CN108543109A - It is low to grind dual antibacterial titanium-based nano composite material bone implant and its manufacturing process - Google Patents

It is low to grind dual antibacterial titanium-based nano composite material bone implant and its manufacturing process Download PDF

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Publication number
CN108543109A
CN108543109A CN201810203105.5A CN201810203105A CN108543109A CN 108543109 A CN108543109 A CN 108543109A CN 201810203105 A CN201810203105 A CN 201810203105A CN 108543109 A CN108543109 A CN 108543109A
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titanium
bone implant
composite material
titanium alloy
nano composite
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CN108543109B (en
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夏木建
李年莲
林岳宾
刘爱辉
丁红燕
陈中
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Huaiyin Institute of Technology
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    • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/02—Inorganic materials
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    • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/02—Inorganic materials
    • A61L27/04—Metals or alloys
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    • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
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    • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/50—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
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    • B22F5/00—Manufacture of workpieces or articles from metallic powder characterised by the special shape of the product
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y10/00—Processes of additive manufacturing
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    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C32/00—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ
    • C22C32/001—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ with only oxides
    • C22C32/0015—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ with only oxides with only single oxides as main non-metallic constituents
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    • A61L2300/00—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
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    • A61L2300/00—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
    • A61L2300/10—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices containing or releasing inorganic materials
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    • A61L2300/00—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
    • A61L2300/40—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices characterised by a specific therapeutic activity or mode of action
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    • A61L2430/00—Materials or treatment for tissue regeneration
    • A61L2430/02—Materials or treatment for tissue regeneration for reconstruction of bones; weight-bearing implants
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Abstract

The present invention discloses the dual antibacterial titanium-based nano composite material bone implant of the low mill of one kind and its manufacturing process, which, which is generated in-situ biphase antibiotic nano silver and titanium dioxide ceramic, enhances titanium alloy bone implant；The titanium-based nano composite material bone implant possesses excellent durable antibiotic function and wear-resisting property.Its manufacturing process is：(1) bone implant threedimensional model is obtained；(2) dry after then being mixed with Medical spherical titanium alloy powder wet ball-milling to micron silver oxide particle vacuum drying treatment, obtain dry micrometers silver oxide titanium alloy composite material powder；(3) under high-purity argon gas protection; it is scattered in titanium alloy bone implant by laser gain material manufacturing process shaped in situ nano silver particles and silica, realizes the labyrinth of high-performance titanium based nano composite material bone implant, the integrated precision manufactureing of nanocomposite and dual antibacterial functions.

Description

It is low to grind dual antibacterial titanium-based nano composite material bone implant and its manufacturing process
Technical field
The present invention relates to a kind of composite material bone implant and manufacturing process, more particularly to a kind of low dual antibacterial titanium-based of mill Nanocomposite bone implant and its manufacturing process.
Background technology
Titanium or titanium alloy is widely used in surgical implant neck because of its good biocompatibility and biomechanical property Domain, the novel low modulus beta titanium alloy especially researched and developed in recent years, the Ti- developed such as Smith＆Nephew Riehards companies 13Nb-13Zr alloys, are added to non-toxic element nb and Zr, and elasticity modulus is close with people's bone.Although titanium alloy is in artificial bone Implant field have significant advantage, but there are still activity it is low, safety is insufficient the problems such as.Especially titanium alloy belongs to inertia Material, itself although using sterile working in implantation process, and coordinates antibiotic usage, because of titanium alloy pair without antibiotic property Bacterial adhesion is more sensitive, is vulnerable to bacterium infection and influences the combination of itself and bone tissue.
Currently, one is to deposit antimicrobial coating in titanium alloy implant surfaces to improve implant by surface modifying method Antibacterial ability；Second is that shaping titanium-copper antimicrobial form implant by using hot pressed sintering or laser 3D printing method.These measures one Determine to improve the antibacterial effect of titanium alloy bone implant in degree, but there is also following deficiencies：(1) antimicrobial coating with it is titanium alloy-based Body bond strength is limited, during bone implant is on active service under the conditions of human body complex physiologic, often with surrounding it is soft/sclerous tissues occur phase The hip joint of interaction, especially high-mechanic often interacts stress with knee joint with people's bone generation, and it is easy to easily lead to antimicrobial coating Failure, and then deteriorate conditions of patients；(2) by " the antibacterial copper Cu of Environmental Protection Agency's certification+" it is partial to bacteriostasis property, in antibacterial side Face effect is undesirable.
On the other hand, titanium alloy bone implant because its wearability deficiency, in human body be on active service during corrosive wear because Element leads to the dissolution of harmful metal elements in vivo in metal material, and then causes the allergy and inflammation of metal implant surrounding tissue Disease reaction, local necrosis even canceration.Currently, mainstream mainly has to the approach for improving titanium alloy bone implant wearability：Base In material surface modifying technology high-wearing feature ceramic membrane is obtained in titanium alloy surface；Followed by burnt by vacuum pressing and casting, powder Ceramics enhancing titanium matrix composite prepared by the techniques such as knot is to improve its wearability.It is tested through range of clinical, there are one for measure Fixed deficiency, is in particular in：(1) because ceramic membrane hardness itself is high, brittleness is big, it can be obviously improved the wearability of titanium alloy, but Because of ceramics and the physical property mismatch of titanium alloy substrate, it is weak with substrate combinating strength to often result in ceramic membrane, at the same during military service Under shock loading or point contact stress, ceramic membrane easily cracks, or even cracking, eventually leads to failure；(2) for pottery Porcelain enhance titanium matrix composite, because ceramics with titanium alloy substrate physical difference, cause its boundary moisture performance poor, with people's bone In friction process, ceramic particle is detached from titanium alloy substrate under the force effect that rubs, and easy infection implant surrounding tissue is ground in corrosion It damages in environment, infection phenomenons are especially apparent.
Invention content
Goal of the invention：The present invention for existing titanium-based bone implant there are the problem of, a kind of low dual antibacterial of mill is provided Titanium-based nano composite material bone implant, and provide a kind of manufacturing process of the titanium matrix composite bone implant.
Technical solution：The low dual antibacterial titanium-based nano composite material bone implant of mill of the present invention, is in-situ preparation Biphase antibiotic nano silver and titanium dioxide ceramic enhance titanium alloy bone implant.
Preferably, nano silver particles and nano-titanium dioxide ceramics by titanium alloy powder and micron silver oxide particle in high energy The lower reaction in-situ of laser beam effect obtains, and reaction in-situ process is：2Ag2O+Ti→TiO2+4Ag；Wherein, micron silver oxide particle Quality account for its 1~10% with titanium alloy powder gross mass.
The manufacturing process of the low dual antibacterial titanium-based nano composite material bone implant of mill of the present invention, including following steps Suddenly：
(1) bone implant threedimensional model is obtained, and hierarchy slicing processing is carried out to the threedimensional model；
(2) to micron silver oxide particle vacuum drying treatment, by the micron silver oxide particle and titanium alloy powder after drying Dry, the dry micrometers silver oxide-titanium alloy composite material powder being uniformly mixed after wet ball-milling mixing；
(3) by laser gain material manufacturing process that dry micrometers silver oxide-titanium alloy is multiple under high-purity argon gas protective atmosphere Condensation material powder shaped in situ nano silver particles are scattered in nano silicon dioxide ceramics in titanium alloy bone implant, obtain low mill Dual antibacterial titanium-based nano composite material bone implant.
In above-mentioned steps (2), vacuum drying treatment process conditions are preferably：Vacuum drying temperature is 60~80 DEG C, dry Time is 5~10h.
In shaping raw material, the quality of preferably dry micrometers silver oxide particle account for its 1 with titanium alloy powder gross mass~ 10%.Wherein, titanium alloy powder is Medical spherical titanium alloy powder, can be that medical pure titanium, Ti-Nb-Zr alloys or Ti-Ta are closed Gold.Further, the grain size of titanium alloy powder is 10~60 μm, purity 99.5%；Micron silver oxide particle average grain diameter be 15~40 μm, purity 99.9%.
Preferably, in step (2), dry micron silver oxide particle and titanium alloy powder are put into ball grinder, utilized High-energy-milling carries out wet ball-milling mixing, and high-energy-milling condition is：Revolution rotating speed is 100~250rpm, ball grinder Rotation rotating speed is 200~500rpm.
In above-mentioned steps (3), dry micrometers silver oxide-titanium alloy composite material powder can be positioned over to laser gain material manufacture In the filler bin of equipment, opens mechanical pump and shaped cavity is vacuumized, when pressure is less than 0.05Pa in cavity, to cavity It is inside passed through high-purity argon gas, sets laser gain material fabrication process condition, the low dual antibacterial titanium-based nano composite material of mill of precision form Bone implant.
Preferably, laser gain material fabrication process condition is：High energy laser beam physical efficiency metric density is 30~150J/m3, use Fault orthogonal scanning strategy.
Inventive principle：The present invention is based on excellent anti-of the thermodynamic behaviour of titanium and silver oxide reaction in-situ and nano silver particles Bacterium function generates receiving for biphase antibiotic using laser gain material manufacturing technology by reaction in-situ 2Ag2O+Ti → TiO2+4Ag Metrical scale silver and nano-titania particle, greatly strengthen the anti-microbial property of titanium alloy bone implant；Moreover, being based on nano silver It, can be real by changing laser gain material fabrication process parameters with the dependence of the antibacterial ability and its scale of TiO 2 particles The controllable growth of existing in-situ nano particle, and then realize the regulation and control to antibacterial functions；In addition, the physical property based on silver oxide low melting point Feature, the silver oxide of micro-meter scale be completely melt under high energy laser beam effect, the nanometer titanium dioxide generated with titanium reaction in-situ Titanium ceramics have good interface bond strength with titanium alloy substrate, are scattered in titanium alloy substrate, enhance titanium alloy plant Enter body Human Physiology condition wear-resisting property.
Advantageous effect：Compared with prior art, the beneficial effects of the present invention are：(1) titanium-based nano of the invention is compound The nanometer-level silver and TiO 2 particles of the biphase antibiotic of fabricated in situ are dispersed in material bone implant, relative to single antibacterial For Type Titanium Alloy bone implant, possesses excellent durable antibiotic function, extend the service life of implant；(2) this hair Bright generated in-situ nano-titanium dioxide ceramics are scattered in titanium alloy bone implant, can further promote titanium alloy bone implant Intensity, reduce corrosive wear rate, titanium alloy bone implant military service have excellent performance, have good market prospects；(3) of the invention Using advanced laser gain material manufacturing process, realizes the labyrinth of high-performance titanium based nano composite material bone implant, receives The integrated precision manufactureing of nano composite material and dual antibacterial functions, the manufacturing process is simple for process, is not necessarily to follow-up complicated technology, Manufacture efficiency is substantially improved, the economic cost that Alternative is brought is avoided to be invaded with extraneous bacterium；In addition, by changing laser gain material Fabrication process parameters can realize the controllable growth of in-situ nano particle, and then realize the regulation and control to antibacterial functions.
Description of the drawings
Fig. 1 is the micro-organization chart for the dual antibacterial titanium-based nano composite material bone implant of low mill that embodiment 1 shapes；
Fig. 2 is the dual antibacterial titanium-based nano composite material bone implant of low mill of the forming of embodiment 2 in simulated body fluid Friction coefficient；
Fig. 3 is the dual antibacterial titanium-based nano composite material bone implant of low mill of Examples 1 to 6 forming in simulated body fluid Wear rate figure.
Specific implementation mode
Technical scheme of the present invention is described further below in conjunction with the accompanying drawings.
The present invention the dual antibacterial titanium-based nano composite material bone implant of low mill be titanium alloy bone implant, inside contain There are nano silver and titanium dioxide two-phase particle with anti-microbial property；Wherein, nano silver particles and nano-titanium dioxide ceramics are logical The mode for crossing fabricated in situ is formed and is scattered in titanium alloy bone implant.
Nano silver particles and nano-titanium dioxide ceramics can be by titanium alloy powders and micron silver oxide particle in superlaser Reaction in-situ obtains under Shu Zuoyong, and reaction in-situ process is：2Ag2O+Ti→TiO2+4Ag；In raw material, micron silver oxide particle Quality accounts for its 1~10% with titanium alloy powder gross mass.
The thermodynamics and dynamics condition generated based on nanoscale silver and titanium dioxide biphase antibiotic particles in-situ (2Ag2O+Ti→TiO2+ 4Ag), according to titanium alloy artificial bone implant, the military services function such as low abrasion, high antibiotic property needs in human body It asks and the manufacture requirement of bone implant precision form, the present invention realizes high-performance titanium-based by means of laser gain material manufacturing technology The labyrinth of nanocomposite bone implant, the integrated precision manufactureing of nanocomposite and dual antibacterial functions.
Embodiment 1
(1) skeleton model that patient's lesion is scanned by CT scan machine, obtains space three-dimensional model, Defect point is carried out using topological optimization software to be repaired, and generates complete bone implant model, and layering is carried out to model and is cut Piece processing；
(2) micron silver oxide particle is implanted into vacuum drying oven, sets drying temperature as 70 DEG C, drying time 5h, Remove the moisture of particle surface absorption；
(3) dry micron silver oxide particle and Medical spherical titanium alloy powder are divided by the quality of micron silver oxide particle Number accounting is positioned over after being weighed for 1% in ball grinder, wherein silver oxide average grain diameter is 15 μm, purity 99.9%, spherical titanium Alloy is medical pure titanium, and grain size is 10~60 μm, purity 99.5%, and is added into ball grinder and is no less than the anhydrous second of 200ml Alcohol, using high-energy-milling to dry after the progress wet ball-milling mixing of weighed powder, revolution rotating speed is 200rpm, ball milling Tank rotation rotating speed is 400rpm, the dry micrometers silver oxide-titanium alloy composite material powder being uniformly mixed；
(4) dry micrometers silver oxide-titanium alloy composite material powder is positioned over to the filler bin of laser gain material manufacturing equipment In, it opens mechanical pump and shaped cavity is vacuumized, when pressure is passed through high-purity argon into cavity less than 0.05Pa in cavity Gas sets high energy laser beam physical efficiency metric density as 30J/m3, using fault orthogonal scanning strategy, the low mill of precision form, nano silver With the dual antibacterial titanium-based nano composite material bone implant of titanium dioxide.
Microscopic structure such as Fig. 1 of the dual antibacterial titanium-based nano composite material bone implant of low mill of this implementation forming, can be with See, the nano silver particles with antibacterial functions and nanometer titanium dioxide carbon ceramics of forming are scattered in titanium alloy bone implant in situ In, and nano-titania particle and titanium alloy-based body interface no significant defect, interface cohesion are good.
Anti-microbial Performance Tests are carried out to the dual antibacterial titanium-based nano composite material bone implant of low mill of the present embodiment forming, Select staphylococcus aureus for subjects, according to QB/T2591-2003《Antibiotic plastic-Anti-microbial Performance Tests method and anti- Bacterium effect》The anti-microbial property of artificial hip joint is detected, the results show that after experiment for 24 hours, titanium alloy hip joint is to Staphylococcus aureus The bacteriostasis rate of bacterium reaches 99.8%, and bacteriostasis rate still reaches 99.6% after testing 96h, has good durable antibiotic performance.
Embodiment 2
The low dual antibacterial titanium-based nano composite material bone implant of mill is prepared with reference to the manufacturing process of embodiment 1, difference exists In：For the titanium alloy used in the present embodiment step (3) for Ti-Ta alloys, silver oxide average grain diameter is 40 μm；It is high in step (4) Energy laser beam body energy density is 150J/m3。
Anti-microbial Performance Tests are carried out to the dual antibacterial titanium-based nano composite material bone implant of low mill of the present embodiment forming, Select staphylococcus aureus for subjects, according to QB/T2591-2003《Antibiotic plastic-Anti-microbial Performance Tests method and anti- Bacterium effect》The anti-microbial property of artificial hip joint is detected, the results show that after experiment for 24 hours, titanium alloy hip joint is to Staphylococcus aureus The bacteriostasis rate of bacterium reaches 99.5%, and bacteriostasis rate still reaches 99.4% after testing 96h, has good durable antibiotic performance.
Wear resistance test is carried out to the dual antibacterial titanium-based nano composite material bone implant of low mill of the present embodiment forming, Such as Fig. 2, it can be seen that friction coefficient of the dual antibacterial titanium-based nano composite material bone implant of low mill in simulated body fluid be only 0.05, and friction coefficient shows that friction process is more steady without fluctuating.
Embodiment 3
The low dual antibacterial titanium-based nano composite material bone implant of mill is prepared with reference to the manufacturing process of embodiment 2, difference exists In：The mass fraction accounting of micron silver oxide is 5% in the present embodiment step (3), and silver oxide average grain diameter is 15 μm, use Titanium alloy is Ti-Nb-Zr alloys.
Anti-microbial Performance Tests are carried out to the dual antibacterial titanium-based nano composite material bone implant of low mill of the present embodiment forming, Select staphylococcus aureus for subjects, according to QB/T2591-2003《Antibiotic plastic-Anti-microbial Performance Tests method and anti- Bacterium effect》The anti-microbial property of artificial hip joint is detected, the results show that after experiment for 24 hours, titanium alloy hip joint is to Staphylococcus aureus The bacteriostasis rate of bacterium reaches 99.9%, and bacteriostasis rate still reaches 99.8% after testing 96h, has good durable antibiotic performance.
Embodiment 4
The low dual antibacterial titanium-based nano composite material bone implant of mill is prepared with reference to the manufacturing process of embodiment 3, difference exists In：For the titanium alloy used in the present embodiment step (3) for medical pure titanium, silver oxide average grain diameter is 40 μm；High energy in step (4) Laser beam body energy density is 90J/m3。
Anti-microbial Performance Tests are carried out to the dual antibacterial titanium-based nano composite material bone implant of low mill of the present embodiment forming, Select staphylococcus aureus for subjects, according to QB/T2591-2003《Antibiotic plastic-Anti-microbial Performance Tests method and anti- Bacterium effect》The anti-microbial property of artificial hip joint is detected, the results show that after experiment for 24 hours, titanium alloy hip joint is to Staphylococcus aureus The bacteriostasis rate of bacterium reaches 99.9%, and bacteriostasis rate still reaches 99.7% after testing 96h, has good durable antibiotic performance.
Embodiment 5
The low dual antibacterial titanium-based nano composite material bone implant of mill is prepared with reference to the manufacturing process of embodiment 4, difference exists In：The titanium alloy used in the present embodiment step (3) is Ti-Ta alloy, and silver oxide average grain diameter is 15 μm, micron silver oxide Mass fraction accounting is 10%.
Anti-microbial Performance Tests are carried out to the dual antibacterial titanium-based nano composite material bone implant of low mill of the present embodiment forming, Select staphylococcus aureus for subjects, according to QB/T2591-2003《Antibiotic plastic-Anti-microbial Performance Tests method and anti- Bacterium effect》The anti-microbial property of artificial hip joint is detected, the results show that after experiment for 24 hours, titanium alloy hip joint is to Staphylococcus aureus The bacteriostasis rate of bacterium reaches 99.9%, and bacteriostasis rate still reaches 99.8% after testing 96h, has good durable antibiotic performance.
Embodiment 6
The low dual antibacterial titanium-based nano composite material bone implant of mill is prepared with reference to the manufacturing process of embodiment 5, difference exists In：For the titanium alloy used in the present embodiment step (3) for Ti-Nb-Zr alloys, silver oxide average grain diameter is 40 μm；In step (4) High energy laser beam physical efficiency metric density is 120J/m3。
Anti-microbial Performance Tests are carried out to the dual antibacterial titanium-based nano composite material bone implant of low mill of the present embodiment forming, Select staphylococcus aureus for subjects, according to QB/T2591-2003《Antibiotic plastic-Anti-microbial Performance Tests method and anti- Bacterium effect》The anti-microbial property of artificial hip joint is detected, the results show that after experiment for 24 hours, titanium alloy hip joint is to Staphylococcus aureus The bacteriostasis rate of bacterium reaches 99.7%, and bacteriostasis rate still reaches 99.4% after testing 96h, has good durable antibiotic performance.
The dual antibacterial titanium-based nano composite material bone implant of low mill of Examples 1 to 6 forming is with staphylococcus aureus Carried out for 24 hours and 96h antibacterial experiments for subjects, the results showed that, for 24 hours after suppression of the titanium alloy hip joint to staphylococcus aureus Bacterium rate is above 99.5%, while titanium alloy hip joint is above 99.4% to the bacteriostasis rate of staphylococcus aureus after 96h, can See, the low dual antibacterial titanium-based nano composite material bone implant of mill produced by the present invention has excellent antibiotic rate and antibacterial lasting Property.
The dual antibacterial titanium-based nano composite material bone implant of low mill of Examples 1 to 6 forming is resistance in simulated body fluid Grind performance such as Fig. 3, it can be seen that the dual antibacterial titanium-based nano composite material bone implant abrasion of low mill of above-described embodiment forming Rate is below 4.5 × 10-5mm3/N·m；As it can be seen that the dual antibacterial titanium-based nano of low mill shaped under the differing formed technique of the present invention Composite material bone implant not only possesses good Durability of antimicrobial effect, and possesses good anti-corrosion wear performance, above-mentioned performance Test result illustrates that the low dual antibacterial titanium-based nano composite material bone implant of mill provided by the invention has excellent comprehensive clothes Use as a servant performance.

Claims (10)

1. a kind of low dual antibacterial titanium-based nano composite material bone implant of mill, which is characterized in that the titanium-based nano composite material Bone implant, which is generated in-situ biphase antibiotic nano silver and titanium dioxide ceramic, enhances titanium alloy bone implant.
2. the low dual antibacterial titanium-based nano composite material bone implant of mill according to claim 1, which is characterized in that described Nano silver particles and nano-titanium dioxide ceramics are former under high energy laser beam effect by titanium alloy powder and micron silver oxide particle Position reaction obtains, wherein the quality of micron silver oxide particle accounts for its 1~10% with titanium alloy powder gross mass.
3. a kind of manufacturing process of the low dual antibacterial titanium-based nano composite material bone implant of mill described in claim 1, special Sign is, includes the following steps：
(1) bone implant threedimensional model is obtained, and reparation and hierarchy slicing processing are carried out to the threedimensional model；
(2) to micron silver oxide particle vacuum drying treatment, by the micron silver oxide particle and titanium alloy powder wet type after drying It is dry after ball milling mixing, the dry micrometers silver oxide-titanium alloy composite material powder being uniformly mixed；
(3) under high-purity argon gas protective atmosphere, by laser gain material manufacturing process by dry micrometers silver oxide-titanium alloy composite wood Feed powder end shaped in situ nano silver particles are scattered in nano silicon dioxide ceramics in titanium alloy bone implant, and it is dual to obtain low mill Antibacterial titanium-based nano composite material bone implant.
4. the manufacturing process of the low dual antibacterial titanium-based nano composite material bone implant of mill according to claim 3, special Sign is, in step (2), the vacuum drying treatment process conditions are：Vacuum drying temperature is 60~80 DEG C, and drying time is 5~10h.
5. the manufacturing process of the low dual antibacterial titanium-based nano composite material bone implant of mill according to claim 3, special Sign is, in step (2), the quality of the dry micrometers silver oxide particle accounts for its 1~10% with titanium alloy powder gross mass.
6. the manufacturing process of the low dual antibacterial titanium-based nano composite material bone implant of mill according to claim 3, special Sign is, in step (2), dry micron silver oxide particle and titanium alloy powder is put into ball grinder, high-energy ball milling is utilized Technique carries out wet ball-milling mixing, and the high-energy-milling condition is：Revolution rotating speed is 100~250rpm, ball grinder rotation Rotating speed is 200~500rpm.
7. the manufacturing process of the low dual antibacterial titanium-based nano composite material bone implant of mill according to claim 3, special Sign is, in step (2), the titanium alloy powder is Medical spherical titanium alloy powder, which is medical pure Titanium, Ti-Nb-Zr alloys or Ti-Ta alloys.
8. the manufacturing process of the low dual antibacterial titanium-based nano composite material bone implant of mill according to claim 3, special Sign is, in step (2), the grain size of the titanium alloy powder is 10~60 μm, purity 99.5%；The micron silver oxide Grain average grain diameter is 15~40 μm, purity 99.9%.
9. the manufacturing process of the low dual antibacterial titanium-based nano composite material bone implant of mill according to claim 3, special Sign is, in step (3), the dry micrometers silver oxide-titanium alloy composite material powder is positioned over laser gain material manufacture dress In standby filler bin, opens mechanical pump and shaped cavity is vacuumized, when pressure is less than 0.05Pa in cavity, into cavity It is passed through high-purity argon gas, sets laser gain material fabrication process condition, the low dual antibacterial titanium-based nano composite material bone of mill of precision form Implant.
10. the manufacturing process of the low dual antibacterial titanium-based nano composite material bone implant of mill according to claim 3, special Sign is, in step (3), the laser gain material fabrication process condition is：High energy laser beam physical efficiency metric density is 30~150J/ m3, using fault orthogonal scanning strategy.
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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110039041A (en) * 2019-04-22 2019-07-23 依波精品（深圳）有限公司 Anti-bacteria stainless steel composite granule, anti-bacteria stainless steel and preparation method thereof
CN111922340A (en) * 2020-06-30 2020-11-13 吉林大学 Method for preparing medical titanium alloy material by laser sintering
EP3757257A1 (en) 2019-06-25 2020-12-30 Politechnika Slaska The formation method of porous antibacterial coatings on titanium and titanium alloys surface
EP3816327A1 (en) 2019-06-25 2021-05-05 Politechnika Slaska The formation method of porous antibacterial coatings on titanium and titanium alloys surface

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1152775A1 (en) * 1999-02-26 2001-11-14 Advanced Cardiovascular Systems, Inc. Composite super elastic/shape memory alloy and malleable alloy stent
CN102758202A (en) * 2012-08-11 2012-10-31 西北有色金属研究院 Method for preparing biomedical titanium and titanium alloy surface antibacterial coatings
CN105435305A (en) * 2015-12-17 2016-03-30 西南交通大学 Porous titanium composite material and preparation method thereof
CN106745237A (en) * 2016-12-30 2017-05-31 尹宗杰 A kind of layer type casting moulding Graphene non-metallic metal composite and preparation method
CN107130138A (en) * 2017-05-19 2017-09-05 淮阴工学院 The method of medical high abrasion titanium alloy composite material and 3D printing gradient in-situ nano complex phase anti-attrition medical titanium alloy

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1152775A1 (en) * 1999-02-26 2001-11-14 Advanced Cardiovascular Systems, Inc. Composite super elastic/shape memory alloy and malleable alloy stent
CN102758202A (en) * 2012-08-11 2012-10-31 西北有色金属研究院 Method for preparing biomedical titanium and titanium alloy surface antibacterial coatings
CN105435305A (en) * 2015-12-17 2016-03-30 西南交通大学 Porous titanium composite material and preparation method thereof
CN106745237A (en) * 2016-12-30 2017-05-31 尹宗杰 A kind of layer type casting moulding Graphene non-metallic metal composite and preparation method
CN107130138A (en) * 2017-05-19 2017-09-05 淮阴工学院 The method of medical high abrasion titanium alloy composite material and 3D printing gradient in-situ nano complex phase anti-attrition medical titanium alloy

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110039041A (en) * 2019-04-22 2019-07-23 依波精品（深圳）有限公司 Anti-bacteria stainless steel composite granule, anti-bacteria stainless steel and preparation method thereof
EP3757257A1 (en) 2019-06-25 2020-12-30 Politechnika Slaska The formation method of porous antibacterial coatings on titanium and titanium alloys surface
EP3816327A1 (en) 2019-06-25 2021-05-05 Politechnika Slaska The formation method of porous antibacterial coatings on titanium and titanium alloys surface
CN111922340A (en) * 2020-06-30 2020-11-13 吉林大学 Method for preparing medical titanium alloy material by laser sintering

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