CN101518467A - Medicinal porous titanium implant and method for preparing same - Google Patents
Medicinal porous titanium implant and method for preparing same Download PDFInfo
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- CN101518467A CN101518467A CN200910042805A CN200910042805A CN101518467A CN 101518467 A CN101518467 A CN 101518467A CN 200910042805 A CN200910042805 A CN 200910042805A CN 200910042805 A CN200910042805 A CN 200910042805A CN 101518467 A CN101518467 A CN 101518467A
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Abstract
The invention discloses a medicinal porous titanium implant and a method for preparing the same. The porous titanium implant is prepared by a powder coinjection molding method; and a nano HA and TGF loaded sustained-release gelatin microsphere compound coating is deposited on the porous outer layer of the product. The outer layer of the implant has a communicated porous structure, the thickness of the porous layer is 0.4 to 1.1 millimeters, the porosity of the porous layer is 50 to 70 percent, and the aperture of the porous layer is 50 to 400 mum; the surface of the porous layer is deposited; and the binding strength of the outer layer and an inner core is 150 to 300MPa. Compared with the prior medicinal titanium implant material, the material of the medicinal porous titanium implant has higher mechanical strength, is in accordance with the mechanical performance of osseous tissue, avoids stress concentration and stress shielding, promotes stress transmission and growth of new bones, reduces time for osseointegration, and ensures the long-term stability of the implant. The method adopts once-for-all molding without post machining, thereby considerably reducing the cost.
Description
Technical field
The invention belongs to medical porous metal biological implantation material, relate in particular to the porous titanium implant material.
Background technology
Existing titanium implant adopts the machining process manufacturing usually, and operation is various, and processing capacity is big, and spillage of material is many, the cost height, and be full DB structure.Full dense form implantation body exists elastic modelling quantity and sclerotin on every side not to be complementary, and easily produces stress concentration and stress-shielding effect at implant and osseous tissue interface, influences the long-time stability of implantation body.In order to improve the stability of implantation body, existing bulky grain sandblast acid etching, anodic oxidation, surface carburization, plasma spraying titanium slurry or the hydroxyapatite methods such as (HA) of adopting are carried out surface treatment to implantation body more.Though these methods increase the roughness on surface or improve surface activity, promote the mechanical sealed of itself and surrounding bone tissue, but the structural condition that does not provide osseous tissue to grow into implantation body, osseous tissue can only with its surface combination, can not realize biological fixation fully, and the mechanical compatibility problem of unresolved implantation body and surrounding bone tissue; The bond strength of face coat and implantation body is low, in the implant operation process, implants shearing force and easily makes coating shedding, and clinical practice is limited.
In recent years discover that medical porous metal material can impel the area of new bone hole of growing into, promote tissue regeneration and reconstruction, accelerate agglutination, can realize and be replaced the mechanical property that sclerous tissues is complementary, and loose structure can provide support for bioactivity coatings, can avoid implanting the destruction of shearing force.Find that after deliberation the aperture is that 150~400 μ m and the porous material with higher porosity intercommunicating pore structure are suitable for growing into of osseous tissue, and is also higher with the bond strength of sclerotin.Must there be enough fatigue resistances and mechanical property in implantation body as load, muchly functionating.But the intensity of porous metals is not so good as corresponding dense metal, and along with the increase intensity decreases of porosity is obvious.
In order to solve the contradiction of high porosity and intensity, realize the preparation of the medical titanium implantation body of loose structure, the existing at present method that adopts plasma spraying method at dense substrate surface preparation porous coating, but the porosity of this method uncontrollable coating in technical process, aperture and open intercommunicating pore structure, and technological temperature is mostly up to more than 1000 ℃, the cooling back is in the residual stress of substrate and coating interface existence, influence coating and high base strength, therefore this implantation body still comes off in implantation process easily.
Powder metallurgy process as cold pressing+sintering, cold pressing+self propagating high temperature is synthetic, isostatic cool pressing+sintering+high temperature insostatic pressing (HIP) etc., though can prepare the porous metal material of Higher porosity and open communication pore structure, it generally all is whole high porosity materials, its mechanical property often can not satisfy the requirement of implant, and the difficult near-net-shape of realizing, all need following process to handle, and follow-up processing can destroy loose structure.
Titanium is a bio-inert material, and titanium implant lacks in the bone integration process that bone is induced, bone conduction and initiative, and the bone integrating time is longer, and the load healing stage generally needs for 3~June in clinical practice.Discover that both at home and abroad the method for surface-coated bioactivity coatings can improve the biological activity of titanium implant surface, help bone and integrate.The biochemistry modification is by specific albumen, enzyme or peptide being fixed in material surface, inducing special cells differentiation and tissue engineered, promptly controlling generation and the development that bone is integrated by biomolecule being introduced directly into the implantation body interface.For traditional physics and chemical method, the biochemistry modification is more direct effectively.
If prepare the suitable biochemistry modification of a kind of process, existing enough fatigue resistances, with the surrounding bone tissue higher mechanical compatibility and biological activity are arranged again, the medicinal porous titanium implant that the bone integrating time is short and stability is high, then significant to medical metal implantation body material field.
Summary of the invention
The object of the present invention is to provide a kind of nanometer hydroxyapatite (HA) and transforming growth factor (Transforming Growth Factor, TGF) medicinal porous titanium implant of sustained-release micro-spheres composite coating.
The preparation method that the present invention also aims to provide nanometer HA and carry growth factor slow-release microsphere composite coating porous titanium implant.
Porous titanium implant of the present invention comprises the outer and fine and close titanium structure inner core of loose structure, and inner core density is 95~97.5%; Skin is an intercommunicating pore structure, and porous layer thickness is 0.4~1.1mm, and its porosity is 50~70%, and the aperture is 50~400 μ m; Outer bond strength with inner core is 150~300MPa; Pore surface depositing nano HA and year TGF slow-release gelatin microspheres composite coating.
The preparation method of of the present invention layer porous titanium implant is: adopt powder altogether ejection forming method inner core feeding and outer feeding are taken up in order of priority injection moulding, the injection moulding base is sintering after the defat desalination, obtains goods; With the porous outer layer depositing nano HA of electrochemical deposition method at goods, adopt the biphase emulsification condensation polymerization preparation of improvement to carry the TGF slow-release gelatin microspheres, employing is oozed and is coated with technology nanometer HA surface deposition TGF sustained-release micro-spheres formation composite coating in the POROUS TITANIUM hole, obtains the composite coating porous titanium implant body.
The inner core feeding is to be raw material with the titanium valve, adopts oil-paraffin-polyolefin binder system to prepare.The binder system prescription is taking polyethylene glycol 10~40%, vegetable oil 5~20%, polyethylene 15~30%, plasticizer 1~10%, paraffin 15~54% by weight percentage; Binding agent and material powder 56~40: 54~62 mix homogeneously are by volume granulated, and get the inner core feeding.
Outer feeding is to be raw material with the titanium valve, and adding 30~60vol% sodium chloride in titanium valve is pore creating material, and the titantium hydride of 5~20wt% is foaming agent, adopts oil-paraffin-polyolefin binder system to prepare.The binder system prescription is for by weight percentage, taking polyethylene glycol 10~40%, vegetable oil 5~20%, polyethylene 15~30%, plasticizer 1~10%, paraffin 15~54%; Binding agent and material powder be by volume behind 56~40: 54~62 mix homogeneously, granulate outer feeding.
Inner core feeding and outer feeding are taken up in order of priority injection moulding, and described injection moulding process altogether is: 135 ℃~155 ℃ of injection temperatures, injection pressure 80Mpa~100MPa, injection speed 50~65%, under 30 ℃~60 ℃ conditions of mould temperature, be processed into blank, obtain injecting green compact.
Described shaping base defat desalination processes comprises: adopt two step defat methods that binding agent in the shaping base is removed, remove sodium chloride with immersion method then.Promptly at first adopt solvent degreasing, will inject green compact and put into water and be heated to 40 ℃~60 ℃, be detained 1~2h, then blank is put in the normal heptane, dissolving paraffin and vegetable oil component; Water-bath desalination again, with blank insert 60 ℃~70 ℃ go dried up in 4~8h, every 1h change once go dried up; After heat defat under argon gas atmosphere, is heated to 300 ℃ with 10 ℃/min speed, is heated to 720 ℃ with the speed of 15 ℃/min again and carries out hot defat.
Described sintering carries out in vacuum sintering furnace, and vacuum is 10
-4Pa, adopt two kinds of heating rates: 4 ℃ of slow heating rates/min to 525 ℃, fast 10 ℃/min of heating rate is to 1050 ℃~1350 ℃ of sintering temperatures, and insulation 3~5h cools to room temperature at last with the furnace.
The electrochemical deposition nanometer HA coating procedure of described porous outer layer comprises: preparation electrolyte is the Ca (NO of 0.042mol/L
3)
2(NH with 0.025mol/L
4)
2HPO
4Aqueous solution is 4.4 with ammonia and hydrochloric acid conditioning solution pH value, and graphite is as anode, and porous titanium implant is as negative electrode, and the temperature of electrolyte is 55 ℃, and electric current density is 1~1.5mA/cm
2Sedimentation time 1~2h, the NaOH of reuse 1mol/L handles 2h in 80 ℃.
The preparation process of described TGF slow-release gelatin microspheres comprises: the liquid paraffin 30ml that will contain 10g/L Span-80 places there-necked flask to be preheated to 60 ℃, stir the aqueous gelatin solution 4ml that is added dropwise to same temperature down fast, and continue to stir 10min with 600rpm speed; Change ice bath rapidly after forming water in oil emulsion, continue to stir 10min, make its full solidification; 25% glutaraldehyde that adds 0.5ml, stirring is precuring 2h down, and 4 ℃ solidify 24h, with proper amount of acetone, isopropyl alcohol, distilled water washing, drying, get pale yellow powder shape gelatine microsphere.Adding concentration in every 1mg dry microspheres is the TGF solution 5 μ l of 200ng/mL, put into the Ep pipe, the Ep pipe is placed (4 ℃ of shaking tables, 135r/min) fully soak into during PBS buffer solution pH7.4, centrifugal (1200~1500r/min) 15min behind the expansion 24h, microsphere is resuspended in distilled water, wash in the water, the lyophilizing once more of centrifugal back microsphere gets TGF-β 1 slow-release gelatin microspheres.
The preparation process of described porous titanium implant nanometer HA/TGF sustained-release micro-spheres composite coating comprises: under 50 ℃ gelatin is dissolved in the deionized water, the preparation mass fraction is 10% gelatin solution, nanometer HA coating imbedded body in porous titanium is soaked in the above-mentioned gelatin solution, application of vacuum 10min makes gelatin solution fully infiltrate POROUS TITANIUM inside.The TGF gelatine microsphere is scattered in the deionized water, and evenly coats the POROUS TITANIUM sample surfaces, negative pressure is handled, dry 24h.
With respect to existing medical titanium implantation body material, porous titanium implant body inner core density of the present invention is 95~97.5%, has higher mechanical strength, and the mechanical property that is complementary with osseous tissue is arranged, avoid stress concentration and stress shielding phenomenon, help stress conduction and new bone growth.Porous layer has the high porosity intercommunicating pore structure, and porous layer thickness is 0.4~1.1mm, and porosity is 50~70%, and the aperture is 50~400 μ m, helps freshman bone tissue's porous layer of growing into, and forms biological fixation; Outer bond strength with inner core is 150~300MPa, and porous layer and compacted zone are difficult for breaking away from.Material of the present invention has nanometer HA and carries the somatomedin gelatin releases the microcapsule composite coating, can improve the initiative that bone is integrated, and shortens the bone integrating time, realizes the long-term stability of implantation body.
The present invention adopts common ejection forming method to prepare fine and close inner core of implantation body and porous outer layer, and this method once-forming need not back machining, reduces cost greatly.And compare with respect to the method for spraying porous layer on compacted zone in the past, the porous layer of the material that this method obtains and internal layer bond strength significantly improve difficult drop-off.
Description of drawings
Fig. 1 is the tooth implant structural representation with material preparation of the present invention;
Fig. 2 is a nanometer HA coating sem photograph (* 2000);
Fig. 3 is the sem photograph (* 300) that carries TGF-β 1 sustained-release micro-spheres coating;
Fig. 4 is that the material of embodiment 1 preparation and osteoblast are cultivated the Electronic Speculum figure after 7 days altogether;
Fig. 5 is that the porous titanium implant of embodiment 1 preparation is implanted the slice map of dog femoral after March.
The specific embodiment
Embodiment 1 nanometer HA of the present invention and year somatomedin gelatin are released the preparation of microcapsule composite coating porous titanium material
(1) prepares material powder: preparation porous outer layer material powder: by weight percentage, get titanium valve 85%, hydride powder 15% is put four jars of blenders; By volume percentage ratio is got sodium chloride powder 45vol% again, with the powder stock mix homogeneously, is mixed with the porous outer layer material powder.The internal dense lamella material powder is a titanium valve.
(2) preparation binding agent: by weight percentage, taking polyethylene glycol 30%, vegetable oil 10%, polyethylene 20%, plasticizer 8%, paraffin 32% is put in the vane type batch mixer, mixes 1 hour under 140 ℃ of temperature;
(3) batching: with binding agent respectively with the porous outer layer material powder and the titanium valve of mixing, cooperated, and in batch mixer, under 140 ℃ of temperature, mixed 1.5h in by volume 55: 45.
(4) injection moulding: adopt bimodulus injecting method altogether, above-mentioned batch mixing is placed in the injection machine, with 145 ℃ of injection temperatures, injection pressure 100MPa, injection speed 65% under 55 ℃ of conditions of mould temperature, is processed into the porous titanium implant blank by implantation body's shape need;
(5) defat desalination: at first blank is put into water and be heated to 60 ℃, be detained 1.5h, then blank is put in the normal heptane, dissolving paraffin wax and vegetable oil component; 70 ℃ of blanks are removed dried up middle water-bath desalination 6h, every 1h changes a water again; Then in argon gas atmosphere, heating up with 10 ℃/min speed is heated to 300 ℃, heating up with the speed of 15 ℃/min then is heated to 720 ℃ and carries out hot defat.
(6) sintering: in vacuum sintering furnace blank is carried out sintering, vacuum is 10
-4Pa, adopt two kinds of heating rates: 4 ℃ of slow heating rates/min to 525 ℃, fast 10 ℃/min of heating rate is to 1050 ℃ of sintering temperatures, and insulation 3h cools to room temperature at last with the furnace.
(7) electrochemical deposition nanometer HA: preparation electrolyte is the Ca (NO of 0.042mol/L
3)
2(NH4) with 0.025mol/L
2HPO
4Aqueous solution is 4.4 with ammonia and hydrochloric acid conditioning solution pH value, and graphite is as anode, and porous titanium implant is as negative electrode, and the temperature of electrolyte is 55 ℃, and electric current density is 1.5mA/cm
2, sedimentation time 2h, the NaOH of reuse 1mol/l handles 2h in 80 ℃.
(8) preparation TGF-β 1 slow-release gelatin microspheres: the liquid paraffin 30ml that will contain 10g/L Span-80 places there-necked flask to be preheated to 60 ℃, stir the aqueous gelatin solution 4ml that is added dropwise to same temperature down fast, and regulate mixing speed (600rpm), continue to stir 10min; Change ice bath rapidly after forming water in oil emulsion, continue to stir 10min, make its full solidification; 25% glutaraldehyde that adds 0.5ml, stirring is precuring 2h down, and 4 ℃ solidify 24h, and with proper amount of acetone, isopropyl alcohol, distilled water washing, drying gets pale yellow powder shape gelatine microsphere.The TGF-β 1 solution 5 μ l that add 200ng/ml in every 1mg dry microspheres, put into the Ep pipe, the Ep pipe is placed (4 ℃ of shaking tables, 135r/min) fully soak into during PBS buffer solution pH 7.4, behind the expansion 24h, centrifugal (1400r/min) 15min, microsphere is resuspended in distilled water, washs in the water, microsphere lyophilizing once more behind the heart gets TGF-β 1 slow-release gelatin microspheres.
(8) nanometer HA/TGF-β 1 sustained-release micro-spheres composite coating preparation: under 50 ℃, gelatin is dissolved in the deionized water, the preparation mass fraction is 10% gelatin solution, nanometer HA coating porous titanium implant is soaked in the above-mentioned gelatin solution, application of vacuum 10min makes gelatin solution fully infiltrate POROUS TITANIUM inside.TGF-β 1 gelatine microsphere is scattered in the deionized water, and evenly coats the POROUS TITANIUM sample surfaces, negative pressure is handled, dry 24h.
Porous outer layer material powder: by weight percentage, get titanium valve 90% and hydride powder 10%; By volume percentage ratio is got sodium chloride powder 50vol% again, puts four jars of blenders, with the powder stock mix homogeneously.The powder of internal dense lamella is a titanium valve.Binding agent is with embodiment 1.Binding agent respectively with the porous outer layer material powder and the titanium valve of mixing, by volume 50:50 batching.All the other preparation methoies and technological parameter prepare nanometer HA/TGF-β 1 sustained-release micro-spheres composite coating titanium implant of the present invention all with embodiment 1.
Embodiment 3
Porous outer layer material powder: by weight percentage, get titanium valve 80% and hydride powder 20%; By volume percentage ratio is got sodium chloride powder 40vol% again, puts four jars of blenders, with the powder stock mix homogeneously.The powder of internal dense lamella is a titanium valve.Binding agent is with embodiment 1.Binding agent respectively with the porous outer layer material powder and the titanium valve of mixing, by volume 45:55 batching.All the other preparation methoies and technological parameter prepare nanometer HA/TGF-β 1 sustained-release micro-spheres composite coating titanium implant of the present invention all with embodiment 1.
Embodiment 4 usefulness material preparation tooth implant of the present invention and clinical practice thereof
Make loose structure titanium dental implant (referring to accompanying drawing 1) by the method for embodiment 1, it is shaped as column, is made up of coupling part and implant part.The coupling part is fine and close titanium, and density is 96%.Implant part comprises: DB inner core 1, porous layer 2 and coating 3.DB inner core 1 is fine and close titanium, and density is 96%, and its fatigue resistance can satisfy clinical requirement; The thickness of porous layer 2 is 1.1mm, and its porosity is 70%, and pore diameter range is 50~400 μ m; The interface bond strength of porous outer layer and inner core DB is 230MPa.Porous layer face coat 3 is divided into two parts: internal layer is nanometer HA coating (referring to an accompanying drawing 2), and Fig. 2 is a nanometer HA coating scanning electron microscope picture, amplification * 2000; Outer for carrying TGF-β 1 sustained-release micro-spheres coating (referring to accompanying drawing 3), Fig. 3 is for carrying sem photograph * 300 of TGF-β 1 sustained-release micro-spheres coating.
Prove that through clinical trial porous titanium implant and osteoblast are united cultivation, find that the porous layer surface has surface bioactive, can promote osteoblasticly to stick, breed, break up; In sticking process, find the trend of growing in the oriented hole of cell inside (referring to accompanying drawing 4).Accompanying drawing 4 is after porous titanium implant material of the present invention and osteoblast are cultivated 7 days altogether, makees the picture of electron-microscope scanning.
The composite coating porous titanium implant of this present invention preparation is implanted in the femur experiment of Canis familiaris L., porous layer after the discovery modification helps area of new bone and grows into, postoperative can be realized biological fixation (referring to accompanying drawing 5) in 3 months, and accompanying drawing 5 is done undecalcified femur upper segment bone implantation body slice map for implantation body's implantation after 3 months.
Claims (6)
1. a medicinal porous titanium implant comprises POROUS TITANIUM structural outside layers and fine and close titanium structure inner core, and it is characterized in that: inner core density is 95~97.5%; Skin is an intercommunicating pore structure, and porous layer thickness is 0.4~1.1mm, and porosity is 50~70%, and the aperture is 50~400 μ m; Outer bond strength with inner core is 150~300MPa; Porous layer surface deposition nanometer HA and year TGF slow-release gelatin microspheres composite coating.
2. the preparation method of implantation body according to claim 1 is characterized in that may further comprise the steps: adopt powder altogether ejection forming method inner core feeding and outer feeding are taken up in order of priority injection moulding, the injection moulding base is sintering after the defat desalination, obtains goods; With the porous outer layer depositing nano HA of electrochemical deposition method at goods, adopt the preparation of biphase emulsification condensation polymerization to carry the TGF slow-release gelatin microspheres, employing is oozed and is coated with technology nanometer HA surface deposition TGF sustained-release micro-spheres formation composite coating in the POROUS TITANIUM hole, obtains the composite coating porous titanium implant body; Described inner core feeding is to be raw material with the titanium valve, adopts oil-paraffin-polyolefin binder system to prepare; Outer feeding is to be raw material with the titanium valve, and adding 30~60vol% sodium chloride in titanium valve is pore creating material, and the titantium hydride of 5~20wt% is foaming agent, adopts oil-paraffin-polyolefin binder system to prepare.
3. preparation method as claimed in claim 2, it is characterized in that: described oil-paraffin-polyolefin binder system prescription is by weight percentage, taking polyethylene glycol 10~40%, vegetable oil 5~20%, polyethylene 15~30%, plasticizer 1~10%, paraffin 15~54%; Binding agent mixes 56~40:54~62 by volume with material powder.
4. preparation method as claimed in claim 2 is characterized in that described depositing nano HA coating procedure is: preparation electrolyte is the Ca (NO of 0.042mol/L
3)
2(NH with 0.025mol/L
4)
2HPO
4Aqueous solution is 4.4 with ammonia and hydrochloric acid conditioning solution pH value, and graphite is as anode, and porous titanium implant is as negative electrode, and the temperature of electrolyte is that 55 ℃ of electric current densities are 1~1.5mA/cm
2, deposition 1~2h, the NaOH of reuse 1mol/L handles 2h in 80 ℃.
5. preparation method as claimed in claim 2, it is characterized in that the described process that nanometer HA surface deposition TGF sustained-release micro-spheres forms composite coating in the POROUS TITANIUM hole is: it is in 10% the gelatin solution that nanometer HA coating porous titanium implant is soaked in mass fraction, application of vacuum 10min, the TGF gelatine microsphere is scattered in the deionized water, and evenly coat implant surface, negative pressure is handled, drying.
6. as the preparation method one of as described in the claim 2~5, it is characterized in that: described injection molding process condition altogether is: 135 ℃~155 ℃ of injection temperatures, injection pressure 80Mpa~100MPa, injection speed 50~65%, 30 ℃~60 ℃ of mould temperature; Described shaping base defat desalination processes is: will inject green compact and put into water and be heated to 40 ℃~60 ℃, be detained 1~2h, then blank is put in the normal heptane, dissolving paraffin and vegetable oil component, water-bath desalination again, under argon gas atmosphere, be heated to 300 ℃ at last, be heated to 720 ℃ with the speed of 15 ℃/min again and carry out hot defat with 10 ℃/min speed; The vacuum of described vacuum-sintering is 10
-4Pa, 4 ℃ of slow heating rates/min to 525 ℃, fast 10 ℃/min of heating rate is to 1050 ℃~1350 ℃ of sintering temperatures, and insulation 3~5h cools to room temperature at last with the furnace.
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2009
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