CN110420358B - Bone nail capable of promoting bone growth and being completely absorbed by bone and preparation method thereof - Google Patents

Bone nail capable of promoting bone growth and being completely absorbed by bone and preparation method thereof Download PDF

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CN110420358B
CN110420358B CN201910629761.6A CN201910629761A CN110420358B CN 110420358 B CN110420358 B CN 110420358B CN 201910629761 A CN201910629761 A CN 201910629761A CN 110420358 B CN110420358 B CN 110420358B
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鄢腊梅
王米航
吴建能
张祥泉
陈禹轩
夏嘉璐
蒋小花
郭渝慧
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Hangzhou Dianzi University
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Abstract

The invention discloses a bone nail capable of promoting bone growth and being completely absorbed by bones and a preparation method thereof. The bone nail comprises 0.5 to 2.0 percent of nano zirconia; 1.5 to 3.0 percent of nano zinc oxide; 2.5 to 5.0 percent of nano magnesium oxide; 1.5-2.5% of vanadium; 3-8% of calcium; the balance being magnesium. The components are ball-milled, then directly molded by a German Yioensi SLM laser powder-laying 3D printer EOSM100 machine, and finally sterilized by an ethylene-acetone aqueous solution. The tensile strength and the yield strength of the bone nail generated by the invention are both larger than the minimum standard 300Mpa required by the bone nail, and the elongation is also larger than the minimum standard 16% required by the bone nail. The bone nail has good bone inductivity, is beneficial to forming stable bone combination, and has biological controllable degradability.

Description

Bone nail capable of promoting bone growth and being completely absorbed by bone and preparation method thereof
Technical Field
The invention relates to a bone nail capable of promoting bone growth and being completely absorbed by bones and a preparation method thereof.
Background
Bone nails, also known as medical devices and fracture fixation screws, are commonly used for fixation of internal fractures or dislocations, and achieve fixation of fractures by directly screwing in two different pieces of bone or internal implants such as a bone plate, etc., positioning bones and promoting healing thereof. The bone screw material must serve 2 functions: (1) has sufficient mechanical strength to support the healing of injured bones, and (2) has biological activity and is degraded and absorbed by human body after the bones are healed.
Based on the traditional bone screw with the fixing function, the traditional bone screw is mostly made of titanium alloy or stainless steel at present, and the bone screw has the trouble that the bone screw needs to be taken out after the recovery through a secondary operation. The magnesium alloy is an alloy formed by adding other elements on the basis of magnesium. The method is characterized in that: the alloy has the advantages of low density (about 1.8g/cm3 magnesium alloy), high strength, large elastic modulus, good heat dissipation, good shock absorption, larger impact load bearing capacity than aluminum alloy, and good organic matter and alkali corrosion resistance. The medical magnesium alloy bone nail has good biocompatibility and certain mechanical strength, and is compared with a revolutionary biomaterial. The degradable high-purity magnesium bone nail has the greatest difficulty that the degradable high-purity magnesium bone nail is degraded and disappears before the injured bone heals due to the excessively high degradation rate. The research on the material and the manufacturing method of the magnesium alloy can ensure that the magnesium alloy bone nail has enough mechanical strength, can promote the rapid growth of bones, can disappear by itself after the bones are healed, and is a research hotspot in the medical material field at present and a difficult problem which needs to be solved urgently.
Disclosure of Invention
It is an object of the present invention to address the deficiencies of the prior art by providing a bone screw that promotes bone growth and is fully absorbed by bone.
The bone nail capable of promoting bone growth and being completely absorbed by bones comprises the following components in parts by weight: nano zirconium oxide (ZrO)2)0.5 to 2.0 percent; 1.5 to 3.0 percent of nano zinc oxide (ZnO); 2.5 to 5.0 percent of nano magnesium oxide (MgO); 1.5-2.5% of vanadium; 3-8% of calcium; the balance being magnesium;
nano zirconium oxide (ZrO)2): the nano zirconia is compounded with the nano zinc oxide, the nano magnesium oxide and the metal vanadium, calcium and magnesium, so that the high-temperature oxidation resistance of the material can be greatly improved, and the fracture toughness, the bending strength and the like of the material are improved. The particle size is 2-50 nm.
Nano zinc oxide (ZnO): the nano zinc oxide is a stable compound, has good tear resistance and elasticity, and also has antibacterial and anti-inflammatory effects, and the preparation method comprises the following steps: heating zinc ingots prepared by an electrolytic method to 580-750 ℃ for melting, putting the zinc ingots into a high-temperature-resistant crucible for melting and gasifying at 1280-1380 ℃, introducing hot air for oxidation, cooling and performing cyclone separation on the generated zinc oxide, and trapping fine particles by a cloth bag to obtain a zinc oxide finished product. The particle size is 2-50 nm.
Zn+CO+O2＝ZnO+CO2。
The nano-scale magnesium oxide (MgO) has obvious small-size effect, surface effect, quantum size effect and macroscopic tunnel effect, has no agglomeration phenomenon after modification treatment, has a plurality of specific functions and important application values in the aspects of optics, catalysis, magnetism, mechanics, chemical engineering and the like, has very wide prospects, and is an important new material in the 21 st century. In the invention, the magnesium oxide has the functions of an antacid, an adsorbent, a desulfurizer, a deleading agent, a complexing filter aid and a pH regulator, and can inhibit and relieve the generation of hydrogen caused by corrosion of metal magnesium in human body environment. Therefore, the corrosion inhibition capability of the bone screw can be greatly improved by adding the nano magnesium oxide (MgO). The particle size is 2-50 nm.
Figure BDA0002128342790000021
Mg+2H2O→Mg(OH)2+H2↑。
Calcium: calcium is the most abundant inorganic salt component element in human body, and accounts for about 1.5% -2.0% of body weight. 99% of the calcium is present in bones and teeth in the form of bone salts. Bone calcium is mainly amorphous calcium hydrogen phosphate (CaHPO)4) And crystalline hydroxyapatite (3 Ca)3PO4×Ca(OH)2) Two forms exist. More calcium hydrogen phosphate is contained in the new bone than the old bone, and the bone is gradually changed into hydroxyapatite in the process of maturing. The calcium is added, so that the growth of new bones can be accelerated, the dynamic balance between bone calcium and calcium in blood can be kept, and the bone calcium can be absorbed by a human body after healing.
Vanadium: is a silver gray metal. The invention adds vanadium, which can promote the regeneration and repair of skeleton and wound, and the vanadium can be metabolized and discharged by human body after the skeleton is repaired.
Magnesium: magnesium is one of the lightest structural metal materials, has high specific strength and specific rigidity and good damping property and cutting property, is the main cation in human cells, is concentrated in mitochondria, is inferior to potassium and phosphorus, is inferior to sodium and calcium in extracellular fluid, and is an essential substance for basic biochemical reactions of various cells in vivo. At present, magnesium alloy wheelchairs, rehabilitation and medical appliances and the like. The main component of the invention is metal magnesium, and the processed bone nail has light weight, high mechanical strength and biocompatibility.
Another object of the present invention is to provide a method for preparing the bone nail, which is used for enhancing the mechanical property and the biological property of the bone nail, and specifically comprises the following steps:
step (1), ball milling
Pouring all magnesium alloy powder components into an all-directional planetary ball mill, wherein the rotating speed of a ball milling tank is 500-950 r/min, rolling the planetary disc and the ball milling tank at 180-360 degrees simultaneously in the ball milling process, generating stronger and uniform friction and impact energy between the magnesium alloy powder and grinding balls, and adopting a grinding mode of dry grinding, vacuum grinding and pressurized grinding, so that the magnesium alloy powder can be fully crushed, mixed and homogenized, and simultaneously, the oxidation and deterioration of metal powder such as magnesium and the like in the air are avoided.
The magnesium alloy powder comprises the following components in percentage by weight: nano zirconium oxide (ZrO)2)0.5 to 2.0 percent; 1.5 to 3.0 percent of nano zinc oxide (ZnO); 2.5 to 5.0 percent of nano magnesium oxide (MgO); 1.5-2.5% of vanadium; calcium 3 ℃8 percent; the balance being magnesium;
the omnibearing planetary ball mill adopts a model DECO-PBM-AD-0.4L, wherein the grinding balls are stainless steel balls, the grinding balls account for 1/4-1/3 of the volume of the ball milling tank, the diameters of the steel balls are divided into 3 grades, namely a large grade, a medium grade and a small grade, and the ratio is 1: 4: 5.
And (2) directly forming by 3D printing.
The bone nail is directly molded by adopting a German Yi Europe SLM laser powder laying 3D printer EOSM100 machine. The bone pins to be printed are first designed into a CAD model and then printed using the STL data file format input to EOSM 100. The laser type is an ytterbium fiber laser of 180-200 watts, the diameter of a light spot is 20-40 mu m, the movement speed of a scraper is 80-180 mm/s, and the forming speed is 25-35 cm3The groove cutting distance of the automatic powder layering device is 0.15-0.18 mm, and the thickness of each powder layer is 0.01-0.04 mm. Preheating an EOSM100 machine to 480-680 ℃, then heating to 1480-1600 ℃ at 30-60 ℃/s, inputting protective gas argon, preserving heat for 8-10 hours, and then cooling to room temperature at a cooling rate of 20-55 ℃/s.
And (3) putting the bone nail manufactured by the method into an ethylene-acetone aqueous solution, and sterilizing a sample to obtain a smooth and clear metallographic structure.
The volume ratio of ethylene to acetone to distilled water in the ethylene-acetone aqueous solution is (75-100): (2-6): (24-30).
Compared with the prior art, the scheme provided by the invention has the following advantages:
1. the invention adopts metal oxide powder: zirconia (ZrO2), zinc oxide (ZnO) and magnesium oxide (MgO), wherein the three powders are prepared into nano-particles with the particle size of 2-50 nanometers, and due to the fine and micro crystal grains, the electronic structure and the crystal structure on the surface of the nano-particles are changed, so that the quantum size effect, high dispersibility and the like which are not possessed by macroscopic objects are generated, and the mechanical property and the corrosion resistance of the bone screw can be greatly enhanced. The tensile strength and the yield strength of the bone nail generated by the invention are both larger than the minimum standard 300Mpa required by the bone nail, and the elongation is also larger than the minimum standard 16% required by the bone nail. Therefore, compared with the existing selective laser sintering SLS method, the bone nail provided by the invention has more ideal mechanical strength.
2. Good biocompatibility:
the bone nail has good bone inductivity, is beneficial to forming stable bone combination, and has biological controllable degradability.
Drawings
FIG. 1 is a CAD model of a bone nail designed according to the present invention;
FIG. 2 is a CAD design model of FIG. 1 showing a bone screw model produced using the present invention and the SLS method, respectively;
FIG. 3 is a scanning electron microscope image and elemental EDX microscopy analysis of the bone screw model of FIG. 2 produced by the method of example 1 and SLS processes of the present invention; wherein (a) the process of example 1 of the present invention, (b) the SLS process;
FIG. 4 is a microscopic view of bone growth observed in animal experiments; wherein (a) is 10 days; (b)30, of a nitrogen-containing gas; (c) and (4) 120 days.
Detailed Description
The present invention is further analyzed with reference to the following specific examples.
The particle sizes of the zirconia (ZrO2), zinc oxide (ZnO), and magnesium oxide (MgO) used in the following examples were all 2 to 50 nm.
Example 1
And (1) performing ball milling.
The following magnesium alloy powder components in weight percentage are mixed: 2.0% of nano zirconium oxide (ZrO 2); 3.0 percent of nano zinc oxide (ZnO); 5.0 percent of nano magnesium oxide (MgO); 2.5 percent of vanadium; 8% of calcium; the balance of magnesium is poured into an omnibearing planetary ball mill DECO-PBM-AD-0.4L. The grinding ball material is stainless steel ball, the grinding ball occupies about 1/4 of the ball milling tank volume, the diameter of the steel ball is divided into 3 grades, large, medium and small, and the proportion is 1: 4: 5. The rotation speed of the ball milling tank is 500r/min, the planetary disc and the ball milling tank simultaneously roll for 180 degrees in the ball milling process, stronger and uniform friction and impact energy are generated between the magnesium alloy powder and the grinding balls, and the grinding modes of dry grinding, vacuum grinding and pressurized grinding (with the size of 80kpa) are adopted, so that the magnesium alloy powder can be fully crushed, mixed and homogenized, and meanwhile, the oxidation and deterioration of the metal powder such as magnesium and the like in the air are avoided.
And (2) directly forming by 3D printing.
The bone nail is directly molded by adopting a German Yi Europe SLM laser powder laying 3D printer EOSM100 machine. Firstly, designing a bone nail to be printed into a CAD model (shown in figure 1), and then inputting the bone nail to EOSM100 for printing by adopting an STL data file format, wherein the laser type is a 180-watt ytterbium fiber laser, the light spot diameter is 20 mu m, the movement speed of a scraper is 80mm/s, and the forming speed is 25cm3The grooving distance of the automatic powder layering device is 0.15mm, and the thickness of the powder layer is 0.04 mm. Firstly, preheating an EOSM100 machine to 480 ℃, then heating to 1480 ℃ at the speed of 30 ℃/s, inputting protective gas argon, and preserving heat for 8 hours. Then cooling to room temperature at a cooling rate of 20 ℃/s.
Step (3) the bone pin obtained by the above manufacturing was put into the following ethylene-acetone aqueous solution (24 ml of distilled water, 75 ml of ethylene and 2 ml of acetone), and the sample was sterilized and a smooth and clear metallographic structure was obtained.
Comparative example 1: an SLS method.
The german eisi SLM laser powder-laying 3D printer EOSM100 machine in step (2) in example 1 was changed to a german EOS laser (metal) powder sintering system SLS with a scanning speed of 2m/s, power supplies 220V, 25A, a power of 1000W, and other experimental conditions were the same as in example 1.
Example 2
Step (1) ball milling mode
The following magnesium alloy powder components in weight percentage are mixed: 1.0% of nano zirconium oxide (ZrO 2); 2.0 percent of nano zinc oxide (ZnO); 3.0 percent of nano magnesium oxide (MgO); 2.5 percent of vanadium; 4% of calcium; the balance of magnesium is poured into an omnibearing planetary ball mill DECO-PBM-AD-0.4L. The grinding ball material is stainless steel ball, the grinding ball occupies about 1/4 of the ball milling tank volume, the diameter of the steel ball is divided into 3 grades, large, medium and small, and the proportion is 1: 4: 5. The rotation speed of the ball milling tank is 650r/min, the planetary disc and the ball milling tank roll at 270 ℃ simultaneously in the ball milling process, stronger and uniform friction and impact energy are generated between the magnesium alloy powder and the grinding balls, and the grinding modes of dry grinding, vacuum grinding and pressurized grinding (with the size of 100kpa) are adopted, so that the magnesium alloy powder can be fully crushed, mixed and homogenized, and meanwhile, the oxidation and deterioration of the metal powder such as magnesium and the like in the air are avoided.
And (3) directly forming by 3D printing.
The bone nail is directly molded by adopting a German Yi Europe SLM laser powder laying 3D printer EOSM100 machine. Firstly, designing a bone nail to be printed into a CAD model (shown in figure 1), and then inputting the bone nail to EOSM100 for printing by adopting an STL data file format, wherein a laser type 200-watt ytterbium fiber laser has a light spot diameter of 30 mu m, a scraper movement speed of 150mm/s and a forming speed of 30cm3The grooving distance of the automatic powder layering device is 0.16mm, and the thickness of the powder layer is 0.03 mm. Firstly, preheating an EOSM100 machine to 580 ℃, then heating to 1580 ℃ at the speed of 50 ℃/s, inputting protective gas argon, and preserving heat for 9 hours. Then cooling to room temperature at a cooling rate of 35 ℃/s.
And (3) putting the bone nail manufactured by the method into an ethylene-acetone aqueous solution (28 ml of distilled water, 85 ml of ethylene and 3 ml of acetone), sterilizing a sample and obtaining a smooth and clear metallographic structure.
Comparative example 2: an SLS method.
The german eisi SLM laser powder-laying 3D printer EOSM100 machine in step (2) in example 2 was changed to a german EOS laser (metal) powder sintering system SLS with a scanning speed of 5m/s, power supplies 380V, 16A, power 2000W, and other experimental conditions were the same as in example 2.
Example 3
Step (1) ball milling mode
The following magnesium alloy powder components in weight percentage are mixed: 0.5% of nano zirconia (ZrO 2); 2.0 percent of nano zinc oxide (ZnO); 5.0 percent of nano magnesium oxide (MgO); 1.5 percent of vanadium; 6 percent of calcium; the balance being magnesium; pouring into an omnibearing planetary ball mill DECO-PBM-AD-0.4L. The grinding ball material is stainless steel ball, the grinding ball occupies about 1/3 of the ball milling tank volume, the diameter of the steel ball is divided into 3 grades, large, medium and small, and the proportion is 1: 4: 5. The rotation speed of the ball milling tank is 750r/min, the planetary disc and the ball milling tank roll at 260 degrees simultaneously in the ball milling process, stronger and uniform friction and impact energy are generated between the magnesium alloy powder and the grinding balls, and the grinding modes of dry grinding, vacuum grinding and pressurized grinding (with the size of 120kpa) are adopted, so that the magnesium alloy powder can be fully crushed, mixed and homogenized, and meanwhile, the oxidation and deterioration of the metal powder such as magnesium and the like in the air are avoided.
And (3) directly forming by 3D printing.
The bone nail is directly molded by adopting a German Yi Europe SLM laser powder laying 3D printer EOSM100 machine. Firstly, designing a bone nail to be printed into a CAD model (shown in figure 1), and then inputting the bone nail to an EOSM100 machine for printing by adopting an STL data file format, wherein the laser type is a 200-watt ytterbium fiber laser, the light spot diameter is 40 mu m, the movement speed of a scraper is 160mm/s, and the forming speed is 35cm3The grooving distance of the automatic powder layering device is 0.16mm, and the thickness of the powder layer is 0.03 mm. Firstly, preheating an EOSM100 machine to 600 ℃, then heating to 1580 ℃ at the speed of 50 ℃/s, inputting protective gas argon, and preserving heat for 9 hours. Then cooling to room temperature at a cooling rate of 35 ℃/s.
And (3) putting the bone nail manufactured by the method into an ethylene-acetone aqueous solution (24 ml of distilled water, 79 ml of ethylene and 3 ml of acetone), sterilizing a sample and obtaining a smooth and clear metallographic structure.
Comparative example 3: an SLS method.
The german eisi SLM laser powder laying 3D printer EOSM100 machine in step (2) in example 3 was changed to a german EOS laser (metal) powder sintering system SLS with a scanning speed of 4m/s, power supplies 380V, 16A, power 1500W, and other experimental conditions were the same as in example 3.
Example 4
Step (1) ball milling mode
The following magnesium alloy powder components in weight percentage are mixed: 1.0% of nano zirconium oxide (ZrO 2); 1.5 percent of nano zinc oxide (ZnO); 3.5 percent of nano magnesium oxide (MgO); 2.5 percent of vanadium; 4% of calcium; the balance being magnesium; pouring into an omnibearing planetary ball mill DECO-PBM-AD-0.4L. The grinding ball material is stainless steel ball, the grinding ball occupies about 1/3 of the ball milling tank volume, the diameter of the steel ball is divided into 3 grades, large, medium and small, and the proportion is 1: 4: 5. The rotation speed of the ball milling tank is 950r/min, the planetary disc and the ball milling tank simultaneously roll for 360 degrees in the ball milling process, stronger and uniform friction and impact energy are generated between the magnesium alloy powder and the grinding balls, and the grinding modes of dry grinding, vacuum grinding and pressurized grinding (with the size of 150kpa) are adopted, so that the magnesium alloy powder can be fully crushed, mixed and homogenized, and meanwhile, the oxidation and deterioration of the metal powder such as magnesium and the like in the air are avoided.
And (3) directly forming by 3D printing.
The bone nail is directly molded by adopting a German Yi Europe SLM laser powder laying 3D printer EOSM100 machine. Firstly, designing a bone nail to be printed into a CAD model (shown in figure 1), and then inputting the bone nail to EOSM100 for printing by adopting an STL data file format, wherein the laser type is a 200-watt ytterbium fiber laser, the light spot diameter is 40 mu m, the movement speed of a scraper is 180mm/s, and the forming speed is 35cm3The grooving distance of the automatic powder layering device is 0.18mm, and the thickness of the powder layer is 0.01 mm. Firstly, preheating an EOSM100 machine to 680 ℃, then heating to 1600 ℃ at 60 ℃/s, inputting protective gas argon, and preserving heat for 10 hours. Then cooling to room temperature at a cooling rate of 55 ℃/s.
And (3) putting the bone nail manufactured by the method into an ethylene-acetone aqueous solution (26 ml of distilled water, 80 ml of ethylene and 4 ml of acetone), sterilizing a sample and obtaining a smooth and clear metallographic structure.
Comparative example 4: an SLS method.
The german eastern SLM laser powdering 3D printer EOSM100 machine in step (2) of example 4 was changed to the german EOS laser (metal) powder sintering system SLS, scan speed 4m/s, power supply 380V, 16A, power.
1800W, other experimental conditions were the same as in example 4.
The mechanical properties of the prepared products of the above-described Selective Laser Sintering (SLS) processes of examples 1-4 and comparative examples 1-4 were compared, as shown in Table 1.
TABLE 1
Figure BDA0002128342790000081
As can be seen from table 1, the tensile strength, yield strength and elongation of the bone screws produced using examples 1-4 are significantly higher than those of the bone screw samples produced by the comparative examples. The bone screws produced in examples 1-4 had tensile strength and yield strength greater than 300Mpa, and elongation greater than 16% of the minimum standard required for bone screws. Therefore, the bone nail produced by the method has more ideal mechanical strength compared with the SLS method of selective laser sintering.
Referring to fig. 2, it can be seen that the bone screw model manufactured by the inventive method (step 2) and the SLS method according to the CAD design model of fig. 1, respectively, has a smoother surface. Fig. 3 is a scanning electron microscope image and elemental EDX microscopy analysis of the bone screw model of fig. 2 made using the method of example 1 and SLS method of the present invention. As can be seen from fig. 3, the bone screw obtained by the method of example 1 of the present invention has a smoother and clearer metallographic structure than the SLS method.
Application examples
The bone pins generated in example 1 were implanted into injured tibias of live mini-pigs and the microstructure of bone growth was observed after 10, 30, and 120 days, respectively. As can be seen from fig. 4, the bone screw was gradually degraded with the passage of time, and at 120 days, the bone screw had been completely degraded and disappeared, and the tibia of the piglet was completely repaired, and there was no local inflammatory reaction. The experiment shows that the bone nail manufactured by the method has good osteoinductivity and biological controllable degradability, and the main reasons are as follows: the larger the content of nano magnesium oxide (MgO), the stronger the corrosion inhibition resistance of the bone screw, and if the content of nano magnesium oxide is reduced, the degradation of the bone screw in a human body can be accelerated.
The above embodiments are not intended to limit the present invention, and the present invention is not limited to the above embodiments, and all embodiments are within the scope of the present invention as long as the requirements of the present invention are met.

Claims (3)

1. The bone nail capable of promoting bone growth and being completely absorbed by bones is characterized by comprising the following magnesium alloy powder components in percentage by weight: nano zirconium oxide ZrO20.5 to 2.0 percent; nano oxidation1.5 to 3.0 percent of zinc ZnO1; nano magnesium oxide MgO2.5-5.0%; 1.5-2.5% of vanadium; 3 to 8 percent of calcium; the balance being magnesium;
nano zirconium oxide ZrO2The grain diameters of the nano zinc oxide ZnO and the nano magnesium oxide MgO are 2-50 nanometers;
the bone nail is prepared by the following steps:
step (1), ball milling
Pouring the magnesium alloy powder components into an all-dimensional planetary ball mill, wherein the rotating speed of a ball milling tank is 500-950 r/min, rolling the planetary disc and the ball milling tank 180-360 degrees simultaneously in the ball milling process, and fully crushing, mixing and homogenizing by adopting a grinding mode of dry grinding, vacuum grinding and pressurized grinding while avoiding oxidation and deterioration in the air;
step (2), 3D printing direct forming
Adopting a German Yi Europe SLM laser powder laying 3D printer EOSM100 machine to directly form the bone nail; firstly, designing a bone nail to be printed into a CAD model, and then inputting the bone nail to the EOSM100 for printing by adopting an STL data file format; the laser type is an ytterbium fiber laser of 180-200 watts, the diameter of a light spot is 20-40 mu m, the movement speed of a scraper is 80-180 mm/s, and the forming speed is 25-35 cm3The groove cutting distance of the automatic powder layering device is 0.15-0.18 mm, and the thickness of each powder layer is 0.01-0.04 mm; preheating an EOSM100 machine to 480-680 ℃, then heating to 1480-1600 ℃ at 30-60 ℃/s, inputting protective gas argon, preserving heat for 8-10 hours, and then cooling to room temperature at a cooling rate of 20-55 ℃/s;
and (3) putting the bone nail manufactured by the method into an ethylene-acetone aqueous solution, and sterilizing a sample to obtain a smooth and clear metallographic structure.
2. The bone nail of claim 1, wherein the omni-directional planetary ball mill is of a type DECO-PBM-AD-0.4L, wherein the grinding balls are stainless steel balls, the grinding balls occupy 1/4-1/3 of the volume of the ball mill pot, and the diameters of the steel balls are classified into 3 grades, i.e., large, medium and small, in a ratio of 1: 4: 5.
3. The bone nail according to claim 1, wherein the volume ratio of ethylene, acetone and distilled water in the ethylene-acetone aqueous solution is (75-100): (2-6): (24-30).
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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008122595A2 (en) * 2007-04-05 2008-10-16 Cinvention Ag Biodegradable therapeutic implant for bone or cartilage repair
CN107760946A (en) * 2017-10-26 2018-03-06 中南大学 A kind of Biological magnesium alloy containing nano magnesia and Nano Silver and preparation method thereof
CN109439986A (en) * 2018-11-26 2019-03-08 杭州电子科技大学 A kind of novel magnesium alloy with higher medical performance

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* Cited by examiner, † Cited by third party
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EP2169090B3 (en) * 2008-09-30 2014-06-25 Biotronik VI Patent AG Implant made of a biodegradable magnesium alloy
CN104313391B (en) * 2014-09-26 2016-12-07 中南大学 A kind of Ti-Mg alloy material and its preparation method and application

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008122595A2 (en) * 2007-04-05 2008-10-16 Cinvention Ag Biodegradable therapeutic implant for bone or cartilage repair
CN107760946A (en) * 2017-10-26 2018-03-06 中南大学 A kind of Biological magnesium alloy containing nano magnesia and Nano Silver and preparation method thereof
CN109439986A (en) * 2018-11-26 2019-03-08 杭州电子科技大学 A kind of novel magnesium alloy with higher medical performance

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
improved mechanical properties of the new ti 15ta xZr alloys fabricated by selective laser melting for biomedical application;lamei YAN;《Journal of alloys and compounds》;20160704;全文 *

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