阅读说明：本技术 一种微米有序纳米无序图案结构在钛基底上的制备方法 (A kind of preparation method of the unordered patterning of micro ordered nanometer in titanium substrate ) 是由 吴水林 付杰妮 刘想梅 于 2019-08-05 设计创作，主要内容包括：本发明提供了一种微米有序纳米无序图案结构在钛基底上的制备方法,包括以下步骤：(1)钛片处理,(2)微米有序结构在钛基底上的构建,(3)纳米无序结构在微米有序结构钛片基底的构建。本发明使用选择性激光熔覆制备微米有序结构方法简单,以碱热一段时间在微米结构上修饰一层纳米结构形成微米有序纳米无序图案结构,并且通过两者的协调作用可改善其各自的缺点,使其具有更加优异的生物功能,本发明制备方法设备投入少,实施难度小,制备方法简单易行,并且对环境并无太大影响。(The present invention provides a kind of preparation method of unordered patterning of micro ordered nanometer in titanium substrate, the following steps are included: (1) titanium sheet is handled, (2) building of the micro ordered structure in titanium substrate, building of (3) the nanometer disordered structure in micro ordered structure titanium sheet substrate.The present invention is simple using selective laser cladding preparation micro ordered structural approach, one layer of nanostructure is modified on micrometer structure with alkali heat a period of time forms the unordered patterning of micro ordered nanometer, and its disadvantage respectively can be improved by the coordinative role of the two, make it have more excellent biological function, preparation method equipment investment of the present invention is few, enforcement difficulty is small, and preparation method is simple, and has no too big influence to environment.)

1. a kind of preparation method of unordered patterning of micro ordered nanometer in titanium substrate, it is characterised in that including following step It is rapid:

1) titanium sheet is handled

By titanium disk with after sand paper step by step surface polishing, successively it is cleaned by ultrasonic in acetone, distilled water, alcohol, and in room The complete titanium sheet of drying, is then placed in mixed acid solution and impregnates two minutes, then put in 60-80 DEG C of baking oven by the lower drying of temperature 90 minutes are set, drying sample；

2) building of the micro ordered structure in titanium substrate

The titanium sheet handled well in step 1) is placed in laser processing system, operating platform is along x in the laser processing system The movement rate of axis direction is 0.5-0.7mm/s, and move distance along the y-axis direction is 600-700 μm, after laser treatment titanium sheet, Up to the titanium sheet substrate of micro ordered, it is named as Ti-LA；

3) building of the nanometer disordered structure in micro ordered structure titanium sheet substrate

The Ti-LA that step 2) is obtained is put into the 100mL reaction kettle for filling 70-90mL KOH solution, then by the reaction Kettle, which is put into 100-120 DEG C of baking oven, dries 2-3h, and gained dries product and impregnates 10-15min with deionized water ultrasound, then exists It is placed 90 minutes in 60-80 DEG C of baking oven, there is the titanium sheet base of the unordered patterning of micro ordered nanometer to obtain the final product after the completion of dry Bottom.

2. a kind of preparation method of the unordered patterning of micro ordered nanometer according to claim 1 in titanium substrate, It is characterized in that, titanium disc diameter described in step 1) is 6mm, with a thickness of 2.5mm.

3. a kind of preparation method of the unordered patterning of micro ordered nanometer according to claim 1 in titanium substrate, It is characterized in that, the concentration ratio of mixed acid solution each component described in step 1) is HF:HNO₃:H₂O=1:4:5.

4. a kind of preparation method of the unordered patterning of micro ordered nanometer according to claim 1 in titanium substrate, It is characterized in that, the parameter of laser system described in step 2) is that electric current is 80-100A, and energy is 20-40 J/mm²。

5. a kind of preparation method of the unordered patterning of micro ordered nanometer according to claim 1 in titanium substrate, It is characterized in that, KOH solution concentration described in step 3) is 1-4mol/mL.

Technical field

The invention belongs to biomedical material technologies, and in particular to a kind of unordered patterning of micro ordered nanometer exists Preparation method in titanium substrate.

Background technique

Medical titanium has superior mechanical property, and corrosion resistance is strong, and elasticity modulus is low, and good biocompatibility etc. is excellent Characteristic is the common internal fixation material of current orthopaedics, as implant material especially in load portion in orthopaedics internal fixation operation Position is widely used.However due to medical titanium base material implant and the Integrated implant capability defect of surrounding tissue by More and more people are paid attention to, and are more likely to be differentiated to form cartilage when the not so good substrate of osteocyte contact osseointegration character Cell, and non-formation osteocyte, lead to the failure of bone implant.More pains and economic loss can be not only brought, or even can also Make one amputation or death.In order to improve the success rate of bone implant, there is an urgent need on implant in the item for not influencing its service performance It is modified under part, makes it have the ability of Integrated implant, cell adhesion, proliferation and Osteoblast Differentiation can be promoted.

Extracellular matrix provides the substance and signal of cell normal activities, some signals can influence the life of cell Fortune, such as: Osteoblast Differentiation, the signal that extracellular matrix provides can be divided into physical signal and chemical signal two major classes, physics letter Number because its is cheap, action time is widely studied in recent years for a long time.It is planted therefore, it is possible to consider to construct physical signal in titanium Enter on body, so as to improve the performance of its Integrated implant.

The unordered patterning of micro ordered nanometer can not only stimulate osteoblast, but also can stimulate stem cell skeletonization point Change.On the one hand the hydrophily on titanium implants surface can be enhanced in the unordered patterning of micro ordered nanometer, promote cell in modification Titanium implants surfaces is sticked afterwards；On the other hand the behavior and destiny of cell be can change.

Summary of the invention

In response to this, the preparation the present invention provides a kind of unordered patterning of micro ordered nanometer in titanium substrate Method can be solved the problems, such as effectively of the existing technology.

To achieve the above object, technical solution provided by the invention is as follows: a kind of unordered patterning of micro ordered nanometer Preparation method in titanium substrate, it is characterised in that the following steps are included:

1) titanium sheet is handled

By titanium disk with after sand paper step by step surface polishing, successively it is cleaned by ultrasonic in acetone, distilled water, alcohol, and It is dried at room temperature for, then the complete titanium sheet of drying is placed in mixed acid solution and is impregnated two minutes, then in 60-80 DEG C of baking oven It is middle to place 90 minutes, drying sample；

2) building of the micro ordered structure in titanium substrate

The titanium sheet handled well in step 1) is placed in laser processing system, operating platform in the laser processing system Movement rate along the x-axis direction is 0.5-0.7mm/s, and move distance along the y-axis direction is 600-700 μm, laser treatment titanium sheet Afterwards to get the titanium sheet substrate of micro ordered, it is named as Ti-LA；

3) building of the nanometer disordered structure in micro ordered structure titanium sheet substrate

The Ti-LA that step 2) is obtained is put into the 100mL reaction kettle for filling 70-90mLKOH solution, then will be described anti- It answers kettle to be put into 100-120 DEG C of baking oven and dries 2-3h, gained dries product and impregnates 10-15min with deionized water ultrasound, then exists It is placed 90 minutes in 60-80 DEG C of baking oven, there is the titanium sheet base of the unordered patterning of micro ordered nanometer to obtain the final product after the completion of dry Bottom.

Preferably, titanium disc diameter is 6mm, with a thickness of 2.5mm in the step 1).

Preferably, each component concentration ratio is HF:HNO in mixed acid solution in the step 1)₃:H₂O=1:4:5.

Preferably, it is 80-100A, energy 20-40J/mm that the parameter of laser system, which is electric current, in the step 2)²。

Preferably, KOH solution concentration is 1-4mol/mL in the step 3).

The advantageous effect of present invention is that:

(1) present invention enormously simplifies preparation process using selective laser cladding and alkali heat；

(2) present invention combines micrometer structure and nanostructure so that micro ordered nanometer is unordered for Integrated implant material, There is certain similitude with extracellular matrix, micro-nano hierarchical structure promotes cell sticking on its surface, improves titanium-based The osseointegration character of bottom surface has more excellent biological function；

(3) present invention preparation micro ordered, the unordered pattern structural device less investment of nanometer, enforcement difficulty is small, preparation method It is simple and easy, and too big influence is had no on environment.

Detailed description of the invention

Fig. 1 is that the SEM of titanium sheet of the embodiment 1 after selective laser cladding schemes, the real camera picture of a sample；B sample The SEM of product schemes；

Fig. 2 is the figure of the XRD of titanium sheet after selective laser cladding and alkali heat-treatment；

Fig. 3 is the figure of the contact angle of titanium sheet after selective laser cladding and alkali heat-treatment；

Fig. 4 is SEM figure of the osteoblast on sample, and scale is 1 μm；

Fig. 5 is the figure of fluorescent staining of the mesenchymal stem cell on sample, and scale is 100 μm.

Specific embodiment

In order to make the object, technical scheme and advantages of the embodiment of the invention clearer, below in conjunction with the embodiment of the present invention In attached drawing, technical scheme in the embodiment of the invention is clearly and completely described.

The specific embodiment of the invention is as follows: