阅读说明：本技术 一种节能环保生物材料及其制备方法 (energy-saving environment-friendly biological material and preparation method thereof ) 是由 裴培 丁诗娟 于 2019-08-23 设计创作，主要内容包括：本发明公开了一种节能环保生物材料及其制备方法,属于生物材料制备领域。一种节能环保生物材料及其制备方法,采用粉末冶金的方法,通过原位反应机理制备了生物复合材料,XRD和SEM结果显示,均匀分布于镁基体颗粒间的为Mg合金与HA的复合组织。模拟体液中的浸泡实验和电化学实验分析结果一致表明,生物复合材料与纯镁有相近的腐蚀行为,相对于复合材料,生物复合材料表现出更好的耐一腐蚀性能;同时,生物复合材料中镁基体颗粒周围均匀分布的复合相能大大提高复合材料的力学性能,而且与天然骨的力学性能相当。研究还表明,HA在复合材料中的存在,能提高材料的力学性能。(the invention discloses an energy-saving environment-friendly biological material and a preparation method thereof, belonging to the field of biological material preparation. An energy-saving environment-friendly biological material and a preparation method thereof adopt a powder metallurgy method to prepare a biological composite material through an in-situ reaction mechanism, and XRD and SEM results show that composite tissues of Mg alloy and HA are uniformly distributed among magnesium matrix particles. The results of the immersion experiment and the electrochemical experiment in the simulated body fluid are consistent, which shows that the biological composite material has similar corrosion behavior with pure magnesium, and the biological composite material shows better corrosion resistance compared with the composite material, and simultaneously, the composite phase uniformly distributed around the magnesium matrix particles in the biological composite material can greatly improve the mechanical property of the composite material and is equivalent to the mechanical property of natural bones. Research also shows that the existence of HA in the composite material can improve the mechanical property of the material.)

1. an energy-saving and environment-friendly biological material and a preparation method thereof are characterized in that: comprises the following steps;

S1, preparing nano HA powder by adopting a sol-gel method;

S2, weighing pure magnesium powder, HA powder and magnesium oxide powder according to a certain proportion, fully mixing the raw materials, and then putting the mixture into a die blank to be compacted;

S3, starting a vacuum pump at room temperature and normal pressure to vacuumize the hot-pressing sintering furnace, filling high-purity argon into the refrigerator until the interior of the vacuum sintering furnace returns to the normal pressure, and repeating the process twice;

S4, placing the die blank prepared in the S2 in a hot-pressing sintering furnace, heating and pressurizing under the protection of argon, heating to 110 ℃ and keeping the pressure constant for 10min, heating for 20min under the temperature and the pressure, continuing heating to 560 ℃ and keeping the pressure constant for 25, sintering for 4h, cooling to room temperature, and reducing the pressure to normal pressure to prepare a sintered product;

s5, performing surface pretreatment on the sintered product;

s6, preparing a surface oxidation film on the pretreated product in the S5 by adopting a three-electrode system;

And S7, completely soaking the conforming material with the surface covered with the oxide film in a polylactic acid solution, standing for 10min, naturally drying, and repeating the soaking and drying treatment for more than 4-5 times to prepare the biological composite material.

2. the energy-saving and environment-friendly biomaterial and the preparation method thereof as claimed in claim 1, wherein the biomaterial comprises: the preparation of the nano HA by the sol-gel method in the S1 comprises the following steps:

a1, weighing the materials according to the calcium-phosphorus ratio of 1.66, and preparing a solution with a certain concentration;

a2, stirring the solution at a high speed by a magnetic stirring rotor under the environment of a constant-temperature water bath, and dripping ammonia water into the solution to ensure that the pH value of the solution is 10.5;

a3, slowly dripping the solution to obtain a white solution, and keeping the pH value of the solution at 10.5 by using ammonia water in the titration process;

A4, stirring 1Omin after the reaction is finished, and aging the solution for 14 h;

a5, sequentially filtering the aged suspension, washing with deionized water to the lowest pH value, and washing with absolute alcohol for several times;

A6, drying the sample at 50 ℃ to obtain white powder;

a7, calcining the white powder at 900 ℃ for 1 h.

3. the energy-saving and environment-friendly biomaterial and the preparation method thereof as claimed in claim 1, wherein the biomaterial comprises: pure magnesium powder, HA powder and magnesia powder in the S2 are mixed according to the weight ratio of 7: 2: 1.

4. The energy-saving and environment-friendly biomaterial and the preparation method thereof as claimed in claim 1, wherein the biomaterial comprises: the pure magnesium powder in the S2 is pure magnesium powder with the particle size of 48-52 and the purity of 99.5%.

5. The energy-saving and environment-friendly biomaterial and the preparation method thereof as claimed in claim 1, wherein the biomaterial comprises: the pretreatment in the S5 comprises the following steps: and (3) grinding the sintered product by adopting 800-plus 4000-mesh metallographic abrasive paper, then polishing by using 0.3 corundum polishing powder, ultrasonically removing polishing powder, oil stain and other dirt in deionized water, acetone and deionized water respectively, and finally drying at normal temperature.

6. the energy-saving and environment-friendly biomaterial and the preparation method thereof as claimed in claim 1, wherein the biomaterial comprises: the preparation of the oxide film in S6 comprises the following steps: respectively carrying out anode scanning by using a linear scanning voltammetry at constant temperature of 25 ℃ and 50 ℃, wherein the initial potential is the termination potential of 1.8V, and the scanning speed is 0.003, so as to obtain an anode polarization curve; obtaining an initial passivation potential, a breaking potential and two potential sums between the two potentials, namely <; respectively carrying out anodic oxidation at a constant temperature of 50 ℃ for 2 hours by taking the component (A), (B) and (C) as constant potentials, then carrying out ultrasonic cleaning for 10 minutes by using deionized water, and then naturally airing; and (3) drying the anodic oxide film obtained by the electrochemical method, carrying out heat treatment at 450 ℃ for 4h, taking out, and naturally cooling.

7. the energy-saving and environment-friendly biomaterial and the preparation method thereof as claimed in claim 1, wherein the biomaterial comprises: the polylactic acid solution in the S7 is prepared by dissolving polylactic acid in dichloromethane to be 0.5.

Technical Field

The invention relates to the field of preparation of biological materials, in particular to an energy-saving and environment-friendly biological material and a preparation method thereof.

background

Magnesium is the eighth most abundant element in the earth's content ranks, is the third most abundant metal element next to aluminum and iron in the earth's crust, and its reserve accounts for 2.7% of the earth's crust, and the seawater is also quite abundant, with a content of 0.13%. Magnesium, which has a density of 1.7g/cm3, is one of the lightest metals. In crystallography, magnesium is a crystal of a hexagonal close-packed structure, a =0.321nm, c =0.521nm, and c/a =1.624, and has a close-perfect close-packed structure compared with the c/a value of an ideal hexagonal close-packed structure, and thus has a small slip system at room temperature and poor cold deformability. Therefore, the magnesium alloy has poor plasticity, low strength at normal temperature and poor mechanical property, so that pure magnesium is rarely used as a structural material, and the magnesium alloy is mainly used for manufacturing magnesium alloy and blending other nonferrous alloy materials. However, magnesium is better than both steel and aluminum in view of its combined specific strength and specific stiffness. Magnesium also has an important characteristic of having a very low standard electrode potential, a very high corrosion rate in saline solutions, and particularly a poorer corrosion resistance in human environments containing chloride ions.

The pure magnesium metal material has poor corrosion resistance, short service life when being applied to human bones, and difficult mechanical property reaching long-term use standards.

Disclosure of Invention

The invention aims to solve the problems that pure magnesium metal materials are poor in corrosion resistance, short in service life and difficult to achieve long-term use standards when applied to human bones, and provides an energy-saving environment-friendly biomaterial and a preparation method thereof.

in order to achieve the purpose, the invention adopts the following technical scheme:

an energy-saving and environment-friendly biological material and a preparation method thereof, comprising the following steps;

S1, preparing nano HA powder by adopting a sol-gel method;

S2, weighing pure magnesium powder, HA powder and magnesium oxide powder according to a certain proportion, fully mixing the raw materials, and then putting the mixture into a die blank to be compacted;

s3, starting a vacuum pump at room temperature and normal pressure to vacuumize the hot-pressing sintering furnace, filling high-purity argon into the refrigerator until the interior of the vacuum sintering furnace returns to the normal pressure, and repeating the process twice;

S4, placing the die blank prepared in the S2 in a hot-pressing sintering furnace, heating and pressurizing under the protection of argon, heating to 110 ℃ and keeping the pressure constant for 10min, heating for 20min under the temperature and the pressure, continuing heating to 560 ℃ and keeping the pressure constant for 25, sintering for 4h, cooling to room temperature, and reducing the pressure to normal pressure to prepare a sintered product;

s5, performing surface pretreatment on the sintered product;

S6, preparing a surface oxidation film on the pretreated product in the S5 by adopting a three-electrode system;

and S7, completely soaking the conforming material with the surface covered with the oxide film in a polylactic acid solution, standing for 10min, naturally drying, and repeating the soaking and drying treatment for more than 4-5 times to prepare the biological composite material.

preferably, the preparation of the nano-HA by the sol-gel method in S1 comprises the following steps:

A1, weighing the materials according to the calcium-phosphorus ratio of 1.66, and preparing a solution with a certain concentration;

a2, stirring the solution at a high speed by a magnetic stirring rotor under the environment of a constant-temperature water bath, and dripping ammonia water into the solution to ensure that the pH value of the solution is 10.5;

A3, slowly dripping the solution to obtain a white solution, and keeping the pH value of the solution at 10.5 by using ammonia water in the titration process;

a4, stirring 1Omin after the reaction is finished, and aging the solution for 14 h;

a5, sequentially filtering the aged suspension, washing with deionized water to the lowest pH value, and washing with absolute alcohol for several times;

A6, drying the sample at 50 ℃ to obtain white powder;

A7, calcining the white powder at 900 ℃ for 1 h.

preferably, the pure magnesium powder, the HA powder and the magnesium oxide powder in the S2 are mixed according to the weight ratio of 7: 2: 1.

Preferably, the pure magnesium powder in the S2 is pure magnesium powder with the particle size of 48-52 and the purity of 99.5%.

Preferably, the preprocessing in S5 adopts the following steps: and (3) grinding the sintered product by adopting 800-plus 4000-mesh metallographic abrasive paper, then polishing by using 0.3 corundum polishing powder, ultrasonically removing polishing powder, oil stain and other dirt in deionized water, acetone and deionized water respectively, and finally drying at normal temperature.

Preferably, the preparation of the oxide film in S6 includes the following steps: respectively carrying out anode scanning by using a linear scanning voltammetry at constant temperature of 25 ℃ and 50 ℃, wherein the initial potential is the termination potential of 1.8V, and the scanning speed is 0.003, so as to obtain an anode polarization curve; obtaining an initial passivation potential, a breaking potential and two potential sums between the two potentials, namely <; respectively carrying out anodic oxidation at a constant temperature of 50 ℃ for 2 hours by taking the component (A), (B) and (C) as constant potentials, then carrying out ultrasonic cleaning for 10 minutes by using deionized water, and then naturally airing; and (3) drying the anodic oxide film obtained by the electrochemical method, carrying out heat treatment at 450 ℃ for 4h, taking out, and naturally cooling.

preferably, the polylactic acid solution in S7 is prepared by dissolving polylactic acid in dichloromethane to obtain a 0.5 polylactic acid solution.

Compared with the prior art, the invention provides an energy-saving environment-friendly biological material and a preparation method thereof, and the energy-saving environment-friendly biological material has the following beneficial effects:

1. The invention adopts a powder metallurgy method, prepares the biological composite material by an in-situ reaction mechanism, and XRD and SEM results show that the composite structure of Mg alloy and HA is uniformly distributed among magnesium matrix particles. The results of the immersion experiment and the electrochemical experiment in the simulated body fluid are consistent, which shows that the biological composite material has similar corrosion behavior with pure magnesium, and the biological composite material shows better corrosion resistance compared with the composite material, and simultaneously, the composite phase uniformly distributed around the magnesium matrix particles in the biological composite material can greatly improve the mechanical property of the composite material and is equivalent to the mechanical property of natural bones. Research also shows that the existence of HA in the composite material can improve the mechanical property of the material.

Detailed Description