CN113621858B - Antibacterial and tumor proliferation inhibiting degradable magnesium alloy bone nail and preparation method thereof - Google Patents

Antibacterial and tumor proliferation inhibiting degradable magnesium alloy bone nail and preparation method thereof Download PDF

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CN113621858B
CN113621858B CN202110795470.1A CN202110795470A CN113621858B CN 113621858 B CN113621858 B CN 113621858B CN 202110795470 A CN202110795470 A CN 202110795470A CN 113621858 B CN113621858 B CN 113621858B
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ingot
magnesium
alloy
pure
particles
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CN113621858A (en
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徐春杰
华心雨
杨怡
萨娜·扎珐
李诊娇
田颖晨
李怡春
史妍
李梦阳
武向权
张忠明
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Xi'an Shehetmanno Award New Materials Research Institute Co ltd
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Xian University of Technology
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C23/00—Alloys based on magnesium
    • C22C23/06—Alloys based on magnesium with a rare earth metal as the next major constituent
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61B—DIAGNOSIS; SURGERY; IDENTIFICATION
    • A61B17/00—Surgical instruments, devices or methods, e.g. tourniquets
    • A61B17/56—Surgical instruments or methods for treatment of bones or joints; Devices specially adapted therefor
    • A61B17/58—Surgical instruments or methods for treatment of bones or joints; Devices specially adapted therefor for osteosynthesis, e.g. bone plates, screws, setting implements or the like
    • A61B17/68—Internal fixation devices, including fasteners and spinal fixators, even if a part thereof projects from the skin
    • A61B17/84—Fasteners therefor or fasteners being internal fixation devices
    • A61B17/86—Pins or screws or threaded wires; nuts therefor
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F10/00—Additive manufacturing of workpieces or articles from metallic powder
    • B22F10/20—Direct sintering or melting
    • B22F10/28—Powder bed fusion, e.g. selective laser melting [SLM] or electron beam melting [EBM]
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F5/00—Manufacture of workpieces or articles from metallic powder characterised by the special shape of the product
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y10/00—Processes of additive manufacturing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y70/00—Materials specially adapted for additive manufacturing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y80/00—Products made by additive manufacturing
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/25—Process efficiency

Abstract

The invention discloses a degradable magnesium alloy bone nail capable of resisting bacteria and inhibiting tumor proliferation, which comprises the following components in percentage by weight: ag: 0.01-0.05%, La: 1-2%, Ca: 0.2 to 0.4 percent of magnesium and the balance of magnesium, wherein the sum of the weight percent of the components is 100 percent. The alloy bone nail not only has excellent biocompatibility, but also has the functions of long-acting antibiosis and tumor proliferation inhibition. And provides a preparation method of the degradable magnesium alloy bone nail.

Description

Antibacterial and tumor proliferation inhibiting degradable magnesium alloy bone nail and preparation method thereof
Technical Field
The invention belongs to the technical field of degradable medical metal materials, and particularly relates to a degradable magnesium alloy bone nail capable of resisting bacteria and inhibiting tumor proliferation, and a preparation method of the degradable magnesium alloy bone nail capable of resisting bacteria and inhibiting tumor proliferation.
Background
Magnesium alloys are one of the lightest structural materials known to have high biocompatibility, excellent specific strength and specific stiffness. The density of the pure magnesium is 1.74g/cm3About, the bone density (1.75 g/cm) of human3) Equivalent Young's modulus of magnesium alloyAbout 45GPa, is the bio-friendly metal material which is closest to the elastic modulus (20GPa) of human bones in metal structural materials. Meanwhile, magnesium is an essential nutrient element for human bodies, exists in bones, teeth and soft tissues mostly, is also an essential element for maintaining the structure and the function of bone cells, and can promote the proliferation and the differentiation of the bone cells. Alloy elements with corresponding functions are added into the magnesium alloy, so that the functionalized magnesium alloy can be prepared. In the magnesium alloy, Ag element is added to facilitate antibiosis, La element is added to facilitate inhibition of tumor proliferation, and Ca element is an important component of human skeleton to maintain the hardness of the skeleton. The medical magnesium alloy material and the bone implantation device thereof are praised as revolutionary metal biomaterials due to good biocompatibility, obdurability and in-vivo degradability. The bone setting agent is widely applied to bone implant materials such as fracture internal fixation bone nails, bone plates, bone tissue engineering supports and the like, has the effect of promoting osteogenesis, can be automatically degraded and disappear after bone healing, and can avoid secondary damage to human bodies.
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. The SLM is a rapid cooling and solidification process, so that a non-equilibrium supersaturated solid solution and a uniform and fine microstructure can be obtained, and a workpiece with almost any shape, high molding precision and good mechanical properties can be prepared. Based on the reason, the SLM technology can meet the requirements of customized degradable magnesium alloy bioimplantation required by different individual differences, and has wide prospects and important significance for developing high-performance and complex-structure materials.
The invention discloses a magnesium alloy bone nail with a porous ceramic layer formed on the surface, which is prepared by hot extrusion, drawing and heat treatment (application number: 202010379542.X, publication number: CN111282025A, published as 2020.06.16). However, the preparation process is complex, the structural requirements can be met only by machining, and some biological functional requirements are not considered. The invention uses SLM forming technology, not only can exert the advantages of 3D printing, realize the production of customized complex structure products, but also has simple process and one-step forming. Meanwhile, Ag element and La element are added to achieve the effects of resisting bacteria, inhibiting tumor proliferation and the like.
In practical medical application, the bone nail needs to meet the requirements on complex shape and performance according to the individual difference characteristics of receptors, and the selective laser melting technology of the SLM is most suitable for preparation. Therefore, the SLM process research of the magnesium alloy bone nail has important application prospect.
Disclosure of Invention
The invention aims to provide the degradable magnesium alloy bone nail with the functions of resisting bacteria and inhibiting tumor proliferation, which has excellent biocompatibility and also has the functions of long-acting antibiosis and inhibiting tumor proliferation.
The second purpose of the invention is to provide a preparation method of the degradable magnesium alloy bone nail with antibacterial and tumor proliferation inhibiting functions, which can prepare bone nails with any shapes and complex structures.
The first technical scheme adopted by the invention is that the degradable magnesium alloy bone nail capable of resisting bacteria and inhibiting tumor proliferation comprises the following components in percentage by weight: ag: 0.01-0.05%, La: 1-2%, Ca: 0.2 to 0.4 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 raw materials used by the degradable magnesium alloy bone nail are commercial pure magnesium ingot and pure silver particles with the mass fraction not less than 99.99%, Mg-30% La intermediate alloy ingot and Mg-20% Ca intermediate alloy ingot.
The second technical scheme adopted by the invention is that the preparation method of the antibacterial and tumor proliferation inhibiting degradable magnesium alloy bone nail comprises the following steps:
step 1, polishing oxide skins and impurities on the surfaces of raw materials by using a grinding wheel and abrasive paper to obtain pure raw material blocks;
the raw materials used are commercial pure magnesium ingot, pure silver particles, Mg-30% La intermediate alloy ingot and Mg-20% Ca intermediate alloy ingot with the mass fraction not less than 99.99%;
step 2, weighing raw materials
Weighing each raw material in the step 1, and dividing a commercial pure magnesium ingot into two parts, wherein one part of the commercial pure magnesium ingot is used for wrapping pure silver ingot particles in the commercial pure magnesium ingot;
in the step 2, the pure magnesium ingot is required to be punched, the size of the pure magnesium ingot is determined according to the size of the silver ingot particles, the pure silver ingot particles are required to be placed in the pure magnesium ingot holes, and a pure magnesium ingot sheet can be ensured to cover the holes, so that the pure silver ingot particles are prevented from falling and being insufficiently melted.
Step 3, smelting and atomizing to prepare powder:
sequentially putting the weighed raw materials into an induction smelting furnace of gas atomization equipment for alloy smelting according to the sequence of a commercial pure magnesium ingot, an Mg-30% La intermediate alloy ingot, an Mg-20% Ca intermediate alloy ingot and a pure magnesium ingot with pure silver ingot particles inside; after the alloy is completely melted and uniform, atomizing by using high-purity argon gas with the purity of 99.99% to prepare powder, enabling powder particles after the alloy atomization to enter a powder receiving tank through a cyclone separator, cooling, collecting and sieving to obtain magnesium alloy powder with the required particle size;
and 4, Selective Laser Melting (SLM) forming:
and (3) putting the magnesium alloy powder sieved in the step (3) into selective laser melting equipment, importing the three-dimensional drawing subdivision data of the bone nail, setting parameters such as laser power, scanning speed, scanning distance, layer thickness and path planning, and starting SLM printing and forming.
The present invention is also characterized in that,
in the step 2, the weight ratio of each raw material is as follows: pure silver particles: mg-30% La master alloy ingot casting: mg-20% Ca master alloy ingot casting: commercial pure magnesium ingot casting is 1-5: 333-667: 100-200: 9128-9566.
In step 3, the equipment needs to be vacuumized to 10 DEG-2Introducing inert gas argon below Pa, and controlling the smelting temperature to 750 ℃.
In step 3, the pressure of the atomized argon gas is 3.5 MPa.
In the step 3, the collected magnesium alloy powder is sieved through a sieve to screen powder with the particle size of 30-50 mu m, and the powder is used for the step 4, and selective laser melting SLM forming is carried out.
The process parameters of the selected area laser melting in the step 4 are as follows: laser power 60W, scanning speed 600mm/s, scanning pitch 20 μm, layer thickness 30 μm, zigzag printing path.
In step 4, the whole processing process is carried out in a processing chamber with argon protection.
The degradable magnesium alloy bone nail prepared in the step 4 comprises the following components in percentage by weight: ag: 0.01-0.05%, La: 1-2%, Ca: 0.2 to 0.4 percent of magnesium and the balance of magnesium, wherein the sum of the weight percent of the components is 100 percent.
The invention has the beneficial effects that: the magnesium alloy bone nail prepared by the selective laser melting technology can meet the complex structural requirement of the bone nail and the requirements of surface precision and mechanical property, the added Ag element is beneficial to antibiosis, the La element is beneficial to inhibiting tumor proliferation, and the Ca element is an important component of human skeleton, so that the requirement of the skeleton on the Ca element is maintained.
Detailed Description
The present invention will be described in detail with reference to the following embodiments.
The invention provides a degradable magnesium alloy bone nail capable of resisting bacteria and inhibiting tumor proliferation, which comprises the following components in percentage by weight: ag: 0.01-0.05%, La: 1-2%, Ca: 0.2 to 0.4 percent of magnesium and the balance of magnesium, wherein the sum of the weight percent of the components is 100 percent.
The raw materials used by the degradable magnesium alloy bone nail are commercial pure magnesium ingot and pure silver particles with the mass fraction not less than 99.99%, Mg-30% La intermediate alloy ingot and Mg-20% Ca intermediate alloy ingot.
The invention also provides a preparation method of the antibacterial and tumor proliferation inhibiting degradable magnesium alloy bone nail, which comprises the following steps:
step 1, polishing oxide skins and impurities on the surfaces of raw materials by using a grinding wheel and abrasive paper to obtain pure raw material blocks;
the raw materials used are commercial pure magnesium ingot, pure silver particles, Mg-30% La intermediate alloy ingot and Mg-20% Ca intermediate alloy ingot with the mass fraction not less than 99.99%;
step 2, weighing raw materials
Weighing each raw material in the step 1, and dividing a commercial pure magnesium ingot into two parts, wherein one part of the commercial pure magnesium ingot is used for wrapping pure silver ingot particles in the commercial pure magnesium ingot, so that the situation that the pure silver ingot particles fall off in the smelting process to cause insufficient melting of the silver particles, and thus the alloy components are not uniform is avoided;
in the step 2, the pure magnesium ingot is required to be punched, the size of the pure magnesium ingot is determined according to the size of the silver ingot particles, the pure silver ingot particles are required to be placed in the pure magnesium ingot holes, and a pure magnesium ingot sheet can be ensured to cover the holes, so that the pure silver ingot particles are prevented from falling and being insufficiently melted.
In the step 2, the weight ratio of each raw material is as follows: pure silver particles: mg-30% La master alloy ingot casting: mg-20% Ca master alloy ingot casting: commercial pure magnesium ingot casting is 1-5: 333-667: 100-200: 9128-9566.
Step 3, smelting and atomizing to prepare powder:
sequentially putting the weighed raw materials into an induction smelting furnace of gas atomization equipment for alloy smelting according to the sequence of a commercial pure magnesium ingot, an Mg-30% La intermediate alloy ingot, an Mg-20% Ca intermediate alloy ingot and a pure magnesium ingot with pure silver ingot particles inside; after the alloy is completely melted and uniform, atomizing by using high-purity argon gas with the purity of 99.99% to prepare powder, enabling powder particles after the alloy atomization to enter a powder receiving tank through a cyclone separator, cooling, collecting and sieving to obtain magnesium alloy powder with the required particle size;
in step 3, the equipment needs to be vacuumized to 10 DEG-2Introducing inert gas argon below Pa, and controlling the smelting temperature to 750 ℃;
in the step 3, the pressure of the atomized argon gas is 3.5 MPa;
in the step 3, the collected magnesium alloy powder is screened out by a sieve to obtain powder with the particle size of 30-50 mu m, and the powder is used for the step 4, and selective laser melting SLM forming is carried out;
and 4, Selective Laser Melting (SLM) forming:
putting the magnesium alloy powder sieved in the step 3 into Selective Laser Melting (SLM) equipment, introducing the three-dimensional drawing subdivision data of the bone nail, setting parameters such as laser power, scanning speed, scanning distance, layer thickness and path planning, and starting SLM printing and forming;
the process parameters of the selected area laser melting in the step 4 are as follows: a zigzag printing path with laser power of 60W, scanning speed of 600mm/s, scanning pitch of 20 μm, layer thickness of 30 μm;
in the step 4, the whole processing process is carried out in a processing chamber with argon gas protection to avoid the alloy from reacting with other gases at high temperature;
the degradable magnesium alloy bone nail prepared in the step 4 comprises the following components in percentage by weight: ag: 0.01-0.05%, La: 1-2%, Ca: 0.2 to 0.4 percent of magnesium and the balance of magnesium, wherein the sum of the weight percent of the components is 100 percent.
Examples 1-5 used starting materials: commercial pure magnesium ingot, pure silver particles, Mg-30% La intermediate alloy ingot and Mg-20% Ca intermediate alloy ingot with the mass fraction not less than 99.99%;
example 1
Step 1, removing oxide skin and impurities on the surface of a raw material:
polishing oxide skin and impurities on the surface of the raw material by using a grinding wheel and abrasive paper to obtain a pure raw material block;
step 2, weighing raw materials:
weighing the following raw materials in parts by weight: pure silver particles: mg-30% La master alloy ingot casting: mg-20% Ca master alloy ingot casting: commercial pure magnesium ingots were 1: 333: 100: 9566A mixture of (A) and (B); dividing a commercial pure magnesium ingot into two parts, wherein one part of the commercial pure magnesium ingot (the mass of the part of the commercial pure magnesium ingot is 10 percent of that of the whole commercial pure magnesium ingot) is used for wrapping pure silver ingot particles in the commercial pure magnesium ingot, holes need to be formed in the commercial pure magnesium ingot wrapped with the pure silver ingot particles, the size of the commercial pure magnesium ingot is determined according to the size of the silver ingot particles, the pure silver ingot particles are required to be placed in the pure magnesium ingot holes, and a pure magnesium ingot sheet can be ensured to cover the holes, so that the pure silver ingot particles are prevented from falling and being insufficiently melted;
step 3, smelting and atomizing to prepare powder:
weighing the raw materials according toAccording to the sequence of a pure magnesium ingot, an Mg-30% La intermediate alloy ingot, an Mg-20% Ca intermediate alloy ingot and a pure magnesium ingot with pure silver ingot particles inside, the raw materials are sequentially put into an induction smelting furnace of gas atomization equipment, and the equipment is vacuumized to 10 degrees-2Introducing inert gas argon below Pa, smelting at the smelting temperature of 750 ℃, smelting the alloy, and after the alloy is completely molten and uniform, atomizing with high-purity argon to prepare powder, wherein the pressure of the atomized argon is 3 MPa. Feeding the atomized powder particles of the alloy into a powder collecting tank through a cyclone separator, cooling and collecting, and screening the collected Mg-La-Ca-Ag alloy powder with the particle size of 30-50 mu m through a sieve;
step 4, selective laser melting and forming:
putting the prepared magnesium alloy powder into Selective Laser Melting (SLM) equipment, and introducing the three-dimensional drawing subdivision data of the bone nail, 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 600mm/s, a scanning pitch of 20 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 alloy reacting with other gases at high temperature.
The degradable magnesium alloy bone nail prepared in the step 4 comprises the following components in percentage by weight: 0.01 percent of Ag0, 1 percent of La, 0.2 percent of Ca and the balance of magnesium, wherein the sum of the weight percent of the components is 100 percent.
The obtained bone nail has a magnesium alloy grain size of 1-4 μm, a compactness of 97.3%, and a Vickers hardness of 89.4HV5The room-temperature tensile strength is 321.7MPa, and the elongation is 8.1%.
Example 2
Step 1, removing oxide skin and impurities on the surface of a raw material:
polishing oxide skin and impurities on the surface of the raw material by using a grinding wheel and abrasive paper to obtain a pure raw material block;
step 2, weighing raw materials:
weighing the following raw materials in parts by weight: pure silver particles: mg-30% La master alloy ingot casting: mg-20% Ca master alloy ingot: commercial pure magnesium ingots are 1: 500: 200: 9299; dividing a commercial pure magnesium ingot into two parts, wherein one part of the commercial pure magnesium ingot (the mass of the part of the commercial pure magnesium ingot is 10 percent of that of the whole commercial pure magnesium ingot) is used for wrapping pure silver ingot particles in the commercial pure magnesium ingot, holes need to be formed in the commercial pure magnesium ingot wrapped with the pure silver ingot particles, the size of the commercial pure magnesium ingot is determined according to the size of the silver ingot particles, the pure silver ingot particles are required to be placed in the pure magnesium ingot holes, and a pure magnesium ingot sheet can be ensured to cover the holes, so that the pure silver ingot particles are prevented from falling and being insufficiently melted;
step 3, smelting and atomizing to prepare powder:
putting the weighed raw materials into an induction smelting furnace of gas atomization equipment in sequence according to the sequence of a pure magnesium ingot, an Mg-30% La intermediate alloy ingot, an Mg-20% Ca intermediate alloy ingot and a pure magnesium ingot with pure silver ingot particles inside, vacuumizing the equipment to 10 DEG C-2Introducing inert gas argon below Pa, smelting at the smelting temperature of 750 ℃, smelting the alloy, and after the alloy is completely molten and uniform, atomizing with high-purity argon to prepare powder, wherein the pressure of the atomized argon is 3.4 MPa. Feeding the atomized powder particles of the alloy into a powder collecting tank through a cyclone separator, cooling and collecting, and screening the collected Mg-La-Ca-Ag alloy powder with the particle size of 30-50 mu m through a sieve;
step 4, selective laser melting forming:
putting the prepared magnesium alloy powder into Selective Laser Melting (SLM) equipment, and introducing the three-dimensional drawing subdivision data of the bone nail, 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 600mm/s, a scanning pitch of 20 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 alloy reacting with other gases at high temperature.
The degradable magnesium alloy bone nail prepared in the step 4 comprises the following components in percentage by weight: 0.01 percent of Ags, 1.5 percent of La, 0.4 percent of Ca and the balance of magnesium, wherein the sum of the weight percentages of the components is 100 percent.
The obtained bone nail has a magnesium alloy grain size of 1-4 μm, a density of 98.4%, and a Vickers hardness of 92.5HV5Tensile strength at room temperature of 338.2MPa and elongation of 7.8%.
Example 3
Step 1, removing oxide skin and impurities on the surface of a raw material:
polishing oxide skin and impurities on the surface of the raw material by using a grinding wheel and abrasive paper to obtain a pure raw material block;
step 2, weighing raw materials:
weighing the following raw materials in parts by weight: pure silver particles: mg-30% La master alloy ingot casting: mg-20% Ca master alloy ingot casting: commercial pure magnesium ingots ═ 3: 667: 150: 9180; dividing a commercial pure magnesium ingot into two parts, wherein one part of the commercial pure magnesium ingot (the mass of the part of the commercial pure magnesium ingot is 10 percent of that of the whole commercial pure magnesium ingot) is used for wrapping pure silver ingot particles in the commercial pure magnesium ingot, holes need to be formed in the commercial pure magnesium ingot wrapped with the pure silver ingot particles, the size of the commercial pure magnesium ingot is determined according to the size of the silver ingot particles, the pure silver ingot particles are required to be placed in the pure magnesium ingot holes, and a pure magnesium ingot sheet can be ensured to cover the holes, so that the pure silver ingot particles are prevented from falling and being insufficiently melted;
step 3, smelting and atomizing to prepare powder:
sequentially putting the weighed raw materials into an induction melting furnace of gas atomization equipment according to the sequence of a pure magnesium ingot, an Mg-30% La intermediate alloy ingot, an Mg-20% Ca intermediate alloy ingot and a pure magnesium ingot with pure silver ingot particles inside, vacuumizing the equipment to 10 DEG C-2Introducing inert gas argon below Pa, smelting at the smelting temperature of 750 ℃, smelting the alloy, and after the alloy is completely molten and uniform, atomizing with high-purity argon to prepare powder, wherein the pressure of the atomized argon is 3.1 MPa. Feeding the atomized powder particles of the alloy into a powder collecting tank through a cyclone separator, cooling and collecting, and screening the collected Mg-La-Ca-Ag alloy powder with the particle size of 30-50 mu m through a sieve;
step 4, selective laser melting forming:
putting the prepared magnesium alloy powder into Selective Laser Melting (SLM) equipment, and introducing the three-dimensional drawing subdivision data of the bone nail, 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 600mm/s, a scanning pitch of 20 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 alloy reacting with other gases at high temperature.
The degradable magnesium alloy bone nail prepared in the step 4 comprises the following components in percentage by weight: 0.03 percent of Ags, 0.3 percent of La, and the balance of magnesium, wherein the sum of the weight percentages of the components is 100 percent.
The obtained bone nail has a magnesium alloy grain size of 1-4 μm, a density of 98.6%, and a Vickers hardness of 90.4HV5Tensile strength at room temperature of 329.6MPa, and elongation of 8.5%.
Example 4
Step 1, removing oxide skin and impurities on the surface of a raw material:
polishing oxide skin and impurities on the surface of the raw material by using a grinding wheel and abrasive paper to obtain a pure raw material block;
step 2, weighing raw materials:
weighing the following raw materials in parts by weight: pure silver particles: mg-30% La master alloy ingot casting: mg-20% Ca master alloy ingot casting: commercial pure magnesium ingots ═ 5: 333: 100: 9562; dividing a commercial pure magnesium ingot into two parts, wherein one part of the commercial pure magnesium ingot (the mass of the part of the commercial pure magnesium ingot is 10 percent of that of the whole commercial pure magnesium ingot) is used for wrapping pure silver ingot particles in the commercial pure magnesium ingot, holes need to be formed in the commercial pure magnesium ingot wrapped with the pure silver ingot particles, the size of the commercial pure magnesium ingot is determined according to the size of the silver ingot particles, the pure silver ingot particles are required to be placed in the pure magnesium ingot holes, and a pure magnesium ingot sheet can be ensured to cover the holes, so that the pure silver ingot particles are prevented from falling and being insufficiently melted;
step 3, smelting and atomizing to prepare powder:
putting the weighed raw materials into an induction smelting furnace of gas atomization equipment in sequence according to the sequence of a pure magnesium ingot, an Mg-30% La intermediate alloy ingot, an Mg-20% Ca intermediate alloy ingot and a pure magnesium ingot with pure silver ingot particles inside, vacuumizing the equipment to 10 DEG C-2Introducing inert gas argon below Pa, smelting at the smelting temperature of 750 ℃, smelting the alloy, and after the alloy is completely molten and uniform, atomizing with high-purity argon to prepare powder, wherein the pressure of the atomized argon is 3.2 MPa. The atomized powder particles of the alloy enter a powder receiving tank through a cyclone separator and are cooledCollecting after cooling, and screening the collected Mg-La-Ca-Ag alloy powder with the particle size of 30-50 mu m by a sieve;
step 4, selective laser melting and forming:
putting the prepared magnesium alloy powder into Selective Laser Melting (SLM) equipment, and introducing the three-dimensional drawing subdivision data of the bone nail, 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 600mm/s, a scanning pitch of 20 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 gas protection, so as to avoid the alloy reacting with other gases at high temperature.
The degradable magnesium alloy bone nail prepared in the step 4 comprises the following components in percentage by weight: 0.05 percent of Ags, 1 percent of La, 0.2 percent of Ca and the balance of magnesium, wherein the sum of the weight percentages of the components is 100 percent.
The obtained bone nail has a magnesium alloy grain size of 1-4 μm, a density of 98.3%, and a Vickers hardness of 92.4HV5Tensile strength at room temperature of 328.3MPa, and elongation of 7.7%.
Example 5
Step 1, removing oxide skin and impurities on the surface of a raw material:
polishing oxide skin and impurities on the surface of the raw material by using a grinding wheel and abrasive paper to obtain a pure raw material block;
step 2, weighing raw materials:
weighing the following raw materials in parts by weight: pure silver particles: mg-30% La master alloy ingot casting: mg-20% Ca master alloy ingot casting: commercial pure magnesium ingots ═ 5: 500: 200: 9295; dividing a commercial pure magnesium ingot into two parts, wherein one part of the commercial pure magnesium ingot (the mass of the part of the commercial pure magnesium ingot is 10 percent of that of the whole commercial pure magnesium ingot) is used for wrapping pure silver ingot particles in the commercial pure magnesium ingot, holes need to be formed in the commercial pure magnesium ingot wrapped with the pure silver ingot particles, the size of the commercial pure magnesium ingot is determined according to the size of the silver ingot particles, the pure silver ingot particles are required to be placed in the pure magnesium ingot holes, and a pure magnesium ingot sheet can be ensured to cover the holes, so that the pure silver ingot particles are prevented from falling and being insufficiently melted;
step 3, smelting and atomizing to prepare powder:
sequentially putting the weighed raw materials into an induction melting furnace of gas atomization equipment according to the sequence of a pure magnesium ingot, an Mg-30% La intermediate alloy ingot, an Mg-20% Ca intermediate alloy ingot and a pure magnesium ingot with pure silver ingot particles inside, vacuumizing the equipment to 10 DEG C-2Introducing inert gas argon below Pa, smelting at the smelting temperature of 750 ℃, smelting the alloy, and after the alloy is completely molten and uniform, atomizing with high-purity argon to prepare powder, wherein the pressure of the atomized argon is 3.5 MPa. Feeding the atomized powder particles of the alloy into a powder collecting tank through a cyclone separator, cooling and collecting, and screening the collected Mg-La-Ca-Ag alloy powder with the particle size of 30-50 mu m through a sieve;
step 4, selective laser melting and forming:
putting the prepared magnesium alloy powder into Selective Laser Melting (SLM) equipment, and introducing the three-dimensional drawing subdivision data of the bone nail, 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 600mm/s, a scanning pitch of 20 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 alloy reacting with other gases at high temperature.
The degradable magnesium alloy bone nail prepared in the step 4 comprises the following components in percentage by weight: 0.05% of Ag0, 1.5% of La, 0.4% of Ca and the balance of magnesium, wherein the sum of the weight percentages of the components is 100%.
The obtained bone nail has a magnesium alloy grain size of 1-4 μm, a density of 98.2%, and a Vickers hardness of 91.6HV5Tensile strength at room temperature of 339.5MPa, and elongation of 7.4%.

Claims (5)

1. The degradable magnesium alloy bone nail is characterized by comprising the following components in percentage by weight: ag: 0.01-0.05%, La: 1-2%, Ca: 0.2 to 0.4 percent of magnesium and the balance of magnesium, wherein the sum of the weight percentages of the components is 100 percent;
the preparation method of the degradable magnesium alloy bone nail with the functions of resisting bacteria and inhibiting tumor proliferation comprises the following steps:
step 1, polishing oxide skins and impurities on the surfaces of raw materials by using a grinding wheel and abrasive paper to obtain pure raw material blocks;
the raw materials used are commercial pure magnesium ingot, pure silver particles, Mg-30% La intermediate alloy ingot and Mg-20% Ca intermediate alloy ingot with the mass fraction not less than 99.99%;
step 2, weighing raw materials
Weighing each raw material in the step 1, dividing a commercial pure magnesium ingot into two parts, wherein one part of the commercial pure magnesium ingot is used for wrapping pure silver ingot particles in the commercial pure magnesium ingot;
in the step 2, holes are needed to be punched on the pure magnesium ingot, the size of the holes is determined according to the size of the silver ingot particles, the pure silver ingot particles are required to be placed in the pure magnesium ingot holes, and a pure magnesium ingot sheet can be ensured to cover the holes so as to prevent the pure silver ingot particles from falling and being insufficiently melted;
step 3, smelting and atomizing to prepare powder:
sequentially putting the weighed raw materials into an induction smelting furnace of gas atomization equipment for alloy smelting according to the sequence of a commercial pure magnesium ingot, an Mg-30% La intermediate alloy ingot, an Mg-20% Ca intermediate alloy ingot and a pure magnesium ingot with pure silver ingot particles inside; after the alloy is completely melted and uniform, atomizing by using high-purity argon gas with the purity of 99.99% to prepare powder, enabling powder particles after the alloy atomization to enter a powder receiving tank through a cyclone separator, cooling, collecting and sieving to obtain magnesium alloy powder with the required particle size;
and 4, Selective Laser Melting (SLM) forming:
placing the magnesium alloy powder sieved in the step 3 into selective laser melting equipment, introducing the three-dimensional drawing subdivision data of the bone nail, setting laser power, scanning speed, scanning distance, layer thickness and path planning parameters, and starting SLM printing and forming;
in step 3, the equipment needs to be vacuumized to 10 DEG-2Introducing inert gas argon below Pa, and controlling the smelting temperature to 750 ℃;
in the step 3, the pressure of the atomized argon gas is 3.5 MPa;
in the step 3, the collected magnesium alloy powder is sieved through a sieve to screen powder with the particle size of 30-50 mu m, and the powder is used for the step 4, and selective laser melting SLM forming is carried out.
2. A preparation method of a degradable magnesium alloy bone nail with antibacterial and tumor proliferation inhibiting effects is characterized by comprising the following steps: the method comprises the following steps:
step 1, polishing oxide skins and impurities on the surfaces of raw materials by using a grinding wheel and abrasive paper to obtain pure raw material blocks;
the raw materials used are commercial pure magnesium ingot, pure silver particles, Mg-30% La intermediate alloy ingot and Mg-20% Ca intermediate alloy ingot with the mass fraction not less than 99.99%;
step 2, weighing raw materials
Weighing each raw material in the step 1, and dividing a commercial pure magnesium ingot into two parts, wherein one part of the commercial pure magnesium ingot is used for wrapping pure silver ingot particles in the commercial pure magnesium ingot;
in the step 2, holes are needed to be punched on the pure magnesium ingot, the size of the holes is determined according to the size of the silver ingot particles, the pure silver ingot particles are required to be placed in the pure magnesium ingot holes, and a pure magnesium ingot sheet can be ensured to cover the holes so as to prevent the pure silver ingot particles from falling and being insufficiently melted;
step 3, smelting and atomizing to prepare powder:
sequentially putting the weighed raw materials into an induction smelting furnace of gas atomization equipment for alloy smelting according to the sequence of a commercial pure magnesium ingot, an Mg-30% La intermediate alloy ingot, an Mg-20% Ca intermediate alloy ingot and a pure magnesium ingot with pure silver ingot particles inside; after the alloy is completely melted and uniform, atomizing by using high-purity argon gas with the purity of 99.99% to prepare powder, enabling powder particles after the alloy atomization to enter a powder receiving tank through a cyclone separator, cooling, collecting and sieving to obtain magnesium alloy powder with the required particle size;
and 4, Selective Laser Melting (SLM) forming:
placing the magnesium alloy powder sieved in the step 3 into selective laser melting equipment, introducing the three-dimensional drawing subdivision data of the bone nail, setting laser power, scanning speed, scanning distance, layer thickness and path planning parameters, and starting SLM printing and forming;
in step 3, the equipment needs to be vacuumized to 10 DEG-2Introducing inert gas argon under Pa, and smelting at 75 deg.C0 ℃；
In the step 3, the pressure of the atomized argon gas is 3.5 MPa;
in the step 3, the collected magnesium alloy powder is screened out by a sieve to obtain powder with the particle size of 30-50 mu m, and the powder is used for the step 4, and selective laser melting SLM forming is carried out;
the degradable magnesium alloy bone nail prepared in the step 4 comprises the following components in percentage by weight: ag: 0.01-0.05%, La: 1-2%, Ca: 0.2 to 0.4 percent of magnesium and the balance of magnesium, wherein the sum of the weight percent of the components is 100 percent.
3. The preparation method of the antibacterial and tumor proliferation inhibiting degradable magnesium alloy bone nail according to claim 2, wherein in the step 2, the weight ratio of each raw material is as follows: pure silver particles: mg-30% La master alloy ingot casting: mg-20% Ca master alloy ingot casting: commercial pure magnesium ingot = 1-5: 333-667: 100-200: 9128 to 9566.
4. The preparation method of the antibacterial and tumor proliferation inhibiting degradable magnesium alloy bone nail according to claim 2, wherein the process parameters of laser melting of the selected area in the step 4 are as follows: laser power 60W, scanning speed 600mm/s, scanning pitch 20 μm, layer thickness 30 μm, zigzag printing path.
5. The preparation method of the antibacterial and tumor proliferation inhibiting degradable magnesium alloy bone nail according to claim 2, wherein in the step 4, the whole processing process is carried out in a processing chamber with argon protection.
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