阅读说明：本技术 一种具有表面活性的Nb-Ta-Ti-Si生物医用复合材料的制备方法 (Preparation method of Nb-Ta-Ti-Si biomedical composite material with surface activity ) 是由 刘珏 于 2019-12-05 设计创作，主要内容包括：本发明公开了一种具有表面活性的Nb-Ta-Ti-Si生物医用复合材料的制备方法,属于生物医用材料领域,本发明采用表面预处理+超声电沉积法+后处理的方案,在金属基体表面沉积羟基磷灰石活性层,实验条件温和,能有效避免改善表面活性层与金属基体之间界面结合强度不足的问题；本发明采用特定的预处理机制对合金进行表面处理,通过不同的表面化学处理及热处理,使基体表面获得独有的形貌特征,为后期羟基磷灰石形核与附着提供了有效的位点；基体表面形成氧化物过渡层,有利于羟基磷灰石的化学键合。(The invention discloses a preparation method of a Nb-Ta-Ti-Si biomedical composite material with surface activity, which belongs to the field of biomedical materials, adopts the scheme of surface pretreatment, an ultrasonic electrodeposition method and aftertreatment to deposit a hydroxyapatite active layer on the surface of a metal matrix, has mild experimental conditions, and can effectively avoid the problem of insufficient interface bonding strength between the surface active layer and the metal matrix; the invention adopts a specific pretreatment mechanism to carry out surface treatment on the alloy, and the surface of the substrate obtains unique morphological characteristics through different surface chemical treatments and heat treatments, thereby providing effective sites for hydroxyapatite nucleation and adhesion in the later period; an oxide transition layer is formed on the surface of the substrate, which is beneficial to the chemical bonding of hydroxyapatite.)

1. A preparation method of Nb-Ta-Ti-Si biomedical composite material with surface activity is characterized by comprising the following steps:

(1) respectively weighing high-purity powder according to the mass proportion of each element composition of an alloy system, and mixing the materials to obtain composite powder;

(2) pressing and molding the composite powder in a mold to obtain a pressed green body;

(3) vacuum sintering the green body to obtain an Nb-Ta-Ti-Si alloy material;

(4) surface pretreatment: polishing the surface of the Nb-Ta-Ti-Si alloy material obtained in the step (3), cleaning, and performing surface treatment on the alloy by adopting a specific pretreatment mechanism;

the pretreatment mechanism is one of an acid treatment and alkali treatment process and an acid treatment, alkali treatment and heat treatment process;

(5) surface active treatment: modifying hydroxyapatite on the surface of the alloy material obtained in the step (4) by using an ultrasonic electrodeposition method;

(6) and (3) post-treatment: and (4) placing the hydroxyapatite-modified alloy material obtained in the step (5) in hot alkali liquor for post-treatment so as to increase the bonding strength of the surface active layer and the matrix and promote the conversion of the hydroxyapatite, and then cleaning and drying to obtain the surface active Nb-Ta-Ti-Si biomedical composite material.

2. The preparation method of the Nb-Ta-Ti-Si biomedical composite material with surface activity according to claim 1, wherein the acid treatment and alkali treatment process specifically comprises the following steps:

placing the cleaned alloy material in 2-5 mol/L HCl + HNO₃Soaking the sample in the mixed acid solution for 0.5-1 h, and cleaning the acid-treated sample by using ethanol and deionized water; and then soaking the mixture in 5-8 mol/L NaOH aqueous solution in a constant-temperature water bath kettle at 80 ℃ for 12-24 hours.

3. The preparation method of the Nb-Ta-Ti-Si biomedical composite material with surface activity according to claim 1, wherein the acid treatment, alkali treatment and heat treatment process specifically comprises the following steps:

placing the cleaned alloy material in 2-5 mol/L HCl + HNO₃Soaking the sample in the mixed acid solution for 0.5-1 h, and cleaning the acid-treated sample by using ethanol and deionized water; then soaking the mixture in 5-8 mol/L NaOH aqueous solution in a constant-temperature water bath kettle at 80 ℃ for 12-24 hours; and drying the sample treated by the alkali liquor at 37 ℃ for 24 hours, and putting the sample into a box-type resistance furnace for heat treatment at 300 ℃ for 2-4 hours.

4. The preparation method of the Nb-Ta-Ti-Si biomedical composite material with surface activity according to claim 1, characterized in that in the step (1), the rotation speed in the material mixing process is 200-300 r/min, and the material mixing time is 4-6 h;

the alloy comprises the following components: 10 wt.% Ta-20 wt.% Ti-0.1 wt.% Si, with the balance being Nb.

5. The preparation method of the surface-active Nb-Ta-Ti-Si biomedical composite material according to claim 1, wherein in the step (2), the pressing pressure is 300-400 MPa in the pressing process.

6. The method for preparing the surface-active Nb-Ta-Ti-Si biomedical composite material according to claim 1, wherein in the step (3), the vacuum degree of the vacuum sintering process is not lower than 10^-3Pa, the temperature of vacuum sintering is 1600-1700 ℃, the heat preservation time is 2-3 h, and the heating rate is 5-10 ℃/min.

7. The method for preparing the Nb-Ta-Ti-Si biomedical composite material with surface activity according to claim 1, wherein in the step (4), the Nb-Ta-Ti-Si alloy material is processed into a sheet sample with the diameter of 10mm multiplied by 2mm, the sample is subjected to coarse grinding and fine grinding by using sand paper, and the sheet sample is sequentially washed by acetone, ethanol and deionized water for 15-20 min.

8. The method for preparing the surface-active Nb-Ta-Ti-Si biomedical composite material according to claim 1,the method is characterized in that in the step (5), hydroxyapatite is modified on the surface of the alloy material by utilizing the composite precipitation reaction of soluble calcium salt and phosphate in the electrodeposition process; graphite is used as an anode, and an alloy material is used as a cathode; the electrodeposition temperature is 30-50 ℃, the deposition time is 30 s-15 min, and the current density is 0.5-1.5 mA/cm²(ii) a The ultrasonic frequency is 20-40 kHz, and the ultrasonic time is 1-15 min;

the soluble calcium and phosphate salts include, but are not limited to, Ca (NO)₃)₂And NH₄H₂PO₄Combinations of (a) and (b).

9. The preparation method of the Nb-Ta-Ti-Si biomedical composite material with surface activity according to claim 1, characterized in that in the step (6), the hydroxyapatite-modified alloy material is placed in NaOH solution at 70-80 ℃ and is vibrated at constant temperature for 2-3 h; the pH value of the NaOH solution is 13-14.

10. The Nb-Ta-Ti-Si biomedical composite material prepared by the preparation method according to any one of claims 1 to 9, which is characterized by comprising a matrix, an oxide intermediate layer and a hydroxyapatite surface layer.

Technical Field

The invention belongs to the field of biomedical materials, and particularly relates to a preparation method of an Nb-Ta-Ti-Si biomedical composite material with surface activity.

Background

Biomedical materials are a class of materials used to diagnose, treat, repair, or replace diseased tissues, organs or to enhance the function of living organisms, which are of vital importance in human life, and whose presence is closely related to human health. Biomedical materials can be classified according to material source, clinical use, nature composition. Among them, biomedical materials can be classified into inorganic nonmetallic materials, metallic materials, organic polymer materials and composite materials according to their composition. The biomedical metal material has good mechanical property, excellent corrosion resistance and biocompatibility, and has bright application prospect.

The biomedical metal materials which are most widely applied at present comprise stainless steel, titanium-based alloy and cobalt-based alloy. The biomedical metal material has relatively early development time and outstanding mechanical property and fatigue resistance, so the biomedical metal material is common in the application examples of human hard tissue repair and replacement, medical auxiliary instruments and the like. However, with the development of medical technology and the improvement of economic level, the shortage of biomedical metal materials in clinical application becomes prominent. Although metal materials have excellent biocompatibility, they are still considered as inert materials, and the surface of the material can only form mechanical bonding with bone tissue after being implanted into a living body, and cannot form firm chemical bonding. This will affect the long term stability of the implant, leading to loosening and even failure of the implant, which will cause immeasurable physical and psychological pain to the human body. Therefore, it is necessary to perform an activation treatment on the surface of the metal material, and to coat the surface of the material with bioactive hydroxyapatite by a modification means.

Common methods for coating hydroxyapatite on the surface of a metal substrate include plasma spraying, pulsed laser deposition, hydrothermal method, and the like. The plasma spraying method needs to operate at a high temperature of over 2000 ℃, so that the phase change of the matrix material is easy to occur, and the microstructure and the mechanical property of the material are influenced. Meanwhile, after high-temperature treatment, the coating is rapidly cooled, and the residual stress in the surface active layer can cause the coating to generate cracks and be stripped. The pulse laser method cannot be suitable for workpieces with complex surfaces and small holes, and the surface of a substrate is easy to oxidize in the treatment process, so that the binding force between a coating and the substrate is insufficient. According to the hydrothermal method, a high-pressure reaction kettle is required, the thickness of the obtained hydroxyapatite layer is not uniform, and the reaction process is not controllable.

Disclosure of Invention

Aiming at the technical problems that the long-term stability of an implant is influenced by insufficient surface activity of a metal material, the bonding strength of a surface active layer and a substrate is insufficient, the reaction condition is harsh, the reaction process is uncontrollable, and the thickness of a prepared hydroxyapatite layer is not uniform in the prior art, the invention aims to provide a preparation method of a Nb-Ta-Ti-Si biomedical composite material with surface activity.

In order to achieve the purpose, the invention provides the following technical scheme:

a preparation method of Nb-Ta-Ti-Si biomedical composite material with surface activity comprises the following steps:

(1) respectively weighing high-purity powder according to the mass proportion of each element composition of an alloy system, and mixing the materials to obtain composite powder;

(2) pressing and molding the composite powder in a mold to obtain a pressed green body;

(3) vacuum sintering the green body to obtain an Nb-Ta-Ti-Si alloy material;

(4) surface pretreatment: polishing the surface of the Nb-Ta-Ti-Si alloy material obtained in the step (3), cleaning, and performing surface treatment on the alloy by adopting a specific pretreatment mechanism;

the pretreatment mechanism is one of an acid treatment and alkali treatment process and an acid treatment, alkali treatment and heat treatment process;

(5) surface active treatment: modifying hydroxyapatite on the surface of the alloy material obtained in the step (4) by using an ultrasonic electrodeposition method;

(6) and (3) post-treatment: and (4) placing the hydroxyapatite-modified alloy material obtained in the step (5) in hot alkali liquor for post-treatment so as to increase the bonding strength of the surface active layer and the matrix and promote the conversion of the hydroxyapatite, and then cleaning and drying to obtain the surface active Nb-Ta-Ti-Si biomedical composite material.

In a preferred embodiment, the acid treatment and alkali treatment process specifically comprises:

placing the cleaned alloy material in 2-5 mol/L HCl + HNO₃Soaking the sample in the mixed acid solution for 0.5-1 h, and cleaning the acid-treated sample by using ethanol and deionized water; and then soaking the mixture in 5-8 mol/L NaOH aqueous solution in a constant-temperature water bath kettle at 80 ℃ for 12-24 hours.

In a preferred embodiment, the acid treatment, alkali treatment and heat treatment process specifically includes:

placing the cleaned alloy material in 2-5 mol/L HCl + HNO₃Soaking the sample in the mixed acid solution for 0.5-1 h, and cleaning the acid-treated sample by using ethanol and deionized water; then soaking the mixture in 5-8 mol/L NaOH aqueous solution in a constant-temperature water bath kettle at 80 ℃ for 12-24 hours; and drying the sample treated by the alkali liquor at 37 ℃ for 24 hours, and putting the sample into a box-type resistance furnace for heat treatment at 300 ℃ for 2-4 hours.

In the preferable scheme, in the step (1), the rotating speed in the material mixing process is 200-300 r/min, and the material mixing time is 4-6 h;

the alloy comprises the following components: 10 wt.% Ta-20 wt.% Ti-0.1 wt.% Si, with the balance being Nb.

Preferably, in the step (2), the pressing pressure is 300-400 MPa in the pressing process.

Preferably, in the step (3), the vacuum degree of the vacuum sintering process is not lower than 10^-3Pa, the temperature of vacuum sintering is 1600-1700 ℃, the heat preservation time is 2-3 h, and the heating rate is 5-10 ℃/min.

According to the preferable scheme, in the step (4), the Nb-Ta-Ti-Si alloy material is processed into a sheet test sample with the diameter of phi 10mm multiplied by 2mm, the sample is subjected to coarse grinding and fine grinding by using sand paper, and the sheet test sample is sequentially washed by acetone, ethanol and deionized water for 15-20 min.

Preferably, in the step (5), the electrodeposition process utilizes a composite precipitation reaction of soluble calcium salt and phosphateModifying hydroxyapatite on the surface of the alloy material; graphite is used as an anode, and an alloy material is used as a cathode; the electrodeposition temperature is 30-50 ℃, the deposition time is 30 s-15 min, and the current density is 0.5-1.5 mA/cm²(ii) a The ultrasonic frequency is 20-40 kHz, and the ultrasonic time is 1-15 min.

Further, the soluble calcium salts and phosphates include, but are not limited to, Ca (NO)₃)₂And NH₄H₂PO₄Combinations of (a) and (b).

In the preferable scheme, in the step (6), the alloy material for modifying the hydroxyapatite is placed in a NaOH solution at the temperature of 70-80 ℃ and is vibrated for 2-3 hours at constant temperature; the pH value of the NaOH solution is 13-14.

The invention also provides a Nb-Ta-Ti-Si biomedical composite material which is composed of a matrix, an oxide intermediate layer and a hydroxyapatite surface layer and is expected to become a material for repairing and replacing human bone tissues.

Compared with the prior art, the invention has the beneficial technical effects that:

1) by pretreating the surface of the alloy material (acid treatment and alkali treatment or acid treatment, alkali treatment and heat treatment), an oxide intermediate layer is formed on the surface of the base material after surface pretreatment, so that the roughness of the surface of the material can be effectively improved, and the bonding strength between the base material and the surface layer is improved; through surface coupling treatment (surface pretreatment, surface active treatment and post-treatment), a 'sandwich' structure of a compact matrix layer, an oxide intermediate layer and a surface active layer is formed on the surface of the material.

2) The method deposits the hydroxyapatite active layer on the surface of the metal matrix, has mild experimental conditions, and can effectively avoid the problem of insufficient interface bonding strength between the surface active layer and the metal matrix; the hydroxyapatite active layer on the surface of the alloy material is beneficial to improving the surface inertia of the metal material, overcomes the defect that the long-term stability of the implant is influenced due to insufficient surface activity of the traditional biomedical metal material, and is expected to become a human hard tissue repair or substitute material.

3) The invention adopts a specific pretreatment mechanism to carry out surface treatment on the alloy, and the surface of the substrate obtains unique morphological characteristics through different surface chemical treatments and heat treatments, thereby providing effective sites for hydroxyapatite nucleation and adhesion in the later period; an oxide transition layer is formed on the surface of the substrate, which is beneficial to the chemical bonding of hydroxyapatite.

Drawings

FIG. 1: acid treatment (2mol/L HCl + HNO)₃Soaking a sample in the mixed acid solution for 1 hour) and performing alkali treatment (5mol/L NaOH aqueous solution, and soaking in a constant-temperature water bath at 80 ℃ for 24 hours) to obtain a sample morphology graph.

Fig. 2 (a): acid treatment (2mol/L HCl + HNO)₃Soaking a sample in a mixed acid solution for 1h), treating with an alkali (5mol/L NaOH aqueous solution), soaking in a constant-temperature water bath at 80 ℃ for 24h), and performing heat treatment (keeping the temperature at 300 ℃ for 2h) to obtain a sample morphology graph; fig. 2(b) is an enlarged view of fig. 2 (a).

FIG. 3: the appearance of the surface bone-like apatite after ultrasonic electrodeposition.

FIG. 4: and (3) performing co-culture on the surface of the sample for 24h to obtain a topographic map of MG-63 cells.

FIG. 5: after acid treatment (2mol/L HCl + HNO)₃Soaking the sample in the mixed acid solution for 1h) and obtaining a sample morphology graph.

Detailed Description

The invention is further described with reference to the following figures and specific examples.