CN110420358A - It can promote bone growth and can be completely by bone nail of bone absorption and preparation method thereof - Google Patents

It can promote bone growth and can be completely by bone nail of bone absorption and preparation method thereof Download PDF

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Publication number
CN110420358A
CN110420358A CN201910629761.6A CN201910629761A CN110420358A CN 110420358 A CN110420358 A CN 110420358A CN 201910629761 A CN201910629761 A CN 201910629761A CN 110420358 A CN110420358 A CN 110420358A
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bone
bone nail
ball
nail
nano
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CN110420358B (en
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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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    • A61L31/00—Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
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    • A61L31/00—Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
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    • 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
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Abstract

The present invention, which discloses, can promote bone growth and can be completely by bone nail of bone absorption and preparation method thereof.Bone nail ingredient includes nano zircite 0.5%~2.0%；Nano zine oxide 1.5%~3.0%；Nano magnesia 2.5%~5.0%；Vanadium 1.5~2.5%；Calcium 3~8%；Surplus is magnesium.First by mentioned component ball milling and then Germany easily Ou Si SLM laser powdering 3D printer EOSM100 machine straight forming, it is finally putting into ethylene-aqueous acetone solution sterilization.The bone nail that the present invention generates its tension intensity, yield strength are all larger than the minimum sandards 300Mpa of bone nail requirement, and elongation percentage is also greater than the minimum sandards 16% that bone nail requires.Bone nail of the present invention has good osteoinductive, conducive to stable synosteosis is formed, while having biological controlled degradation.

Description

It can promote bone growth and can be completely by bone nail of bone absorption and preparation method thereof
Technical field
It can promote bone growth and can be completely by bone nail of bone absorption and preparation method thereof the present invention relates to a kind of.
Background technique
Bone nail, also known as medical instrument fracture fixation " screw ", bone nail is usually used in the fixation of internal fracture or dislocation, by straight It connects and is screwed into the fixation that the implants such as two different bone blocks or fixed bone plate realize fracture, position bone and promote its recovery from illness.Bone Nail material must have 2 functions: (1) having enough mechanical strengths that can support the healing of injured bone, (2) have biology living Property, after bone healing, it can be degraded and absorb by human body.
Based on traditional bone " screw " for playing fixed function, titanium alloy or stainless steel is mostly used to be made greatly at present, after rehabilitation The puzzlement for needing second operation to take out.Magnesium alloy is the alloy that other elements composition is added based on magnesium.Its main feature is that: density Small (1.8g/cm3 magnesium alloy or so), intensity is high, and elasticity modulus is big, good heat dissipation, and absorb shock resistance is good, absorbs impact load-carrying ability and compares aluminium Alloy is big, and the corrosive nature of resistance to organic matter and alkali is good.Medical magnesium alloy " bone nail " has good biocompatibility and certain Mechanical strength, by than being described as " revolutionary biomaterial ".Degradable high purity magnesium " bone nail ", maximum difficult point are its degradation rates It is too fast, it has just degraded and has disappeared before injured knitting.The material and manufacturing method for studying magnesium alloy, can ensure that magnesium alloy bone There is nail enough mechanical strengths can promote the fast-growth of bone, and can die away after knitting, be to cure now The research hotspot of material circle and problem in the urgent need to address.
Summary of the invention
It is an object of the invention to, provide to promote bone growth and can be completely by bone in view of the deficiencies of the prior art The bone nail of absorption.
The present invention can promote bone growth and can completely by the bone nail of bone absorption by following weight content each ingredient structure At: nano zircite (ZrO2) 0.5%~2.0%；Nano zine oxide (ZnO) 1.5%~3.0%；Nano magnesia (MgO) 2.5%~5.0%；Vanadium 1.5~2.5%；Calcium 3~8%；Surplus is magnesium；
Nano zircite (ZrO2): by nano zircite and nano zine oxide of the invention, nano magnesia, vanadium metal, Calcium, magnesium are compound, can greatly improve the high temperature oxidation resistance of material, improve its fracture toughness, bending strength etc..Partial size is 2 ~50 nanometers.
Nano zine oxide (ZnO): nano zine oxide is stable compound, has good tear resistance and elasticity, together When there are also antibacterial and anti-inflammatory effect, preparation method: after zinc ingot metal made from electrolysis method is heated to 580~750 DEG C of meltings, be placed in In high-temperature crucible, it is allowed to fusion and gasification under 1280~1380 DEG C of high temperature, hot-air is imported and is aoxidized, the zinc oxide warp of generation Cooling, cyclonic separation, fine particle is trapped with cloth bag, obtains zinc oxide finished product.Partial size is 2~50 nanometers.
Zn+CO+O2=ZnO+CO2
Nano magnesia (MgO): nanoscale magnesium has apparent small-size effect, skin effect, quantum size effect Should with macroscopical tunnel-effect, modified processing, soilless sticking phenomenon, optics, catalysis, magnetism, mechanics, in terms of have permitted More exceptional functions and significant application value, prospect is boundless, is 21 century important new material.In the present invention, magnesia is made For antiacid, adsorbent, desulfurizing agent, deleading reagent, the effect of filter aid, PH regulator is complexed, and can inhibit and alleviate magnesium metal Corrode in human body environment and generates hydrogen.Be thus added in the present invention nano magnesia (MgO) can bone screws significantly inhibition Corrosive power.Partial size is 2~50 nanometers.
Mg+2H2O→Mg(OH)2+H2↑
Calcium: calcium is the inorganic salts component that content is most in human body, about the 1.5%~2.0% of percentage of liveweight.Wherein 99% Calcium be present in bone and tooth in the form of bone salts.Bone calcium is mainly with non-crystal calcium monohydrogen phosphate (CaHPO4) and crystal hydroxyl Apatite (3Ca3PO4×Ca(OH)2) two kinds of forms exist.Calcium monohydrogen phosphate is more than outmoded bone in area of new bone, during skeletal maturation It is gradually transformed into hydroxyapatite.The present invention adds calcium, can promote the tachyauxesis of area of new bone, and bone calcium and blood calcium is made to keep dynamic flat Weighing apparatus, while can be absorbed by the body after knitting.
Vanadium: being a kind of silver-gray metal.With very high ductility, and vanadium is the essential trace elements of the human body, In People's in-vivo content is about 25mg, and the present invention adds vanadium, can promote the Regeneration and Repair of bone and wound, and bone repair with Afterwards, vanadium can be metabolized and be discharged by human body natural.
Magnesium: magnesium is most light one of structural metallic material, and has specific strength and specific stiffness height, damping and amortization and machinability It is good, be dominant cation in human body cell, be concentrated in mitochondria, be only second to potassium and phosphorus, extracellular fluid be only second to sodium and Calcium occupies third position, is the necessary material of the basic biochemical reaction of internal various kinds of cell.Currently, magnesium alloy wheel chair, rehabilitation and Medical treatment device Tool etc..Ingredient of the invention is mainly magnesium metal, and the bone nail of processing has light-weight, high mechanical strength and biocompatibility.
It is a further object to provide the preparation method of above-mentioned bone nail, enhance its mechanical performance and biological Can, specifically:
Step (1), ball milling
Each magnesium alloy powder ingredient is poured into omnidirectional planetary ball mill, ball grinder revolving speed is 500~950r/min, In In mechanical milling process, planetary disk and ball grinder carry out 180~360 ° of rollings simultaneously, produce between above-mentioned magnesium alloy powder and mill ball Life is more strong and uniformly rubs, Impact energy, the lapping mode ground using dry grinding, vacuum and pressurization, thus magnesium alloy powder End is able to adequately crush, mixing, be homogenized, while the metal powders such as above-mentioned magnesium being avoided to aoxidize and go bad in air.
Each magnesium alloy powder ingredient is made of following weight content component: nano zircite (ZrO2) 0.5%~2.0%； Nano zine oxide (ZnO) 1.5%~3.0%；Nano magnesia (MgO) 2.5%~5.0%；Vanadium 1.5~2.5%；Calcium 3~ 8%；Surplus is magnesium；
Omnidirectional planetary ball mill uses model DECO-PBM-AD-0.4L, and wherein grinding ball material is stainless steel ball, mill Ball accounts for the 1/4~1/3 of ball milling tank volume, and steel ball size is divided into large, medium and small 3 ranks, ratio 1: 4: 5.
Step (2), 3D printing straight forming
Using German easily Ou Si SLM laser powdering 3D printer EOSM100 machine straight forming bone nail of the invention.First will The bone nail to be printed is designed to CAD model, is then input to EOSM100 using .STL document format data and is printed.Laser Device type is 180~200 watts of ytterbium optical fiber laser, and spot diameter is 20~40 μm, the movement velocity of scraper is 80~ 180mm/s, shaping speed are 25~35cm3/ h, the cutting spacing of automatic Powder decker are 0.15~0.18mm, each powder Last layer is with a thickness of 0.01~0.04mm.EOSM100 machine is preheating to 480~680 DEG C first, is then warming up to 30~60 DEG C/s 1480~1600 DEG C, input protection gas argon gas keeps the temperature 8~10 hours, is then down to room temperature with rate of temperature fall for 20~55 DEG C/s .
The resulting bone nail of above-mentioned manufacture is put into ethylene-aqueous acetone solution by step (3), and sample is able to sterilize and obtains light Sliding and clearly metallographic structure.
Ethylene in ethylene-aqueous acetone solution, acetone, distilled water three volume ratio be (75~100): (2~6): (24~ 30)。
Compared with prior art, scheme proposed by the present invention has the advantage that
1. the present invention uses metal oxide powder: zirconium oxide (ZrO2), zinc oxide (ZnO), magnesia (MgO), by this Nanometer is made in three kinds of powder, and granular size is 2~50 nanometers, due to the imperceptibility of crystal grain, Electronic Structure and crystalline substance Body structure changes, and produces quantum size effect and polymolecularity etc. that macro object does not have, therefore can big university degree hair Its mechanical property of the enhancing of shark bone screw and erosion-resisting ability.The bone nail that the present invention generates its tension intensity, yield strength are equal Greater than the minimum sandards 300Mpa that bone nail requires, elongation percentage is also greater than the minimum sandards 16% that bone nail requires.Bone of the present invention as a result, Nail has more preferably mechanical strength compared to existing precinct laser sintering SLS method.
2. good biocompatibility:
Bone nail of the present invention has good osteoinductive, conducive to stable synosteosis is formed, while having biological controllable drop Xie Xing.
Detailed description of the invention
Fig. 1 is the bone nail CAD model that the present invention designs；
Fig. 2 is the bone nail model manufactured respectively with the present invention and SLS method according to the CAD design model of Fig. 1；
Fig. 3 is the scanning electron microscope (SEM) photograph of the bone nail model to be manufactured in Fig. 2 with the method for the embodiment of the present invention 1 and SLS method Picture and element EDX microscopic analysis；The wherein method of (a) embodiment of the present invention 1, (b) SLS method；
Fig. 4 is the micro-structure diagram of animal experimental observation bone growth；Wherein 10 days (a)；(b)30；(c) 120 days.
Specific embodiment
The present invention is further analyzed combined with specific embodiments below.
Zirconium oxide (ZrO2) that following embodiment uses, zinc oxide (ZnO), magnesia (MgO) its granular size be 2~ 50 nanometers.
Embodiment 1
Step (1), ball milling method
By each magnesium alloy powder ingredient of following weight content: nano zircite (ZrO2) 2.0%；Nano zine oxide (ZnO) 3.0%；Nano magnesia (MgO) 5.0%；Vanadium 2.5%；Calcium 8%；Surplus is magnesium, pours into omnidirectional planetary ball mill DECO-PBM-AD-0.4L.Grinding ball material is stainless steel ball, and abrading-ball accounts for about the 1/4 of ball milling tank volume, steel ball size be divided into it is big, Middle or small 3 ranks, ratio 1: 4: 5.Ball grinder revolving speed is 500r/min, and in mechanical milling process, planetary disk and ball grinder are same 180 ° of Shi Jinhang rollings generate more strong and uniform friction, Impact energy, adopt between above-mentioned magnesium alloy powder and mill ball With dry grinding, vacuum and pressurization mill (size 80kpa) lapping mode, thus magnesium alloy powder be able to adequately crush, mixing, Homogenizing, while the metal powders such as above-mentioned magnesium being avoided to aoxidize and go bad in air.
Step (2), 3D printing straight forming
Using German easily Ou Si SLM laser powdering 3D printer EOSM100 machine straight forming bone nail of the invention.First will The bone nail to be printed is designed to CAD model (as shown in Figure 1), then using .STL document format data be input to EOSM100 into Row printing, the ytterbium optical fiber laser that laser type is 180 watts, spot diameter are 20 μm, and the movement velocity of scraper is 80mm/s, Shaping speed is 25cm3/ h, the cutting spacing of automatic Powder decker is 0.15mm, layer thickness 0.04mm.First EOSM100 machine is preheating to 480 DEG C, is then warming up to 1480 DEG C with 30 DEG C/s, input protection gas argon gas keeps the temperature 8 hours.Then With rate of temperature fall for 20 DEG C/s, it is down to room temperature.
The resulting bone nail of above-mentioned manufacture is put into following ethylene-aqueous acetone solution (24 milliliters of distilled water, 75 millis by step (3) Rise ethylene and 2 milliliters of acetone) in, sample is able to sterilize and obtain smooth and clearly metallographic structure.
Comparative example 1:SLS method
Germany's easily Ou Si SLM laser powdering 3D printer EOSM100 machine in step (2) in embodiment 1 is changed to The German powder sintered system SLS of EOS laser (metal), scanning speed 2m/s, power supply 220V, 25A, power 1000W, other experiments Condition is same as Example 1.
Embodiment 2
Step (1) ball milling method
By each magnesium alloy powder ingredient of following weight content: nano zircite (ZrO2) 1.0%；Nano zine oxide (ZnO) 2.0%；Nano magnesia (MgO) 3.0%；Vanadium 2.5%；Calcium 4%；Surplus is magnesium, pours into omnidirectional planetary ball mill DECO-PBM-AD-0.4L.Grinding ball material is stainless steel ball, and abrading-ball accounts for about the 1/4 of ball milling tank volume, steel ball size be divided into it is big, Middle or small 3 ranks, ratio 1: 4: 5.Ball grinder revolving speed is 650r/min, and in mechanical milling process, planetary disk and ball grinder are same 270 ° of Shi Jinhang rollings generate more strong and uniform friction, Impact energy, adopt between above-mentioned magnesium alloy powder and mill ball With dry grinding, the lapping mode of vacuum and pressurization mill (size 100kpa), thus magnesium alloy powder is able to adequately crush, mix It closes, homogenizing, while the metal powders such as above-mentioned magnesium being avoided to aoxidize and go bad in air.
Step (2) 3D printing straight forming
Using German easily Ou Si SLM laser powdering 3D printer EOSM100 machine straight forming bone nail of the invention.First will The bone nail to be printed is designed to CAD model (as shown in Figure 1), then using .STL document format data be input to EOSM100 into Row printing, 200 watts of laser type of ytterbium optical fiber laser, spot diameter are 30 μm, and the movement velocity of scraper is 150mm/s, Shaping speed is 30cm3/ h, the cutting spacing of automatic Powder decker is 0.16mm, layer thickness 0.03mm.First EOSM100 machine is preheating to 580 DEG C, is then warming up to 1580 DEG C with 50 DEG C/s, input protection gas argon gas keeps the temperature 9 hours.Then With rate of temperature fall for 35 DEG C/s, it is down to room temperature.
The resulting bone nail of above-mentioned manufacture is put into ethylene-aqueous acetone solution (28 milliliters of distilled water, 85 milliliters of second by step (3) Alkene and 3 milliliters of acetone) in, sample is able to sterilize and obtain smooth and clearly metallographic structure.
Comparative example 2:SLS method
Germany's easily Ou Si SLM laser powdering 3D printer EOSM100 machine in step (2) in embodiment 2 is changed to The German powder sintered system SLS of EOS laser (metal), scanning speed 5m/s, power supply 380V, 16A, power 2000W, other experiments Condition is same as Example 2.
Embodiment 3
Step (1) ball milling method
By each magnesium alloy powder ingredient of following weight content: nano zircite (ZrO2) 0.5%；Nano zine oxide (ZnO) 2.0%；Nano magnesia (MgO) 5.0%；Vanadium 1.5%；Calcium 6%；Surplus is magnesium；Pour into omnidirectional planetary ball mill DECO-PBM-AD-0.4L.Grinding ball material is stainless steel ball, and abrading-ball accounts for about the 1/3 of ball milling tank volume, steel ball size be divided into it is big, Middle or small 3 ranks, ratio 1: 4: 5.Ball grinder revolving speed is 750r/min, and in mechanical milling process, planetary disk and ball grinder are same 260 ° of Shi Jinhang rollings generate more strong and uniform friction, Impact energy, adopt between above-mentioned magnesium alloy powder and mill ball With dry grinding, the lapping mode of vacuum and pressurization mill (size 120kpa), thus magnesium alloy powder is able to adequately crush, mix It closes, homogenizing, while the metal powders such as above-mentioned magnesium being avoided to aoxidize and go bad in air.
Step (2) 3D printing straight forming
Using German easily Ou Si SLM laser powdering 3D printer EOSM100 machine straight forming bone nail of the invention.First will The bone nail to be printed is designed to CAD model (as shown in Figure 1), is then input to EOSM100 machine using .STL document format data It is printed, the ytterbium optical fiber laser that laser type is 200 watts, spot diameter is 40 μm, and the movement velocity of scraper is 160mm/s, shaping speed 35cm3/ h, the cutting spacing of automatic Powder decker is 0.16mm, layer thickness is 0.03mm.EOSM100 machine is preheating to 600 DEG C first, is then warming up to 1580 DEG C with 50 DEG C/s, input protection gas argon gas is protected Temperature 9 hours.Then room temperature is down to for 35 DEG C/s with rate of temperature fall.
The resulting bone nail of above-mentioned manufacture is put into ethylene-aqueous acetone solution (24 milliliters of distilled water, 79 milliliters of second by step (3) Alkene and 3 milliliters of acetone) in, sample is able to sterilize and obtain smooth and clearly metallographic structure.
Comparative example 3:SLS method
Germany's easily Ou Si SLM laser powdering 3D printer EOSM100 machine in step (2) in embodiment 3 is changed to The German powder sintered system SLS of EOS laser (metal), scanning speed 4m/s, power supply 380V, 16A, power 1500W, other experiments Condition is same as Example 3.
Embodiment 4
Step (1) ball milling method
By each magnesium alloy powder ingredient of following weight content: nano zircite (ZrO2) 1.0%；Nano zine oxide (ZnO) 1.5%%；Nano magnesia (MgO) 3.5%；Vanadium 2.5%；Calcium 4%；Surplus is magnesium；Pour into comprehensive planetary type ball-milling Machine DECO-PBM-AD-0.4L.Grinding ball material is stainless steel ball, and abrading-ball accounts for about the 1/3 of ball milling tank volume, steel ball size be divided into it is big, Middle or small 3 ranks, ratio 1: 4: 5.Ball grinder revolving speed is 950r/min, and in mechanical milling process, planetary disk and ball grinder are same 360 ° of Shi Jinhang rollings generate more strong and uniform friction, Impact energy, adopt between above-mentioned magnesium alloy powder and mill ball With dry grinding, the lapping mode of vacuum and pressurization mill (size 150kpa), thus magnesium alloy powder is able to adequately crush, mix It closes, homogenizing, while the metal powders such as above-mentioned magnesium being avoided to aoxidize and go bad in air.
Step (2) 3D printing straight forming
Using German easily Ou Si SLM laser powdering 3D printer EOSM100 machine straight forming bone nail of the invention.First will The bone nail to be printed is designed to CAD model (as shown in Figure 1), then using .STL document format data be input to EOSM100 into Row printing, the ytterbium optical fiber laser that laser type is 200 watts, spot diameter are 40 μm, and the movement velocity of scraper is 180mm/ S, shaping speed 35cm3/ h, the cutting spacing of automatic Powder decker is 0.18mm, layer thickness 0.01mm.It is first EOSM100 machine is first preheating to 680 DEG C, is then warming up to 1600 DEG C with 60 DEG C/s, input protection gas argon gas keeps the temperature 10 hours. Then room temperature is down to for 55 DEG C/s with rate of temperature fall.
The resulting bone nail of above-mentioned manufacture is put into ethylene-aqueous acetone solution (26 milliliters of distilled water, 80 milliliters of second by step (3) Alkene and 4 milliliters of acetone) in, sample is able to sterilize and obtain smooth and clearly metallographic structure.
Comparative example 4:SLS method
Germany's easily Ou Si SLM laser powdering 3D printer EOSM100 machine in step (2) in embodiment 4 is changed to The German powder sintered system SLS of EOS laser (metal), scanning speed 4m/s, power supply 380V, 16A, power
1800W, other experiment conditions are same as Example 4
The product for preparing of above-described embodiment 1-4 and comparative example 1-4 precinct laser sintering (SLS) method is subjected to mechanical performance Compare, is shown in Table 1.
Table 1
Find out from table 1, bone nail its tension intensity, yield strength and the elongation percentage generated using embodiment 1-4 is all obvious The bone nail sample generated higher than comparative example.Bone nail its tension intensity that embodiment 1-4 is generated, yield strength are all larger than bone nail requirement Minimum sandards 300Mpa, elongation percentage is also greater than the minimum sandards 16% that bone nail requires.The bone nail of the method for the present invention production as a result, There is more preferably mechanical strength compared to precinct laser sintering SLS method.
Referring to Fig. 2, the bone manufactured respectively with the method for the present invention (step 2) and SLS method according to the CAD design model of Fig. 1 Dolly set type, it can be seen that the bone nail model surface obtained using the present invention is more smooth.Fig. 3 is that the embodiment of the present invention 1 is used in Fig. 2 Method and SLS method manufacture bone nail model scanning electron microscope image and element EDX microscopic analysis.From figure 3, it can be seen that adopting There is more smooth and clearly metallographic structure with the bone nail that the method for the embodiment of the present invention 1 ratio SLS method obtains.
Application Example
In the shin bone that embodiment 1 is generated to bone nail implantation mini piggy injury living, observed after 10,30,120 days The microstructure of bone growth.From fig. 4, it can be seen that bone nail is over time, bone nail was gradually being degraded, at 120 days When bone nail it is degradable and disappear, the shin bone of piggy is also repaired completely, while also without local inflammatory response.This reality It tests and shows that the bone nail of the method for the present invention manufacture has good osteoinductive and biological controlled degradation, the main reason is that: it receives Rice magnesia (MgO) content is bigger, and the anti-inhibition corrosive power of bone screws is stronger, if reducing the content of nano magnesia, can add Fast bone screws are degraded in human body.
Above-described embodiment is not for limitation of the invention, and the present invention is not limited only to above-described embodiment, as long as meeting The present invention claims all belong to the scope of protection of the present invention.

Claims (4)

1. bone growth can be promoted and can be completely by the bone nail of bone absorption, it is characterised in that by each ingredient of following weight content It constitutes: nano zircite (ZrO2) 0.5%~2.0%；Nano zine oxide (ZnO) 1.5%~3.0%；Nano magnesia (MgO) 2.5%~5.0%；Vanadium 1.5~2.5%；Calcium 3~8%；Surplus is magnesium；
Nano zircite (ZrO2), nano zine oxide (ZnO), nano magnesia (MgO) partial size be 2~50 nanometers.
2. bone growth can be promoted as described in claim 1 and can be special completely by the preparation method of the bone nail of bone absorption Sign be method includes the following steps:
Step (1), ball milling
Each magnesium alloy powder ingredient described in claim 1 is poured into omnidirectional planetary ball mill, ball grinder revolving speed is 500~ 950r/min, in mechanical milling process, planetary disk and ball grinder carry out 180~360 ° of rollings simultaneously, using dry grinding, vacuum and increasing The lapping mode for pressing mill, is adequately crushed, is mixed, is homogenized, while avoiding aoxidizing and going bad in air；
Step (2), 3D printing straight forming
Using German easily Ou Si SLM laser powdering 3D printer EOSM100 machine straight forming bone nail of the invention；It will beat first The bone nail of print is designed to CAD model, is then input to EOSM100 using .STL document format data and is printed；Laser class The ytterbium optical fiber laser that type is 180~200 watts, spot diameter are 20~40 μm, and the movement velocity of scraper is 80~180mm/s, Shaping speed is 25~35cm3/ h, the cutting spacing of automatic Powder decker are 0.15~0.18mm, each layer thickness For 0.01~0.04mm；EOSM100 machine is preheating to 480~680 DEG C first, then 1480 are warming up to 30~60 DEG C/s~ 1600 DEG C, input protection gas argon gas keeps the temperature 8~10 hours, is then down to room temperature with rate of temperature fall for 20~55 DEG C/s；
The resulting bone nail of above-mentioned manufacture is put into ethylene-aqueous acetone solution by step (3), sample be able to sterilize and obtain it is smooth and Clearly metallographic structure.
3. preparation method as claimed in claim 2, it is characterised in that omnidirectional planetary ball mill uses model DECO-PBM- AD-0.4L, wherein grinding ball material is stainless steel ball, and abrading-ball accounts for the 1/4~1/3 of ball milling tank volume, steel ball size be divided into it is big or middle, Small 3 ranks, ratio 1: 4: 5.
4. preparation method as claimed in claim 2, it is characterised in that ethylene, acetone, distilled water three in ethylene-aqueous acetone solution The volume ratio of person is (75~100): (2~6): (24~30).
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113121118A (en) * 2021-03-08 2021-07-16 四川大学 Vanadium-doped silicon-calcium-phosphorus mesoporous bioactive glass powder

Citations (5)

* 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
US20100082092A1 (en) * 2008-09-30 2010-04-01 Biotronik Vi Patent Ag Implant Made of a Biodegradable Magnesium Alloy
CN104313391A (en) * 2014-09-26 2015-01-28 中南大学 A Ti-Mg alloy material, a preparing method thereof and applications of the alloy material
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

Patent Citations (5)

* 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
US20100082092A1 (en) * 2008-09-30 2010-04-01 Biotronik Vi Patent Ag Implant Made of a Biodegradable Magnesium Alloy
CN104313391A (en) * 2014-09-26 2015-01-28 中南大学 A Ti-Mg alloy material, a preparing method thereof and applications of the alloy material
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
LAMEI YAN: "improved mechanical properties of the new ti 15ta xZr alloys fabricated by selective laser melting for biomedical application", 《JOURNAL OF ALLOYS AND COMPOUNDS》 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113121118A (en) * 2021-03-08 2021-07-16 四川大学 Vanadium-doped silicon-calcium-phosphorus mesoporous bioactive glass powder

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