloy.

2. The method for preparing the medical titanium alloy surface manganese-containing hydroxyapatite/titanium dioxide bioceramic coating according to claim 1, wherein the manganese ion concentration in the electrolyte is as follows: 0.05-0.3 mol/L, 0.05-0.3 mol/L of calcium ions, 0.01-0.05 mol/L of phosphate ions, 0.01-0.04 mol/L of film stabilizer and 0.01-0.03 mol/L of glycerol.

3. The method for preparing the medical titanium alloy surface manganese-containing hydroxyapatite/titanium dioxide bioceramic coating according to claim 1, wherein the manganese salt is manganese acetate, manganese gluconate or manganese carbonate, the calcium salt is calcium acetate, the phosphate salt is beta-calcium glycerophosphate, and the film stabilizer is sodium citrate or EDTA.

4. The method for preparing the medical titanium alloy surface manganese-containing hydroxyapatite/titanium dioxide bioceramic coating according to claim 1, wherein the medical titanium alloy is pretreated before being subjected to micro-arc oxidation treatment, and the pretreatment comprises polishing and cleaning.

5. The preparation method of the medical titanium alloy surface manganese-containing hydroxyapatite/titanium dioxide bioceramic coating according to claim 4, wherein the polishing is to polish the medical titanium alloy with 100#, 300#, 600#, 1000#, 1500# and 3000# sandpaper in sequence.

6. The preparation method of the medical titanium alloy surface manganese-containing hydroxyapatite/titanium dioxide bioceramic coating according to claim 4, wherein the cleaning is ultrasonic cleaning of the polished medical titanium alloy with acetone, absolute ethyl alcohol and deionized water in sequence.

7. The preparation method of the medical titanium alloy surface manganese-containing hydroxyapatite/titanium dioxide bioceramic coating according to claim 1, wherein in the step 2), a direct current pulse power supply is adopted during micro-arc oxidation treatment, the pulse voltage is 100-550V, the frequency is 100-1000 Hz, the duty ratio is 10-80%, and the distance between titanium or titanium alloy and stainless steel is 50-100 mm.

8. The method for preparing the manganese-containing hydroxyapatite/titanium dioxide bioceramic coating on the surface of the medical titanium alloy according to claim 1, wherein in the step 2), when the micro-arc oxidation treatment is performed, the temperature of the electrolyte is below 0-50 ℃, and the time of the micro-arc oxidation treatment is 5-40 min.

9. The medical titanium alloy surface manganese-containing hydroxyapatite/titanium dioxide bioceramic coating prepared according to any one of claims 1-8, characterized in that the coating is divided into three layers from inside to outside: an inner layer, an intermediate layer and an outer layer; the middle layer is titanium dioxide, and the outer layer is of a micro-nano porous structure.

10. the medical titanium alloy surface manganese-containing hydroxyapatite/titanium dioxide bioceramic coating according to claim 9, wherein the bonding strength between the coating and the medical titanium alloy is 27.6-35.8 MPa; the outer layer contains manganese hydroxyapatite with the particle size of 70-165 nm.

Technical Field

The invention relates to a biological coating, in particular to a medical titanium alloy surface manganese-containing hydroxyapatite/titanium dioxide biological ceramic coating and a preparation method thereof.

Background

Titanium metal has the advantages of good corrosion resistance, strong chemical stability, high specific strength, excellent biocompatibility and the like, and has important application potential in the aspects of orthopedics, orthopedic surgery, stomatology and the like. However, titanium metal belongs to a biological inert material, cannot form chemical combination with host bones after being implanted into a body, does not have the capacity of promoting the formation of new bones, is easy to be infected by bacteria, and seriously influences the implantation effect, so the surface biological activation modification of the titanium metal is required.

The chemical components of the Hydroxyapatite (HA) are similar to the inorganic components of human bone tissues and hard tooth tissues, have good biological activity, and are widely applied to surface modification of biological materials.

Although the chemical composition of HA is similar to that of biological tissues, the degree of crystallization and structural stability of HA are higher than those of bone apatite crystals in natural bone. Therefore, the implant is not easy to degrade after being implanted into a living body, remains in bone tissues as a heteroplasmon, may become a source of infection and a barrier for implanting some implant devices, and is not beneficial to the recovery of the bone tissues at the part. Therefore, how to improve the crystallinity and degradability of HA so that HA can be well matched and fused with natural bone becomes a new idea and direction for HA research.

After the manganese is doped into the hydroxyapatite, the main biological characteristics of the hydroxyapatite are changed by 1) improving the solubility and increasing the solubility and speed; 2) the biodegradation rate is increased, and the bone forming amount is obviously improved; 3) the mechanical property is improved, and the strength and the hardness are both increased compared with HA; 4) increased cell compatibility and reduced cytotoxicity.

The human bone tissue is formed by assembling micron-level trabeculae, nano-level microfilaments, microtubules, microvilli and the like layer by layer, the surface structure characteristics of the micro-nano structure bone implant material have very important influence on cell behaviors, especially have a vital effect on adhesion, proliferation and osteogenesis of osteoblasts, and then have great influence on the osseointegration of the implant material and surrounding bone tissue and the stability of the implant.

Manganese is a trace element necessary for human bodies, plays an important role in maintaining human health, and mainly has the following points: promoting the normal growth and development of bones. Manganese participates in an enzyme system for activating chondroitin sulfate synthesis to promote bone synthesis, can reduce bone loss and prevent osteoporosis, and when manganese is deficient in vivo, the activity of osteoclasts is enhanced, while the activity of osteoblasts is inhibited; manganese participates in the metabolism of human protein, improves the absorption and utilization of the protein in the human body, and promotes the synthesis of cholesterol in the human body; manganese is indispensable in maintaining normal brain functions and has a certain relation with intelligent development, thinking, emotion and behavior; the superoxide dismutase in vivo can only play a role under the catalysis of manganese ions, so that the manganese has the functions of resisting aging and oxidation; in addition, manganese has the effects of preventing cancer and promoting early training.

The existing methods such as plasma spraying, magnetron sputtering, sol-gel method and the like can prepare hydroxyapatite coating on the surface of a medical titanium metal matrix, mainly bonds two different substances of titanium and hydroxyapatite together, has the difference of the two substance phases, has lower bonding strength with the titanium matrix, and is easy to fall off when being implanted into a body; 2. the hydroxyapatite has poor purity, low biological crystallinity, unstable structure and lack of biological activity; 3. plasma spraying and other methods are expensive and high in cost; 4. the surface of the titanium implant is lack of a micro-nano structure similar to human bone tissues, so that the bionic performance is poor, the bone induction capability is poor, and the titanium implant cannot form osseointegration with the bone tissues; 5. the surface appearance and chemical components of the titanium implant are the key points of bone induction and bone conduction, only the surface chemical components are concerned at present, and the bone formation induction effect of the surface appearance is neglected.

Disclosure of Invention

the invention aims to provide a medical titanium alloy surface manganese-containing hydroxyapatite/titanium dioxide biological ceramic coating and a preparation method thereof.

In order to achieve the purpose, the invention adopts the technical scheme that:

A preparation method of a medical titanium alloy surface manganese-containing hydroxyapatite/titanium dioxide biological ceramic coating comprises the following steps:

1) Preparing an electrolyte:

Dissolving manganese salt, calcium salt, phosphorus salt, glycerol and a film stabilizer in water, and uniformly mixing to prepare electrolyte;

2) Micro-arc oxidation:

the medical titanium alloy is taken as an anode, the stainless steel is taken as a cathode, the medical titanium alloy and the stainless steel are placed in the electrolyte prepared in the step 1), the medical titanium alloy is subjected to micro-arc oxidation treatment, and the manganese-containing hydroxyapatite/titanium dioxide biological ceramic coating is prepared on the surface of the medical titanium alloy.

The further improvement of the invention is that the manganese ion concentration in the electrolyte is as follows: 0.05-0.3 mol/L, 0.05-0.3 mol/L of calcium ions, 0.01-0.05 mol/L of phosphate ions, 0.01-0.04 mol/L of film stabilizer and 0.01-0.03 mol/L of glycerol.

The invention has the further improvement that the manganese salt is manganese acetate, manganese gluconate or manganese carbonate, the calcium salt is calcium acetate, the phosphorus salt is beta-calcium glycerophosphate, and the film stabilizer is sodium citrate or EDTA.

The further improvement of the invention is that the medical titanium alloy is pretreated before being subjected to micro-arc oxidation treatment, and the pretreatment comprises polishing and cleaning.

The further improvement of the invention is that the polishing is to polish the medical titanium alloy by using 100#, 300#, 600#, 1000#, 1500# and 3000# sandpaper in sequence.

The further improvement of the invention is that the cleaning is to carry out ultrasonic cleaning on the polished medical titanium alloy by using acetone, absolute ethyl alcohol and deionized water in sequence.

The further improvement of the invention is that in the step 2), a direct current pulse power supply is adopted during micro-arc oxidation treatment, the pulse voltage is 100-550V, the frequency is 100-1000 Hz, the duty ratio is 10-80%, and the distance between titanium or titanium alloy and stainless steel is 50-100 mm.

The further improvement of the invention is that in the step 2), when the micro-arc oxidation treatment is carried out, the temperature of the electrolyte is below 0-50 ℃, and the time of the micro-arc oxidation treatment is 5-40 min.

The medical titanium alloy surface manganese-containing hydroxyapatite/titanium dioxide biological ceramic coating prepared by the method is divided into three layers from inside to outside: an inner layer, an intermediate layer and an outer layer; the middle layer is titanium dioxide, and the outer layer is of a micro-nano porous structure.

The further improvement of the invention is that the bonding strength of the coating and the medical titanium alloy is 27.6-35.8 MPa; the outer layer contains manganese hydroxyapatite with the particle size of 70-165 nm.

Compared with the prior art, the method has the beneficial effects that:

Firstly, preparing an electrolyte containing manganese ions, calcium ions, phosphate ions and a film stabilizer; then, the medical titanium alloy is taken as an anode, stainless steel is taken as a cathode, and the manganese-containing hydroxyapatite/titanium dioxide biological ceramic coating is directly prepared on the surface of the medical titanium alloy substrate by adopting a micro-arc oxidation method. The electrolyte used by the method is green and environment-friendly, has no pollution to the environment, and the prepared coating is non-toxic and harmless and has good cell nucleus histocompatibility; the method has the advantages of simple steps, simple and convenient operation, high repeatability, easily obtained raw materials, low price, suitability for industrial large-scale production and good application prospect. The electrolyte for micro-arc oxidation treatment prepared by the invention has simple components, is easy to control, does not contain easily decomposed components, has stable process and is beneficial to large-scale batch production of coatings. In addition, the preparation method provided by the invention has no special requirements on the shape of the matrix material, can be suitable for matrixes with complex shapes, and effectively enlarges the application range of the invention.

The manganese-containing hydroxyapatite/titanium dioxide biological ceramic coating prepared by the invention takes medical titanium alloy as a substrate, the coating covers the surface of the medical titanium alloy substrate in a growth mode, the coating and the substrate are firmly combined in a canine-teeth staggered mode, and the coating is divided into three layers from inside to outside: the inner layer is uneven and mutually interpenetrated with the matrix and mutually matched, and the ceramic layer and the matrix are in canine-tooth staggered combination; the middle layer is hard and compact, the thickness of the ceramic coating is mainly determined by the middle layer, the main component is titanium dioxide, the outer layer is of a micro-nano porous structure, the surface of the ceramic coating is covered by grown manganese hydroxyapatite, and the manganese is uniformly doped in the hydroxyapatite coating. The composite coating has no discontinuous interface with the substrate, has high bonding strength and structural stability, is not easy to peel off in the implantation use process, and can be combined with the substrate to construct a human hard tissue repair or replacement device with good mechanical and biological properties. And the composite coating has good biological activity, biocompatibility and osteogenesis function. Compared with the common hydroxyapatite, the solubility of the manganese-containing hydroxyapatite in simulated body fluid is lower, so that the structure of the apatite is more stable, the implantation service life of the apatite can be prolonged, and the possibility of widely applying titanium metal to hard tissue repair or replacement is provided. The doped elements in the hydroxyapatite in the composite coating and the nano-granular form of the doped elements can obviously promote the adhesion and growth of cells, are beneficial to the formation of new bones, and can greatly improve the fusion capacity of titanium metal bones; therefore, the manganese-containing hydroxyapatite/titanium dioxide biological ceramic coating provided by the invention can be widely applied as a multifunctional coating on the surface of a medical implant.

Drawings

Fig. 1 is a SEM image of the surface topography of the manganese-containing hydroxyapatite/titanium dioxide bioceramic coating prepared in example 1, wherein a is at 500 x magnification and b is at 1500 x magnification.

Fig. 2 is a surface EDS energy spectrum of the manganese-containing hydroxyapatite/titanium dioxide bioceramic coating prepared in example 1.

Fig. 3 is a mapping chart of the bioceramic coating containing manganese hydroxyapatite/titanium dioxide prepared in example 1.

FIG. 4 is a diagram showing the results of CCK-8 detection of osteoblasts cultured on the surface of the titanium and the bioceramic coating containing manganese hydroxyapatite/titanium dioxide obtained in example 1 for different periods of time.

FIG. 5 is a graph showing the results of the detection of intracellular alkaline phosphatase activity of osteoblasts cultured for different periods of time on the surfaces of titanium and the bioceramic coating containing manganese hydroxyapatite/titanium dioxide obtained in example 1.

Detailed Description

The present invention will be described in detail below with reference to specific embodiments in conjunction with the accompanying drawings.