阅读说明：本技术 羟基磷灰石掺杂及抑肿瘤增殖的镁合金骨夹板及制备方法 (Magnesium alloy bone splint doped with hydroxyapatite and capable of inhibiting tumor proliferation and preparation method ) 是由 徐春杰 华心雨 王银玉 萨娜·扎珐 史妍 李梦阳 杜薇 李诊娇 田颖晨 武向权 于 2021-07-14 设计创作，主要内容包括：本发明公开的一种羟基磷灰石掺杂及抑肿瘤增殖的镁合金骨夹板,按重量百分由以下组分组成：La：2-3％,羟基磷灰石：3-12％,镁余量,以上各组分重量百分比之和为100％。该合金不仅具备优异的生物相容性,还具有抑制肿瘤增殖的功能。还公开了一种羟基磷灰石掺杂及抑肿瘤增殖的镁合金骨夹板的制备方法,运用选区激光熔化技术可制备任意形状复杂的骨夹板结构,既能满足骨夹板复杂的结构要求,同时也能满足表面精度及力学性能的要求。(The invention discloses a magnesium alloy bone splint doped with hydroxyapatite and inhibiting tumor proliferation, which comprises the following components in percentage by weight: la: 2-3%, hydroxyapatite: 3-12 percent of magnesium and the balance of magnesium, wherein the sum of the weight percent of the components is 100 percent. The alloy not only has excellent biocompatibility, but also has the function of inhibiting tumor proliferation. The preparation method of the magnesium alloy bone splint doped with hydroxyapatite and inhibiting tumor proliferation is also disclosed, and the bone splint structure with any complex shape can be prepared by applying the selective laser melting technology, so that the requirements of the complex structure of the bone splint can be met, and the requirements of surface precision and mechanical properties can also be met.)

1. The magnesium alloy bone splint doped with hydroxyapatite and capable of inhibiting tumor proliferation is characterized by comprising the following components in percentage by weight: la: 2-3%, hydroxyapatite: 3-12 percent of magnesium and the balance of magnesium, wherein the sum of the weight percent of the components is 100 percent.

2. The magnesium alloy bone splint doped with hydroxyapatite and inhibiting tumor proliferation according to claim 1, wherein the magnesium alloy bone splint is prepared from 30-50 μm atomized magnesium powder, 30-50 μm La powder and 30-50 μm hydroxyapatite powder.

3. A preparation method of a magnesium alloy bone splint doped with hydroxyapatite and inhibiting tumor proliferation is characterized by comprising the following steps:

step 1, weighing:

weighing the following raw materials in percentage by weight: la powder: 2-3%, hydroxyapatite powder: 3-12 percent of magnesium powder, and the balance of atomized magnesium powder, wherein the sum of the weight percentages of the components is 100 percent;

step 2, ball milling and powder mixing:

placing the weighed raw material powder into a horizontal high-energy ball mill for ball milling and mixing to promote the hydroxyapatite to be fully mixed with the atomized magnesium powder and the La powder;

and 3, selective laser melting and forming:

and (3) putting the magnesium alloy powder prepared in the step (2) into selective laser melting equipment, introducing a three-dimensional drawing of a bone splint, setting laser power, scanning speed, scanning distance, layer thickness and path planning parameters, and starting SLM printing and forming.

4. The preparation method of the magnesium alloy bone splint doped with hydroxyapatite and inhibiting tumor proliferation according to claim 3, wherein in the step 2, the ball milling technological parameters are as follows: the ball material weight ratio is 1:1, the rotating speed is 100-. Argon is filled into the milling tank to protect the powder from oxidation. The grinding balls used were: boron carbide grinding balls with the diameters of phi 5mm and phi 10mm, wherein the weight ratio of the large balls to the small balls is 1: 1.

5. the preparation method of the magnesium alloy bone splint doped with hydroxyapatite and inhibiting tumor proliferation according to claim 3, wherein in the step 3, the process parameters of the laser melting in the selected area are as follows: the laser power is 60-80W, the scanning speed is 500-700mm/s, the scanning pitch is 30-50 μm, and the layer thickness is 30 μm.

6. The method for preparing a magnesium alloy bone splint doped with hydroxyapatite and inhibiting tumor proliferation according to claim 3, wherein in the step 3, the whole processing process is carried out in a processing chamber with argon protection.

Technical Field

The invention belongs to the technical field of degradable medical metal materials, and particularly relates to a magnesium alloy bone splint doped with hydroxyapatite and capable of inhibiting tumor proliferation, and a preparation method of the magnesium alloy bone splint doped with hydroxyapatite and capable of inhibiting tumor proliferation.

Background

The density of magnesium is 1.74g/cm³The density of all metal structural materials is the minimum and is close to the density of human bones. Magnesium is an essential nutrient element for human body, and the content of magnesium in human body is second to Ca, Na and K. Researches show that the magnesium alloy is used as a bone fixing material, is more matched with the mechanical property of human bones, can provide stable mechanical property at the early stage of fracture healing, can avoid stress shielding effect, thereby accelerating fracture healing and shaping, preventing local osteoporosis and recurrence of fracture, particularly can realize that after the basic healing of human bones, the magnesium alloy is degraded into nontoxic harmless micromolecules and is discharged out of the human body through the circulatory system of the human body, thereby avoiding suffering from diseasesThe patient suffers from the pain of taking out the medicine after the second operation. Hydroxyapatite is the main inorganic component of human and animal bones. It can be chemically bonded with organism tissue on interface, has certain solubility in vivo, can release harmless ions to organism, participate in vivo metabolism, stimulate or induce hyperostosis, promote repair of defective tissue, and exhibit bioactivity. La is a rare earth element, is beneficial to inhibiting the proliferation of tumor cells and has the biological effects of regulating the cellular immune function and the like. The biodegradable magnesium alloy material with excellent performance is prepared by combining the raw materials with different functional effects.

Selective Laser Melting (SLM) is a laser additive manufacturing technology, which uses a high-energy laser beam to selectively irradiate pre-spread metal powder based on the principle of layered superposition, so that the metal powder is completely melted and layered to be formed. Because the rapid cooling and solidification processing process is adopted, a non-equilibrium supersaturated solid solution and a uniform and fine metallographic structure can be obtained, and a customized workpiece with almost any shape, high forming precision and good mechanical property can be prepared. The SLM technology has wide prospect and important significance for developing materials with high performance and complex structures.

At present, the bone splint for clinical application is mainly manufactured by the traditional methods of machining, die forming and the like, however, human bones have personalized differences, which causes the situation that a standardized implant is not matched with the personalized bones, thereby affecting the treatment effect. In addition, the customization of the conventional bone splint requires a complicated and long manufacturing period and a large cost, and consumes a large amount of manpower, material resources and financial resources. In order to solve the problem that the bone splint in the prior art is uncomfortable to wear, the 3D printing technology can design customized bone splint drawing according to CT scanning drawings according to the requirements of different patients, the bone splint suitable for the requirements of the patients is manufactured, and the comfort level of the patients is greatly improved. Therefore, the SLM process research of the magnesium alloy bone splint has important application prospect.

The patent of 'a preparation method of a magnesium-based composite material bone implant and a product thereof' (application number: 201811389545.0, publication number: CN109364292A, published by the Japan: 2019.02.22) adopts a three-dimensional spray printing process to form the magnesium-based composite material bone implant, which can meet individual requirements, but does not consider some functional requirements. The invention not only can prepare the bone splint meeting the individual requirements through selective laser melting forming, but also adds hydroxyapatite and La element, so that the bone splint has good bone conductivity, bone inductivity and biocompatibility, and simultaneously has the biological effects of inhibiting tumor proliferation, regulating cellular immunity and the like.

Disclosure of Invention

The invention aims to provide a magnesium alloy bone splint doped with hydroxyapatite and capable of inhibiting tumor proliferation, and the alloy not only has excellent biocompatibility, but also has the function of inhibiting tumor proliferation.

The second purpose of the invention is to provide a preparation method of magnesium alloy bone splint doped with hydroxyapatite and inhibiting tumor proliferation, which can prepare bone splint structures with any complicated shapes by using a selective laser melting technology, and can meet the requirements of complicated structure of the bone splint and the requirements of surface precision and mechanical property.

The magnesium alloy bone splint comprises the following components in percentage by weight: la: 2-3%, hydroxyapatite: 3-12 percent of magnesium and the balance of magnesium, wherein the sum of the weight percent of the components is 100 percent.

The present invention is also characterized in that,

the magnesium alloy bone splint is prepared from 30-50 μm atomized magnesium powder, 30-50 μm La powder and 30-50 μm hydroxyapatite powder.

The second technical scheme adopted by the invention is that the preparation method of the magnesium alloy bone splint doped with hydroxyapatite and inhibiting tumor proliferation comprises the following steps:

step 1, weighing:

weighing the following raw materials in percentage by weight: la powder: 2-3%, hydroxyapatite powder: 3-12 percent of magnesium powder, and the balance of atomized magnesium powder, wherein the sum of the weight percentages of the components is 100 percent;

step 2, ball milling and powder mixing:

placing the weighed raw material powder into a horizontal high-energy ball mill for ball milling and mixing to promote the hydroxyapatite to be fully mixed with the atomized magnesium powder and the La powder;

and 3, selective laser melting and forming:

and (3) putting the magnesium alloy powder prepared in the step (2) into Selective Laser Melting (SLM) equipment, introducing a three-dimensional drawing of a bone splint, setting laser power, scanning speed, scanning distance, layer thickness and path planning parameters, and starting SLM printing and forming.

The present invention is also characterized in that,

in step 2, ball milling technological parameters are as follows: the ball material weight ratio is 1:1, the rotating speed is 100-. Argon is filled into the milling tank to protect the powder from oxidation. The grinding balls used were: boron carbide grinding balls with the diameters of phi 5mm and phi 10mm, wherein the weight ratio of the large balls to the small balls is 1: 1.

in step 3, the process parameters of selective laser melting are as follows: the laser power is 60-80W, the scanning speed is 500-700mm/s, the scanning pitch is 30-50 μm, and the layer thickness is 30 μm.

In step 3, the whole processing process is carried out in a processing chamber with argon gas protection to avoid the metal reacting with other gases at high temperature.

The invention has the beneficial effects that: the magnesium alloy bone splint prepared by the selective laser melting technology can meet the complex structural requirement of the bone splint, and can also meet the requirements of surface precision and mechanical property, the added hydroxyapatite can promote the repair of defective tissues, and the La element is beneficial to inhibiting tumor proliferation.

Drawings

FIG. 1 is a flow chart of the preparation process of the present invention.

Detailed Description

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

The invention provides a magnesium alloy bone splint doped with hydroxyapatite and inhibiting tumor proliferation, which comprises the following components in percentage by weight: la: 2-3%, hydroxyapatite: 3-12 percent of magnesium and the balance of magnesium, wherein the sum of the weight percent of the components is 100 percent.

The magnesium alloy bone splint for preparing hydroxyapatite doping and inhibiting tumor proliferation adopts the raw materials of 30-50 mu m atomized magnesium powder, 30-50 mu m La powder and 30-50 mu m hydroxyapatite powder.

The invention also provides a preparation method of the magnesium alloy bone splint doped with hydroxyapatite and inhibiting tumor proliferation, which comprises the following steps as shown in figure 1:

step 1, weighing:

weighing the following raw materials in percentage by weight: la powder: 2-3%, hydroxyapatite powder: 3-12 percent of magnesium powder, and the balance of atomized magnesium powder, wherein the sum of the weight percentages of the components is 100 percent;

step 2, ball milling and powder mixing:

placing the weighed raw material powder into a horizontal high-energy ball mill for ball milling and mixing to promote the hydroxyapatite to be fully mixed with the atomized magnesium powder and the La powder;

in step 2, ball milling technological parameters are as follows: the ball material weight ratio is 1:1, the rotating speed is 100-. Argon is filled into the milling tank to protect the powder from oxidation. The grinding balls used were: boron carbide grinding balls with the diameters of phi 5mm and phi 10mm, wherein the weight ratio of the large balls to the small balls is 1: 1.

and 3, selective laser melting and forming:

and (3) putting the magnesium alloy powder prepared in the step (2) into Selective Laser Melting (SLM) equipment, introducing a three-dimensional drawing of a bone splint, setting parameters such as laser power, scanning speed, scanning distance, layer thickness and path planning, and starting SLM printing and forming.

In step 3, the process parameters of selective laser melting are as follows: the laser power is 60-80W, the scanning speed is 500-700mm/s, the scanning pitch is 30-50 μm, and the layer thickness is 30 μm.

In step 3, the whole processing process is carried out in a processing chamber with argon gas protection to avoid the metal reacting with other gases at high temperature.

Example 1

Step 1, weighing:

weighing the following raw materials in percentage by weight: la powder: 2%, hydroxyapatite powder: 3 percent of atomized magnesium powder, and the sum of the weight percentages of the components is 100 percent;

step 2, ball milling and powder mixing:

and (3) placing the weighed powder into a horizontal high-energy ball mill for ball milling and mixing, wherein ball milling technological parameters are as follows: the ball material weight ratio is 1:1, the rotating speed is 100r/min, the ball milling time is 10h, the ball milling device alternately rotates forwards and backwards at intervals of 1h and 10min, and the temperature of the tank body is not overhigh. Argon is filled into the milling tank to protect the powder from oxidation. The grinding balls used were: boron carbide grinding balls with the diameters of phi 5mm and phi 10mm, wherein the weight ratio of the large balls to the small balls is 1: 1;

step 3, selective laser melting and forming:

putting the prepared magnesium alloy powder into Selective Laser Melting (SLM) equipment, and introducing a three-dimensional drawing of a bone splint, wherein the technological parameters of selective laser melting are as follows: the SLM printing was started with a laser power of 80W, a scanning speed of 500mm/s, a scanning pitch of 40 μm, a layer thickness of 30 μm, and a zigzag printing path. The whole processing process is carried out in a processing chamber with argon protection, so as to avoid the metal reacting with other gases at high temperature.

The obtained magnesium alloy has grain size of 2-5 μm, compactness of 97.5%, and Vickers hardness of 89.6HV₅Tensile strength at room temperature of 328.5MPa and elongation of 8.8 percent.

Example 2

Step 1, weighing:

weighing the following raw materials in percentage by weight: la powder: 2.5%, hydroxyapatite powder: 12 percent, and the balance being atomized magnesium powder, wherein the sum of the weight percentages of the components is 100 percent;

step 2, ball milling and powder mixing:

and (3) placing the weighed powder into a horizontal high-energy ball mill for ball milling and mixing, wherein ball milling technological parameters are as follows: the ball material weight ratio is 1:1, the rotating speed is 150r/min, the ball milling time is 8h, the ball milling device alternately rotates forwards and backwards at intervals of 1h and 10min, and the temperature of the tank body is not overhigh. Argon is filled into the milling tank to protect the powder from oxidation. The grinding balls used were: boron carbide grinding balls with the diameters of phi 5mm and phi 10mm, wherein the weight ratio of the large balls to the small balls is 1: 1;

step 3, selective laser melting and forming:

putting the prepared magnesium alloy powder into Selective Laser Melting (SLM) equipment, and introducing a three-dimensional drawing of a bone splint, wherein the technological parameters of selective laser melting are as follows: the SLM printing was started with a laser power of 70W, a scanning speed of 600mm/s, a scanning pitch of 30 μm, a layer thickness of 30 μm, and a zigzag printing path. The whole processing process is carried out in a processing chamber with argon protection, so as to avoid the metal reacting with other gases at high temperature.

The obtained magnesium alloy has grain size of 2-5 μm, compactness of 96.7%, and Vickers hardness of 88.0HV₅Tensile strength at room temperature of 328.1MPa and elongation of 8.9 percent.

Example 3

Step 1, weighing:

weighing the following raw materials in percentage by weight: la powder: 3%, hydroxyapatite powder: 8 percent, and the balance being atomized magnesium powder, wherein the sum of the weight percentages of the components is 100 percent;

step 2, ball milling and powder mixing:

and (3) placing the weighed powder into a horizontal high-energy ball mill for ball milling and mixing, wherein ball milling technological parameters are as follows: the ball material weight ratio is 1:1, the rotating speed is 200r/min, the ball milling time is 12h, the ball milling device alternately rotates forwards and backwards at intervals of 1h and 10min, and the temperature of the tank body is not overhigh. Argon is filled into the milling tank to protect the powder from oxidation. The grinding balls used were: boron carbide grinding balls with the diameters of phi 5mm and phi 10mm, wherein the weight ratio of the large balls to the small balls is 1: 1;

step 3, selective laser melting and forming:

putting the prepared magnesium alloy powder into Selective Laser Melting (SLM) equipment, and introducing a three-dimensional drawing of a bone splint, wherein the technological parameters of selective laser melting are as follows: the SLM printing was started with a laser power of 60W, a scanning speed of 700mm/s, a scanning pitch of 50 μm, a layer thickness of 30 μm, and a zigzag printing path. The whole processing process is carried out in a processing chamber with argon protection, so as to avoid the metal reacting with other gases at high temperature.

The obtained magnesium alloy has grain size of 2-5 μm, compactness of 95.9%, and Vickers hardness of 84.7HV₅Tensile strength at room temperature of 311.4MPa and elongation of 9.2%.

Example 4

Step 1, weighing:

weighing the following raw materials in percentage by weight: la powder: 3%, hydroxyapatite powder: 3 percent of atomized magnesium powder, and the sum of the weight percentages of the components is 100 percent;

step 2, ball milling and powder mixing:

and (3) placing the weighed powder into a horizontal high-energy ball mill for ball milling and mixing, wherein ball milling technological parameters are as follows: the ball material weight ratio is 1:1, the rotating speed is 100r/min, the ball milling time is 8h, the ball milling device alternately rotates forwards and backwards at intervals of 1h and 10min, and the temperature of the tank body is not overhigh. Argon is filled into the milling tank to protect the powder from oxidation. The grinding balls used were: boron carbide grinding balls with the diameters of phi 5mm and phi 10mm, wherein the weight ratio of the large balls to the small balls is 1: 1;

step 3, selective laser melting and forming:

putting the prepared magnesium alloy powder into Selective Laser Melting (SLM) equipment, and introducing a three-dimensional drawing of a bone splint, wherein the technological parameters of selective laser melting are as follows: the SLM printing was started with a laser power of 80W, a scanning speed of 600mm/s, a scanning pitch of 30 μm, a layer thickness of 30 μm, and a zigzag printing path. The whole processing process is carried out in a processing chamber with argon protection, so as to avoid the metal reacting with other gases at high temperature.

The obtained magnesium alloy has grain size of 2-5 μm, density of 98.4%, and Vickers hardness of 89.3HV₅The room-temperature tensile strength was 330.4MPa, and the elongation was 9.0%.

Example 5

Step 1, weighing:

weighing the following raw materials in percentage by weight: la powder: 2%, hydroxyapatite powder: 8 percent, and the balance being atomized magnesium powder, wherein the sum of the weight percentages of the components is 100 percent;

step 2, ball milling and powder mixing:

and (3) placing the weighed powder into a horizontal high-energy ball mill for ball milling and mixing, wherein ball milling technological parameters are as follows: the ball material weight ratio is 1:1, the rotating speed is 200r/min, the ball milling time is 10h, the ball milling device alternately rotates forwards and backwards at intervals of 1h and 10min, and the temperature of the tank body is not overhigh. Argon is filled into the milling tank to protect the powder from oxidation. The grinding balls used were: boron carbide grinding balls with the diameters of phi 5mm and phi 10mm, wherein the weight ratio of the large balls to the small balls is 1: 1;

step 3, selective laser melting and forming:

putting the prepared magnesium alloy powder into Selective Laser Melting (SLM) equipment, and introducing a three-dimensional drawing of a bone splint, wherein the technological parameters of selective laser melting are as follows: the SLM printing was started with a laser power of 60W, a scanning speed of 500mm/s, a scanning pitch of 40 μm, a layer thickness of 30 μm, and a zigzag printing path. The whole processing process is carried out in a processing chamber with argon protection, so as to avoid the metal reacting with other gases at high temperature.

The obtained magnesium alloy has grain size of 2-5 μm, compactness of 96.3%, and Vickers hardness of 86.4HV₅Tensile strength at room temperature of 313.4MPa and elongation of 8.6%.