CN108480626A - High antibiotic property controlled degradation magnesium-based composite material bone implant and its manufacturing process - Google Patents
High antibiotic property controlled degradation magnesium-based composite material bone implant and its manufacturing process Download PDFInfo
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Abstract
The present invention discloses a kind of high antibiotic property controlled degradation magnesium-based composite material bone implant and its manufacturing process, the magnesium-based composite material bone implant includes magnesium alloy abutment of implant, which is dispersed with the antibiotic property nanometer copper particle of fabricated in situ and carries the Mg of controlled degradation function2Si, MgO nanometer reinforcing phase.Its manufacturing process includes the following steps：Obtain bone implant threedimensional model；Spherical magnesium alloy powder, nano oxidized copper powders and nano grade silica particles are weighed, it is uniform in high-purity argon gas and the mixed gas protected lower ball milling mixing of high-purity carbon dioxide, obtain composite formed powder；Under high-purity argon gas and high-purity carbon dioxide mixed atmosphere, forming technology is melted by composite formed powder shaped in situ nanometer copper particle and Mg by selective laser2Si, MgO nanometer reinforcing phase are scattered in magnesium-based composite material bone implant, and vacuum stress relief annealing process is carried out to it；The manufacturing process can realize the controllable manufacture of high antibiotic property magnesium-based composite material bone implant degradation rate.
Description
Technical field
The present invention relates to a kind of composite material bone implant and manufacturing process, more particularly to a kind of high antibiotic property controlled degradation
Magnesium-based composite material bone implant and its manufacturing process.
Background technology
It is big that human body orthopaedics class disease caused by aging of population, traffic accident, unexpected injury etc. has become both domestic and external one
Major issue.China human mortality is numerous, and aging is on the rise, and the patient populations of rehabilitation operation need to be carried out by means of medical implant
Increasingly increase, lead to high military service function metals material implant demand sharp increase.It is implanted into the bio-medical material of human body not
Impaired tissue can only be repaired and can permanently replace the tissue of oneself necrosis, such as bone, joint, to a certain extent at
Work(has cured orthopaedics class disease.Stainless steel, cochrome and titanium alloy have become the main material of current bone implant manufacture
Material, and in clinicing aspect using relatively broad.
But these metal bone implants are primarily present problems with after being implanted into human body：When stress shielding effect, even if
It is that also several times are higher than the elasticity modulus of human normal bone (about to the higher titanium alloy elastic modulus (about 110GPa) of specific strength
20GPa), because of elasticity modulus mismatch between implant and human body bone, stress shielding effect is easily generated, sclerotin around implantation material is caused
Loose or even second fracture；Second is that belonging to inertia implant, these metal implants cannot voluntarily degrade in human body, because
And when human body damaged tissues will heal, need to by second operation take out implant, cause to patient bring it is secondary pain with
Financial burden.Therefore, the research and development and application of high-performance degradable metal bone implant have a very important significance.
Magnesium alloy is because possessing many merits such as excellent mechanical compatibility, biocompatibility and degradability, and e.g., magnesium can
The function of participating in human metabolism, is the activator and confactor of a variety of enzymes, while also greatly taking part in bone and tooth
The composition of tooth；Secondly, the density of magnesium, the density of elasticity modulus and human body natural's bone, elasticity modulus are closest, effectively facilitate new
The growth of bone；Furthermore normal person is both needed to feed the demand of metabolism of a certain amount of food containing magnesium to meet human body daily, together
When, excessive magnesium can voluntarily degrade, and be excreted by urine, and any damage, these advantages will not be caused to make to body
It becomes the research focus of biological medical degradable metal implant material of new generation.
However, active time is limited after implantation human body, wait for that impaired tissue not yet heals completely, magnesium alloy is degraded automatically
It disappears.After magnesium alloy implants, Cl that human body fluid contains-, HPO4 2-, HCO3 -Equal erosion carbon dioxides can penetrate magnesium alloy
The loose hole of surface protection film reaches Mg alloy surface, starts to corrode magnesium alloy substrate.Wherein C1-Aggressivity is relatively strong, can
Soluble MgCl is converted by chemical reaction with the corrosion product for generating Mg alloy surface2So that Corrosion Behaviors of Magnesium Alloys is more
Soon.There is also numerous problems in clinical trial for current magnesium and its alloy implant：(1) degradation rate is very fast, especially in people
Under the physiological environment of body complexity, degradation is especially apparent, and seriously restricts it in clinical application；Currently, most magnesium alloy bone implantation
Body by processing technology for surface modification to reduce its degradation rate, but between face coat and magnesium alloy substrate interface binding power compared with
It is weak, it easily ruptures and fails during its military service, and then deteriorate conditions of patients；(2) bacterium is usually easily adhered to alloy implantation
Body surface face forms biomembrane, and then causes infection；And magnesium and its alloy itself do not have antibacterial functions, lead to magnesium alloy implant
Cause various inflammation during being on active service under the conditions of human body complex physiologic, aggravates the state of an illness of patient；(3) because of skeleton space shape
Shape is complex, and general forming technology (e.g., casting, forging etc.) is more complex, and the accuracy of manufacture is not high, the manufacturing cycle is long, substantially
Increase production cost.
Invention content
Goal of the invention：The present invention for existing magnesium-based bone implant there are the problem of, it is controllable to provide a kind of high antibiotic property
Degradation magnesium-based composite material bone implant, and provide a kind of manufacturing process of the magnesium-based composite material bone implant.
Technical solution：High antibiotic property controlled degradation magnesium-based composite material bone implant of the present invention, including magnesium alloy
Abutment of implant, the intrinsic silicon are dispersed with the antibiotic property nanometer copper particle of fabricated in situ and carry controlled degradation function
Mg2Si, MgO nanometer reinforcing phase.
Preferably, nanometer copper particle and Mg2Si, MgO nanometer reinforcing phase are by spherical magnesium alloy, nano cupric oxide and nanometer two
Silica is generated by reaction in-situ, wherein the mass ratio of spherical magnesium alloy, nano cupric oxide and nano silicon dioxide is 500:
10:1~500:1:10.The process of reaction in-situ is：
Mg+CuO → Cu+MgO,
2Mg+SiO2→ Si+2MgO,
2Mg+Si→Mg2Si。
Above-mentioned spherical shape magnesium alloy can be medical Mg-Al-Zn alloys, Mg-Zn-Mn alloys, Mg-Ca alloys or Mg-Nd-Zn-
Zr alloys.
The manufacturing process of high antibiotic property controlled degradation magnesium-based composite material bone implant of the present invention, including following steps
Suddenly：
(1) bone implant threedimensional model is obtained；
(2) spherical magnesium alloy powder, nano oxidized copper powders and nano grade silica particles are weighed, in high-purity argon gas and height
Ball milling mixing is uniform under the mixed gas protected environment of pure carbon dioxide, obtains composite formed powder；
(3) under high-purity argon gas and high-purity carbon dioxide mixed atmosphere, melting forming technology by selective laser will be described
Composite formed powder shaped in situ nanometer copper particle and Mg2Si, MgO nanometer reinforcing phase are scattered in magnesium-based composite material bone
Implant；
(4) bone implant obtained by step (3) is subjected to vacuum stress relief annealing process.
In above-mentioned steps (2), it is preferred to use cryogenic vacuum protects ball-milling technology to carry out ball milling mixing, and process conditions are：
Temperature control, 0~25 DEG C of ball milling temperature are cooled down using liquid nitrogen, vacuum degree is less than 0.1Pa, and rotating speed is 50~150rpm, often rotates forward ball milling 5
~8min immediately stops 5min, then inverts 5~8min of ball milling, and Ball-milling Time is 2~4h.
Preferably, in step (2), the mass ratio of spherical magnesium alloy, nano cupric oxide and nano silicon dioxide is 500:10:
1~500:1:10.Wherein, the grain size of spherical magnesium alloy powder is preferably 10~60 μm, and sphericity is not less than 90%, and purity is not low
In 99.7；Further, nano cupric oxide is preferably dimensioned to be 10~50nm, and nano silicon dioxide is preferably dimensioned to be 30~
100nm。
In above-mentioned steps (3), selective laser fusing forming process conditions are preferably：Laser beam energy density be 60~
210J/m3, laser beam spot size is 10~70 μm, and powder bed thickness is 20~50 μm, and oxygen content is less than 10ppm.
Specifically, in step (4), vacuum stress relief annealing process process conditions are：Vacuum degree is less than 0.1Pa, destressing
Annealing temperature is 50~150 DEG C, and annealing time is 2~8h
Inventive principle：The manufacturing process of the high antibiotic property controlled degradation magnesium-based composite material bone implant of the present invention is based on Mg
+ CuO → Cu+MgO, 2Mg+SiO2→ Si+2MgO, 2Mg+Si → Mg2The thermodynamic condition of Si reaction in-situs, makes full use of laser
Selective melting technique high energy laser beam and the strong reciprocation of composite material of magnesium alloy powder and high-accuracy forming characteristic, it is in situ
Generate the more complicated nanometer copper particle with high antibiotic property of geometry and corrosion proof Mg2Si, MgO nano ceramics increase
Strong composite material of magnesium alloy implant.At the same time, it is based on Materials design principle and patient cures the period, by adjusting laser
Dioxide-containing silica in selective melting forming technology and magnesium alloy composite granule, can accuracy controlling nanometer Mg2Si, MgO ceramic phase
Content, to realize the controllable manufacture of high antibiotic property magnesium-based composite material bone implant degradation rate.
Advantageous effect：Compared with prior art, the beneficial effects of the present invention are：(1) high antibiotic property of the invention is controllable
The degradation generated in-situ nanometer copper particle of magnesium-based composite material bone implant can effectively improve it and the interface of matrix magnesium alloy is tied
Intensity is closed, service life of the implant in human body is significantly extended；On the other hand, by the adjustment of forming technology, it can be achieved that receiving
The rice controllable growth of copper particle and its accuracy controlling of antibacterial functions；Moreover, city can be selected in the raw material for generating nanometer copper ion
Cheap CuO powder is sold, greatly reduces the manufacturing cost of magnesium alloy bone implant, and the in-situ method generation period is short, has good
Good market application prospect；(2) the magnesium-based composite material bone implant of high antibiotic property controlled degradation of the invention is generated in-situ
Corrosion resistant type Mg2Si, MgO nano ceramics mutually can provide equiax crystal for magnesium alloy solidification, and thinning solidification structure is obviously improved anti-corrosion
Performance, and then reduce degradation rate；Meanwhile be based on magnesium-based composite material design science principle, by change forming process conditions and
Dioxide-containing silica in magnesium-based composite material powder is, it can be achieved that corrosion resistant type Mg2The controllable preparation of Si, MgO nano ceramics phase content,
With the degradation rate of accuracy controlling magnesium-based composite material bone implant；(3) manufacturing process of the invention is implanted into based on magnesium alloy bone
The functional requirement and space structure feature of body utilize high energy laser beam and magnesium alloy composite wood by selective laser smelting technology
Feed powder body strong reciprocation provides thermodynamic and kinetic conditions, it can be achieved that magnesium alloy bone implant for reaction in-situ
The accurate Non-mould shaping of integration of labyrinth-material-function, obtains high antibiotic property controlled degradation magnesium-based composite material bone implantation
Body.
Description of the drawings
Fig. 1 is high antibiotic property controlled degradation magnesium-based composite material bone implant made from Examples 1 to 8 in human body simulation body
Liberation of hydrogen volume in liquid.
Specific implementation mode
Technical scheme of the present invention is described further below in conjunction with the accompanying drawings.
A kind of high antibiotic property controlled degradation magnesium-based composite material bone implant of the present invention is magnesium alloy abutment of implant, should
Intrinsic silicon is dispersed with antibiotic property nanometer copper particle and carries the Mg of controlled degradation function2Si, MgO nanometer reinforcing phase；Wherein, it receives
Rice copper particle and Mg2Si, MgO nanometer reinforcing phase one-step method fabricated in situ are simultaneously scattered in magnesium alloy abutment of implant.
Specifically, nanometer copper particle and Mg2Si, MgO nanometer reinforcing phase are by spherical magnesium alloy, nano cupric oxide and nanometer
Silica is generated by reaction in-situ, and the process of reaction in-situ is：
Mg+CuO → Cu+MgO,
2Mg+SiO2→ Si+2MgO,
2Mg+Si→Mg2Si。
The present invention is based on the functional requirement of magnesium alloy bone implant and space structure features, melt skill by selective laser
Art, using high energy laser beam and the strong reciprocation of composite material of magnesium alloy powder, in-situ preparation geometry is complex
Nanometer copper particle with high antibiotic property and corrosion proof Mg2The composite material of magnesium alloy of Si, MgO nano ceramics enhancing is planted
Enter body, is obviously improved the persistence of antibacterial during implant is on active service in human body.
Embodiment 1
(1) patient's lesion bone is scanned using medical high-precision CT machines, obtains bone implant threedimensional model；
(2) the medical Mg-Al-Zn alloys of dedicated spherical shape, nano oxidized copper powders and nanometer two are melted according to selective laser
The weight ratio 500 of silicon oxide powder:10:1 weighs, wherein and the grain size of spherical medical Mg-Al-Zn alloy powders is 10~60 μm,
Sphericity is not less than 90%, and purity is not less than 99.7%, and nano cupric oxide size is 10~50nm, and nano grade silica particles are big
Small is 30~100nm, and under high-purity argon gas and the mixed gas protected environment of high-purity carbon dioxide, ball milling is protected using cryogenic vacuum
Technique is that liquid nitrogen cools down temperature control, 5 DEG C of ball milling temperature, and vacuum degree is less than 0.1Pa, rotating speed 50rpm, often rotates forward 5~8min of ball milling,
Immediately stop 5min, then invert 5~8min of ball milling, Ball-milling Time 2h, to spherical magnesium alloy powder, nano oxidized copper powders with
Nano grade silica particles carry out ball milling mixing, the composite formed powder being uniformly mixed；
(3) the composite formed powder described in step (2) is put into the powder cylinder of selective laser melting unit, is being set
It is passed through the high-purity argon gas and high-purity carbon dioxide of certain flow in standby working chamber, sets laser beam energy density as 60J/m3, swash
Beam and focus size is 10 μm, and powder bed thickness is 20 μm, and oxygen content is less than 10ppm, melts shaped in situ tool by selective laser
There are the nanometer copper particle of high antibiotic property and corrosion proof Mg2Si, MgO nanometer reinforcing phase are scattered in the implantation of magnesium-based composite material bone
Body；
(4) high antibiotic property nano ceramics enhancing magnesium-based composite material bone implant made from step (3) is positioned over vacuum
It is less than 0.1Pa in vacuum degree in induction furnace, stress relief annealing temperature is 50 DEG C, and annealing time carries out destressing under the conditions of being 2h and moves back
Fire processing.
In-vitro antibacterial performance is carried out to the high antibiotic property controlled degradation magnesium-based composite material bone implant of the present embodiment forming
Experiment, selects staphylococcus aureus for subjects, according to QB/T2591-2003《Antibiotic plastic-Anti-microbial Performance Tests method
And antibacterial effect》The anti-microbial property of artificial bone implant is detected, the results show that after experiment for 24 hours, titanium alloy hip joint is to golden yellow
Staphylococcic bacteriostasis rate reaches 99.1%, and bacteriostasis rate still reaches 98.9% after experiment 72h days, has good durable antibiotic
Performance.
Embodiment 2
High antibiotic property controlled degradation magnesium-based composite material bone implant is prepared with reference to the manufacturing process of embodiment 1, difference exists
In：Ball milling temperature is set as 10 DEG C, rotating speed is by the magnesium alloy used in the present embodiment step (2) for Mg-Nd-Zn-Zr
100rpm；Set the energy density in step (3) to 180J/m3, laser beam spot size is 30 μm, and powder bed thickness is adjusted to
40μm；Stress relief annealing temperature in step (4) is set as 125 DEG C, annealing time 6.5h.
In-vitro antibacterial performance is carried out to the high antibiotic property controlled degradation magnesium-based composite material bone implant of the present embodiment forming
Experiment, selects staphylococcus aureus for subjects, according to QB/T2591-2003《Antibiotic plastic-Anti-microbial Performance Tests method
And antibacterial effect》The anti-microbial property of artificial bone implant is detected, the results show that after experiment for 24 hours, titanium alloy hip joint is to golden yellow
Staphylococcic bacteriostasis rate reaches 99.4%, and bacteriostasis rate still reaches 99.1% after experiment 72h days, has good durable antibiotic
Performance.
Embodiment 3
High antibiotic property controlled degradation magnesium-based composite material bone implant is prepared with reference to the manufacturing process of embodiment 2, difference exists
In：For the magnesium alloy used in the present embodiment step (2) for Mg-Zn-Mn, the dedicated medical Mg-Zn-Mn of spherical shape is melted in selective laser
The weight ratio of alloy, nano oxidized copper powders and nano grade silica particles is 500:5:5；By the energy density in step (3)
It is set as 140J/m3；Stress relief annealing temperature in step (4) is set as 150 DEG C.
In-vitro antibacterial performance is carried out to the high antibiotic property controlled degradation magnesium-based composite material bone implant of the present embodiment forming
Experiment, selects staphylococcus aureus for subjects, according to QB/T2591-2003《Antibiotic plastic-Anti-microbial Performance Tests method
And antibacterial effect》The anti-microbial property of artificial bone implant is detected, the results show that after experiment for 24 hours, titanium alloy hip joint is to golden yellow
Staphylococcic bacteriostasis rate reaches 98.3%, and bacteriostasis rate still reaches 98% after experiment 72h days, has good durable antibiotic
Energy.
Embodiment 4
High antibiotic property controlled degradation magnesium-based composite material bone implant is prepared with reference to the manufacturing process of embodiment 3, difference exists
In：Ball milling temperature is set as 20 DEG C, rotating speed 150rpm by the magnesium alloy used in the present embodiment step (2) for Mg-Ca；It will
Energy density in step (3) is set as 180J/m3, laser beam spot size is 50 μm, and powder bed thickness is adjusted to 50 μm；It will step
Suddenly the stress relief annealing temperature in (4) is set as 50 DEG C, annealing time 3.5h.
In-vitro antibacterial performance is carried out to the high antibiotic property controlled degradation magnesium-based composite material bone implant of the present embodiment forming
Experiment, selects staphylococcus aureus for subjects, according to QB/T2591-2003《Antibiotic plastic-Anti-microbial Performance Tests method
And antibacterial effect》The anti-microbial property of artificial bone implant is detected, the results show that after experiment for 24 hours, titanium alloy hip joint is to golden yellow
Staphylococcic bacteriostasis rate reaches 98.6%, and bacteriostasis rate still reaches 98.4% after experiment 72h days, has good durable antibiotic
Performance.
Embodiment 5
High antibiotic property controlled degradation magnesium-based composite material bone implant is prepared with reference to the manufacturing process of embodiment 4, difference exists
In：For the magnesium alloy used in the present embodiment step (2) for Mg-Al-Zn, the dedicated medical Mg-Al-Zn of spherical shape is melted in selective laser
The weight ratio of alloy, nano oxidized copper powders and nano grade silica particles is 500:1:10；By the energy density in step (3)
It is set as 140J/m3；Stress relief annealing temperature in step (4) is set as 75 DEG C, annealing time 6.5h.
In-vitro antibacterial performance is carried out to the high antibiotic property controlled degradation magnesium-based composite material bone implant of the present embodiment forming
Experiment, selects staphylococcus aureus for subjects, according to QB/T2591-2003《Antibiotic plastic-Anti-microbial Performance Tests method
And antibacterial effect》The anti-microbial property of artificial bone implant is detected, the results show that after experiment for 24 hours, titanium alloy hip joint is to golden yellow
Staphylococcic bacteriostasis rate reaches 97.7%, and bacteriostasis rate still reaches 97.5% after experiment 72h days, has good durable antibiotic
Performance.
Embodiment 6
High antibiotic property controlled degradation magnesium-based composite material bone implant is prepared with reference to the manufacturing process of embodiment 5, difference exists
In：Ball milling temperature is set as 15 DEG C, rotating speed 50rpm, ball milling by the magnesium alloy used in the present embodiment step (2) for Mg-Ca
Time is 3h；Set the energy density in step (3) to 210J/m3, laser beam spot size is 70 μm, and powder bed thickness is 30
μm；Stress relief annealing temperature in step (4) is set as 125 DEG C, annealing time 2h.
In-vitro antibacterial performance is carried out to the high antibiotic property controlled degradation magnesium-based composite material bone implant of the present embodiment forming
Experiment, selects staphylococcus aureus for subjects, according to QB/T2591-2003《Antibiotic plastic-Anti-microbial Performance Tests method
And antibacterial effect》The anti-microbial property of artificial bone implant is detected, the results show that after experiment for 24 hours, titanium alloy hip joint is to golden yellow
Staphylococcic bacteriostasis rate reaches 97.4%, and bacteriostasis rate still reaches 97.2% after experiment 72h days, has good durable antibiotic
Performance.
Embodiment 7
High antibiotic property controlled degradation magnesium-based composite material bone implant is prepared with reference to the manufacturing process of embodiment 6, difference exists
In：For the magnesium alloy used in the present embodiment step (2) for Mg-Nd-Zn-Zr, the dedicated medical Mg- of spherical shape is melted in selective laser
The weight ratio of Nd-Zn-Zr alloys, nano oxidized copper powders and nano grade silica particles is 500:6:3；It will be in step (3)
Energy density is set as 100J/m3, powder bed thickness is 50 μm；Stress relief annealing temperature in step (4) is set as 100 DEG C.
In-vitro antibacterial performance is carried out to the high antibiotic property controlled degradation magnesium-based composite material bone implant of the present embodiment forming
Experiment, selects staphylococcus aureus for subjects, according to QB/T2591-2003《Antibiotic plastic-Anti-microbial Performance Tests method
And antibacterial effect》The anti-microbial property of artificial bone implant is detected, the results show that after experiment for 24 hours, titanium alloy hip joint is to golden yellow
Staphylococcic bacteriostasis rate reaches 98.8%, and bacteriostasis rate still reaches 98.5% after experiment 72h days, has good durable antibiotic
Performance.
Embodiment 8
High antibiotic property controlled degradation magnesium-based composite material bone implant is prepared with reference to the manufacturing process of embodiment 7, difference exists
In：For the magnesium alloy used in the present embodiment step (2) for Mg-Zn-Mn, the dedicated medical Mg-Zn-Mn of spherical shape is melted in selective laser
The weight ratio of alloy, nano oxidized copper powders and nano grade silica particles is 500:4:7；By the energy density in step (3)
It is set as 60J/m3；Stress relief annealing temperature in step (4) is set as 125 DEG C, annealing time 5h.
In-vitro antibacterial performance is carried out to the high antibiotic property controlled degradation magnesium-based composite material bone implant of the present embodiment forming
Experiment, selects staphylococcus aureus for subjects, according to QB/T2591-2003《Antibiotic plastic-Anti-microbial Performance Tests method
And antibacterial effect》The anti-microbial property of artificial bone implant is detected, the results show that after experiment for 24 hours, titanium alloy hip joint is to golden yellow
Staphylococcic bacteriostasis rate reaches 98%, and bacteriostasis rate still reaches 97.8% after experiment 72h days, has good durable antibiotic
Energy.
Fig. 1 be in Examples 1 to 8 the high antibiotic property controlled degradation magnesium-based composite material bone implant that manufactures in human body simulation
Liberation of hydrogen volume in body fluid, reflects the degradation rate of implant.Implant was degraded in human body simulation body fluid through 28 days, maximum
Liberation of hydrogen volume is only 4.75mL, less than the degradation rate (liberation of hydrogen of degradation 15 days for the magnesium alloy implant being modified through conventional surface
Volume is 9.1mL), degradation rate is significantly improved, it is seen then that according to the high antibiotic property shaped under the differing formed technique of the present invention
The magnesium-based composite material bone implant of controlled degradation all has higher comprehensive military service performance.Meanwhile the embodiment of the present invention is made
Magnesium alloy bone implant degraded through 28 days in human body simulation body fluid, degradation rate changes greatly that (maximum liberation of hydrogen volume is
4.75mL, minimum liberation of hydrogen volume are 0.52mL), the controllable precise for realizing degradation rate is visible.
Claims (10)
1. a kind of high antibiotic property controlled degradation magnesium-based composite material bone implant, which is characterized in that including magnesium alloy implant base
Body, the intrinsic silicon are dispersed with the antibiotic property nanometer copper particle of fabricated in situ and carry the Mg of controlled degradation function2Si, MgO receive
Rice reinforced phase.
2. high antibiotic property controlled degradation magnesium-based composite material bone implant according to claim 1, which is characterized in that described
Nanometer copper particle and Mg2Si, MgO nanometer reinforcing phase pass through original position by spherical magnesium alloy, nano cupric oxide and nano silicon dioxide
Reaction generates, wherein the mass ratio of the spherical shape magnesium alloy, nano cupric oxide and nano silicon dioxide is 500:10:1~500:
1:10。
3. high antibiotic property controlled degradation magnesium-based composite material bone implant according to claim 2, which is characterized in that described
Spherical magnesium alloy is medical Mg-Al-Zn alloys, Mg-Zn-Mn alloys, Mg-Ca alloys or Mg-Nd-Zn-Zr alloys.
4. a kind of manufacturing process of high antibiotic property controlled degradation magnesium-based composite material bone implant described in claim 1, special
Sign is, includes the following steps：
(1) bone implant threedimensional model is obtained；
(2) spherical magnesium alloy powder, nano oxidized copper powders and nano grade silica particles are weighed, in high-purity argon gas and high-purity two
Ball milling mixing is uniform under carbon dioxide gas mixture environmental protection, obtains composite formed powder；
(3) under high-purity argon gas and high-purity carbon dioxide mixed atmosphere, melting forming technology by selective laser will be described compound
Material forming powder shaped in situ nanometer copper particle and Mg2Si, MgO nanometer reinforcing phase are scattered in the implantation of magnesium-based composite material bone
Body；
(4) bone implant obtained by step (3) is subjected to vacuum stress relief annealing process.
5. the manufacturing process of high antibiotic property controlled degradation magnesium-based composite material bone implant according to claim 4, special
Sign is, in step (2), carries out ball milling mixing using cryogenic vacuum protection ball-milling technology, process conditions are：It is cold using liquid nitrogen
But temperature control, 0~25 DEG C of ball milling temperature, vacuum degree are less than 0.1Pa, and rotating speed is 50~150rpm, often rotates forward 5~8min of ball milling, tightly
It connects and stops 5min, then invert 5~8min of ball milling, Ball-milling Time is 2~4h.
6. the manufacturing process of high antibiotic property controlled degradation magnesium-based composite material bone implant according to claim 4, special
Sign is, in step (2), it is described spherical shape magnesium alloy powder, nano oxidized copper powders and nano grade silica particles mass ratio
It is 500:10:1~500:1:10.
7. the manufacturing process of high antibiotic property controlled degradation magnesium-based composite material bone implant according to claim 4, special
Sign is, in step (2), the grain size of the spherical shape magnesium alloy powder is 10~60 μm, and sphericity is not less than 90%, and purity is not low
In 99.7.
8. the manufacturing process of high antibiotic property controlled degradation magnesium-based composite material bone implant according to claim 4, special
Sign is, in step (2), the size of the nano cupric oxide is 10~50nm, the size of nano silicon dioxide is 30~
100nm。
9. the manufacturing process of high antibiotic property controlled degradation magnesium-based composite material bone implant according to claim 4, special
Sign is, in step (3), the selective laser fusing forming process conditions are：Laser beam energy density is 60~210J/m3,
Laser beam spot size is 10~70 μm, and powder bed thickness is 20~50 μm, and oxygen content is less than 10ppm.
10. the manufacturing process of antibiotic property controlled degradation magnesium-based composite material bone implant according to claim 4, feature
It is, in step (4), the vacuum stress relief annealing process process conditions are：Vacuum degree is less than 0.1Pa, stress relief annealing temperature
Degree is 50~150 DEG C, and annealing time is 2~8h.
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| US20220344096A1 (en) * | 2021-04-22 | 2022-10-27 | China Jiliang University | Method for preparing high-performance anisotropic rare-earth-free permanent magnets |
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