CN103721297A - Absorbable orthopedic instrument material capable of prompting growth of bone tissues and preparation method thereof - Google Patents
Absorbable orthopedic instrument material capable of prompting growth of bone tissues and preparation method thereof Download PDFInfo
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- CN103721297A CN103721297A CN201410006749.7A CN201410006749A CN103721297A CN 103721297 A CN103721297 A CN 103721297A CN 201410006749 A CN201410006749 A CN 201410006749A CN 103721297 A CN103721297 A CN 103721297A
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Abstract
The invention discloses an absorbable orthopedic instrument material capable of prompting growth of bone tissues and a preparation method thereof. The material is prepared by compounding a medical absorbable high-molecular polymer, a degradable pure magnesium or magnesium alloy which is loaded with BaTiO3 piezoelectric ceramics, can conduct piezoelectric signals and serves as a conductive carrier material, and grapheme for improving the electric polarization effect. When the absorbable orthopedic instrument material is in use, an electric signal produced by the piezoelectric ceramics under the action of an external load can be effectively conducted to organism tissues around an orthopedic instrument by the conductive carrier material to stimulate the growth of early hard tissues at a bone injury position and promote healing of the bone tissues. The BaTiO3 piezoelectric ceramics is loaded on the conductive carrier material through a dual loading technology consisting of electrophoresis-micro-arc oxidation and sol sealing, coating and film forming. Meanwhile, the conductive carrier material and the grapheme can also enhance the polarization effect and stress sensitivity of the piezoelectric ceramics. A bar material or a plate material is prepared firstly by means of a thermal die pressing, extruding or pulling method, and the orthopedic instrument is made by means of polarization and machining.
Description
Technical field
The present invention relates to adsorbable bone section apparatus having specific function and preparation method thereof, in use procedure, can form the piezoelectric signal that promotes union of fracture, bone growth, belong to orthopedic instrument technical field, be specially a kind of adsorbable bone section apparatus that promotes bone growth and preparation method thereof.
Background technology
In the last few years, with degradable high polymer material, received increasing concern because of advantages such as degradable, stress-shielding effect are little as orthopedic fixation device tools such as the absorbable bone peg of the processing such as polylactic acid, polyglycolic acid preparation, hone lamellas.But with being orthopedic instrument, also there is the problems such as X-ray absorbability is weak, development effect is poor in them, meanwhile, can not produce the signal of telecommunication that can stimulate bone growth.
As known, the healing of fracture is a long-term process, and the suitable signal of telecommunication can stimulate the early stage sclerous tissues growth at bone injury position, promotes normal bone growth, shortens healing time.Piezoelectric can produce the signal of telecommunication while being subject to load as important functional material, therefore, by piezoelectric implant into body, can utilize organism displacement to produce piezoelectric effect to implant and form electricity irritation, promotes union of fracture.There are some researches show that bio piezoelectric ceramic not only has piezoelectric effect, and have good biocompatibility (Wang Peng, etc., West China Journal of Stomatology, 2008,26(2): 133-136; R.Baxter, et al.J Mater Sci:Mater Med (2009) 20:1697-1708), but bio piezoelectric ceramic plasticity is poor, is difficult to directly make orthopedic fixer tool.
By piezoelectric ceramics and polymer is compound can overcome the poor problem of piezoelectric ceramics plasticity, obtain having the composite (Liu Xiaofang of piezoelectric property, PZT/ polymer-matrix structures of piezoelectric composite and performance study [D], Wuhan: Wuhan University of Technology, 2005), therefore, if adopting suitable method introduces piezoelectric ceramics in the absorbable polymer nail, hone lamella etc. of current clinical use, utilize organism displacement to produce piezoelectric effect to implant and form electricity irritation, promote union of fracture, can realize the multifunction of adsorbable bone section apparatus.
The absorbed macromolecule orthopaedics apparatus of current clinical use does not have the bone growth of promotion and developing function, and healing cycle is long, and in implantation process, cannot carry out regularly diagnosis of X-ray and monitoring to its degraded and absorbed behavior in vivo.By BaTiO
3piezoelectric ceramics is introduced in such orthopedic instrument, utilizes organism displacement to produce piezoelectric effect to implant and forms electricity irritation, promotes union of fracture, can realize the multifunction of adsorbable bone section apparatus.
But because polymer dielectric properties and poor electric conductivity, elastic modelling quantity are low, make BaTiO
3piezoelectric ceramics polarization effect and piezoelectric effect are poor, and the ultra-weak electronic signal of generation is also difficult for by conduction to body tissue; Meanwhile, BaTiO
3piezoelectric ceramics and polymer wellability are poor, and interface is in conjunction with undesirable, and it adds membership and worsens such orthopedic instrument itself with regard to undesirable mechanical property.
Summary of the invention
Technical problem: the object of this invention is to provide a kind of adsorbable bone section device material that can promote bone growth and preparation method thereof, key technical problem to be solved is how to realize BaTiO in such absorbable polymer orthopedic instrument
3the load of piezoelectric ceramics, polarization and signal conduction, do not reduce again its mechanical property simultaneously, is specifically related to selection and the BaTiO of degradable conductive carrier material
3effective conduction, electrically conductive carrier material and the BaTiO of the improvement of the load technology of piezoelectric ceramics, piezoelectric ceramics polarization effect, the raising of stress sensitivity and faint piezoelectric signal
3the technical problems such as raising of piezoelectric ceramics interface bond strength.
Technical scheme: a kind of adsorbable bone section device material that can promote bone growth for achieving the above object, is achieved through the following technical solutions: described orthopedic instrument material is to be distributed in polymer and to be had BaTiO for improving Graphene, the area load of electric polarization effect by Medical absorbable high molecular polymer and disperse
3the electrically conductive carrier material that piezoelectric ceramics function film also can conduct piezoelectric signal forms, and be prepared from through thermal pressure molding and electric polarization processing, wherein, described electrically conductive carrier material is pure magnesium or magnesium alloy silk material or sheet material, its volume fraction is 10%～75%, adopt electrophoresis-micro-arc oxidation to apply in conjunction with colloidal sol sealing of hole the dual carrying method that embrane method is compounded to form, by BaTiO
3piezoelectric ceramics function film loads on electrically conductive carrier material, BaTiO
3piezoelectric ceramics function film bed thickness is 1～200 μ m, and the percent by volume of Graphene is 0.01%～5%.
Described Medical absorbable high molecular polymer is a kind of of absorbable polylactic acid, polyglycolic acid, polycaprolactone, Polyethylene Glycol, polyamide or wherein two or more their copolymer or blend.
In described Medical absorbable high molecular polymer, can also add a small amount of graphite, CNT or conductive nano white carbon black to improve polarization effect.
The preparation method of a kind of adsorbable bone section device material that can promote bone growth as claimed in claim 1 of the present invention is as follows:
1) processing of electrically conductive carrier material: the pure magnesium of electrically conductive carrier material or magnesium alloy are made to a material or sheet material by drawing, rolling or pressing method;
2) BaTiO
3the first load of electrophoresis-micro-arc oxidation of piezoelectric ceramics function film: by the BaTiO preparing in advance
3colloid solution joins in differential arc oxidation alkaline electrolyte, with electrophoresis-differential arc oxidation treatment method, at the pure magnesium of electrically conductive carrier material or magnesium alloy silk material or plate surface, prepares containing BaTiO
3the porous function film of piezoelectric ceramics, electrophoresis-differential arc oxidation voltage is 100～600V, the processing time is 2～60min;
3) BaTiO
3the colloidal sol sealing of hole coating film forming secondary load of piezoelectric ceramics function film: in step 2), on basis, electrically conductive carrier material is impregnated into BaTiO again
30.5～10h in sol solution, carries out BaTiO
3the colloidal sol sealing of hole of piezoelectric ceramics function film applies film forming secondary load, takes out afterwards dry;
4) processing and forming of orthopedic instrument is processed with electric polarization: the polymer paste forming through organic solvent dissolution or high-temperature fusion is mixed homogeneously with Graphene and formed mixed slurry, then have BaTiO through dipping or coating processes and load
3the compound prefabricated blank of making of carrier material of piezoelectric ceramics function film, or first load is had to BaTiO
3the carrier material of piezoelectric ceramics function film is arranged in mold cavity, aforementioned mixed slurry reinjects, then, forming method processing by hot moulding, extruding, injection moulding or drawing is prepared into bar or sheet material, again in HVDC oil bath device to the processing that polarizes of prepared bar and sheet material, finally by the orthopedic instrument that is machined into desired structure.
Described Medical absorbable high molecular polymer is a kind of of absorbable polylactic acid, polyglycolic acid, polycaprolactone, Polyethylene Glycol, polyamide or wherein two or more their copolymer or blend.
In described Medical absorbable high molecular polymer, can also add a small amount of graphite, CNT or conductive nano white carbon black to improve polarization effect.
Beneficial effect: beneficial effect of the present invention is as follows:
1) there is piezoelectric effect, promote union of fracture.The present invention adopts electrophoresis-micro-arc oxidation to apply in conjunction with colloidal sol sealing of hole the dual load technology that embrane method is compounded to form, by BaTiO
3piezoelectric ceramics function film loads on electrically conductive carrier material, between two kinds of carrying methods, be related, it not simple combination, first by electrophoresis-micro-arc oxidation, on electrically conductive carrier material surface, form firmly porous ceramic film of combination, on this basis, adopt colloidal sol sealing of hole to apply into embrane method and carry out quadratic B aTiO
3the load of piezoelectric ceramics, formed BaTiO
3piezoelectric ceramics function film is combined firmly with electrically conductive carrier material, and film thickness is easy to control.Under load, BaTiO
3the piezoelectric signal that piezoelectric ceramics function film produces can stimulate the early stage sclerous tissues growth of damage location by the effective conduction of the electrically conductive carrier material of silk material or sheet material shape to orthopedic instrument body tissue around, promotes normal tissue growth, improves curative effect.
2) piezoelectric ceramics polarization effect and stress sensitivity are good.Compare with biological absorbable high molecular polymer, electrically conductive carrier material--magnesium and alloy thereof have higher elastic modelling quantity and better electric conductivity, the silk material of the pure magnesium as electrically conductive carrier material or magnesium alloy or sheet material are aligned in Biodegradable high-molecular polymer with directed or nondirectional form, not only can improve piezoelectric ceramics polarization effect, can also improve the stress sensitivity of orthopedic instrument, the external force that orthopedic fixer tool is subject to passes to rapidly piezoelectric ceramics., compare with other material with carbon element, Graphene has better dielectric and electric conductivity meanwhile, and a small amount of Graphene adds can significantly improve the electric polarization effect of piezoelectric ceramic particle in polymer and the conduction of faint piezoelectric signal.
3) faint piezoelectric signal can effectively be conducted to body tissue.Electrically conductive carrier material--magnesium and alloy wire thereof and sheet material have good electric conductivity, and continuous magnesium alloy silk material and sheet material can form the continuous conduction pathway of the signal of telecommunication from orthopedic instrument inside to outer surface, the faint piezoelectric signal that the inner piezoelectric ceramics of apparatus can be produced passes to body tissue around, the early stage sclerous tissues growth that stimulates bone injury position, improves curative effect.
4) there is developing function.BaTiO
3piezoelectric ceramics function film can improve the X ray assimilation effect that can absorb high molecular polymer orthopedic instrument, thereby can by X ray, observe implantation and the degraded situation of implant, is convenient to diagnose clinically to improve curative effect.
5) good biocompatibility, absorbability energy and mechanical property.This orthopedic instrument material therefor is comprised of the Material cladding with good biocompatibility and degradability, after union of fracture, can be degraded in time, absorb, and piezoelectric ceramics used and Graphene are nontoxic, can be deposited in freshman bone tissue or through human body internal circulation system and excrete, show good biocompatibility.Meanwhile, Graphene, magnesium alloy silk material or sheet material can also form certain strengthening and toughening effect to absorbing high molecular polymer orthopedic instrument.
The specific embodiment
The present invention is a kind of adsorbable bone section device material that can promote bone growth and preparation method thereof, and described orthopedic instrument material is to be distributed in polymer and to be had BaTiO for improving Graphene, the area load of electric polarization effect by Medical absorbable high molecular polymer, disperse
3piezoelectric ceramics function film also can conduct the pure magnesium of degradable of piezoelectric signal or electrically conductive carrier material that magnesium alloy serves as forms, through thermal pressure molding and electric polarization processing, form again, in use procedure, the external load function lower piezoelectric pottery generation signal of telecommunication can effectively be conducted to orthopedic instrument body tissue around by electrically conductive carrier material, can stimulate the early stage sclerous tissues growth at bone injury position, promote osseous tissue healing, wherein, BaTiO
3the dual load technology that piezoelectric ceramics function film applies into embrane method formation by electrophoresis-micro-arc oxidation in conjunction with colloidal sol sealing of hole is loaded on electrically conductive carrier material, the volume fraction of described pure magnesium or magnesium alloy silk material or sheet material electrically conductive carrier material is 10%～75%, BaTiO
3piezoelectric ceramics function film bed thickness is 1～200 μ m, and the percent by volume of Graphene is 0.01%～5%, and the concrete preparation process of this orthopedic instrument material is as follows:
1) processing of electrically conductive carrier material: the pure magnesium of electrically conductive carrier material or magnesium alloy are made to a material or sheet material by drawing, rolling or pressing method.Magnesium and magnesium alloy are a kind of medical degradable metals, compare with biological absorbable high molecular polymer, magnesium and alloy thereof have higher elastic modelling quantity and better electric conductivity, pure magnesium as electrically conductive carrier material or magnesium alloy silk material or sheet material are aligned in Biodegradable high-molecular polymer with directed or nondirectional form, not only can improve piezoelectric ceramics polarization effect, can also improve the stress sensitivity of orthopedic instrument, the external force that orthopedic fixer tool is subject to passes to rapidly piezoelectric ceramics, simultaneously, continuous magnesium alloy silk material and sheet material conductive carrier can form the continuous conduction pathway of the signal of telecommunication from orthopedic instrument inside to outer surface, the faint piezoelectric signal that the inner piezoelectric ceramics of apparatus can be produced passes to body tissue around, stimulate the early stage sclerous tissues growth at bone injury position, improve curative effect.Therefore, select magnesium and alloy wire thereof or sheet material as degradable carrier material of the present invention and conductive material, can improve piezoelectric ceramics polarization effect, improve stress sensitivity, faint piezoelectric signal is effectively conducted, and form certain strengthening and toughening effect to absorbing high molecular polymer orthopedic instrument.
2) BaTiO
3the first load of electrophoresis-micro-arc oxidation of piezoelectric ceramics function film: by the BaTiO preparing in advance
3colloid solution joins in differential arc oxidation alkaline electrolyte, with electrophoresis-differential arc oxidation treatment technology, at the pure magnesium of electrically conductive carrier material or magnesium alloy silk material or plate surface, prepares containing BaTiO
3the porous function film of piezoelectric ceramics, electrophoresis-differential arc oxidation voltage is 100～600V, oxidization time is 2～60min.At magnesium alloy electrically conductive carrier material surface by micro-arc oxidation, process and can generate porous oxide ceramic layer, the micropore in oxidation ceramic layer can form channeling, in differential arc oxidation process, can make BaTiO
3colloid charged particle enters inside by electrophoresis motion, and high specific surface area can be provided, and is conducive to improve load capacity in follow-up colloidal sol sealing of hole coating procedure.According to colloidal theory, can there is electrophoresis directed movement in charged colloidal particle granule, based on this principle, add BaTiO in alkaline electrolyte under electric field action
3colloid, electronegative thereby colloidal solid can adsorb anion, afterwards under the electric field action of differential arc oxidation, BaTiO
3colloidal solid anode electrophoresis motion, generates containing BaTiO at pure magnesium or magnesium alloy surfaces of carrier materials
3the porous function film of piezoelectric ceramics, should be containing BaTiO
3the porous function film of piezoelectric ceramics is to generate in electrically conductive carrier material surface in situ oxidation, and therefore, the interface bond strength between itself and electrically conductive carrier material is high, incrust.
3) BaTiO
3the colloidal sol sealing of hole coating film forming secondary load of piezoelectric ceramics function film: in step 2), on basis, surface is impregnated into BaTiO again with the electrically conductive carrier material that electrophoresis-micro-arc oxidation is prepared porous function film
30.5～10h in sol solution, carries out BaTiO
3the colloidal sol sealing of hole of piezoelectric ceramics function film applies film forming secondary load, takes out afterwards dry.Because forming function film after aforementioned electrophoresis-differential arc oxidation is processed, electrically conductive carrier material surface there is loose structure, BaTiO
3colloidal sol is easy to enter in its surface hole defect, can form colloidal sol sealing of hole effect to it on the one hand, on the other hand, can also further increase BaTiO
3the thickness of piezoelectric ceramics function film and load capacity, and micropore strengthening effect makes interface bond strength higher.
4) processing and forming of orthopedic instrument is processed with electric polarization: after the polymer paste forming through organic solvent dissolution or high-temperature fusion is mixed homogeneously with Graphene, then have BaTiO through dipping or coating processes and load
3the compound prefabricated blank of making of carrier material of piezoelectric ceramics function film, or first load is had to BaTiO
3the carrier material of piezoelectric ceramics function film is arranged in mold cavity, mixed slurry reinjects, then, forming method processing by hot moulding, extruding, injection moulding or drawing is prepared into bar or sheet material, again in HVDC oil bath device to the processing that polarizes of prepared bar and sheet material, finally by the orthopedic instrument that is machined into desired structure.Embodiment 1
The Biodegradable high-molecular polymer of selecting is polylactic acid PLLA, and pure magnesium silk material is as load BaTiO
3the carrier of piezoelectric ceramics function film and conductor, volume fraction is 25%, preparation process is as follows:
1) pure magnesium is drawn into the silk material that diameter is 0.3mm;
2) preparation BaTiO
3sol solution and electrophoresis-differential arc oxidation is processed: under room temperature, take the Ba (OH) of 0.25mol
28H
2o is dissolved in the CH of 170ml
3in COOH, be heated to 70 ℃ and strong agitation, cooling for reflux 1h, is cooled to room temperature simultaneously, measures the butyl titanate of 85ml, then adds 250ml dehydrated alcohol, after rapid stirring is cooling, dropwise adds in cooling for reflux solution, and vigorous stirring 20min, obtains BaTiO simultaneously
3sol solution.Measure 200mL colloid solution and join in 4L differential arc oxidation electrolyte, electrolyte main component is 10g/L sodium silicate, 2g/L NaOH and 8g/L hydroxyapatite nanoparticle.Magnesium silk material is dipped in wherein, applies 420V voltage, the differential arc oxidation carrying out 10 minutes is processed, and makes its surface in situ generate one deck containing BaTiO
3the porous function film of piezoelectric ceramics, the average micropore size of porous function film is 25 μ m;
3) BaTiO
3the colloidal sol sealing of hole of piezoelectric ceramics function film applies film forming secondary load: the magnesium silk material above-mentioned electrophoresis-differential arc oxidation processing rear surface to porous function film is impregnated into BaTiO again
3in sol solution, carry out colloidal sol sealing of hole coating processing, dip time takes out dry after 4 hours, the BaTiO making
3the average bed thickness of piezoelectric ceramics function film is about 80 μ m;
4) PLLA polymer is heated to, after 190 ℃ of meltings, have BaTiO with above-mentioned area load
3the magnesium alloy silk material electrically conductive carrier material of piezoelectric ceramics function film, Graphene (volume fraction is 0.05%) mix, and process and be prepared into bar by hot-extrusion method, again in HVDC oil bath device to the bar the obtaining processing that polarizes, polarization temperature is 90 ℃, polarization time is 20min, polarizing voltage is 4000V, finally by being machined into the fixator for orthopedics department parts such as pin, screw, nail.
Embodiment 2
The high molecular polymer of selecting degradable to absorb is the copolymer p GLA of polylactic acid and polyglycolic acid, and AZ31B magnesium alloy plate is as load BaTiO
3the carrier of piezoceramics film and conductor, volume fraction is 40%, preparation process is as follows:
1) magnesium alloy is rolled into the sheet material of 0.5mm;
2) preparation BaTiO
3sol solution and electrophoresis-differential arc oxidation is processed: under room temperature, take the Ba (OH) of 0.25mol
28H
2o is dissolved in the CH of 200mL
3in COOH, be heated to 70 ℃ and strong agitation, cooling for reflux 2h, is cooled to room temperature simultaneously, measures the butyl titanate of 85ml, then adds 250ml dehydrated alcohol, after rapid stirring is cooling, dropwise adds in cooling for reflux solution, and vigorous stirring 30min, obtains BaTiO simultaneously
3sol solution.Measuring 200mL colloid solution joins in 5L differential arc oxidation electrolyte, electrolyte main component is 8g/L sodium silicate, 2g/L NaOH, and magnesium alloy plate is dipped in wherein, applies 380V voltage, the differential arc oxidation carrying out 20 minutes is processed, and its surface in situ is generated containing BaTiO
3the porous function film of piezoelectric ceramics, the average micropore size of porous function film is 30 μ m;
3) BaTiO
3the colloidal sol sealing of hole of piezoelectric ceramics function film applies film forming secondary load: the magnesium silk material above-mentioned electrophoresis-differential arc oxidation processing rear surface to porous function film is impregnated into BaTiO again
3in sol solution, carry out colloidal sol sealing of hole coating processing, dip time takes out dry after 5 hours, the BaTiO making
3the average bed thickness of piezoelectric ceramics function film is about 90 μ m;
4) sodium iodide, Graphene (volume fraction is 0.5%) are joined in the chloroform soln that is dissolved with polymer P GLA and make slurry, then have BaTiO with above-mentioned area load
3the magnesium alloy plate electrically conductive carrier material of piezoelectric ceramics function film mixes, after vacuum drying, by the processing of hot moulding method, be prepared into sheet material, again in HVDC oil bath device to the sheet material the obtaining processing that polarizes, polarization temperature is 100 ℃, polarization time is 20min, polarizing voltage is 3000V, last, by common mach method, is processed into the fixator for orthopedics department parts such as hone lamella.
Embodiment 3
It is polyglycolic acid (PGA) that the degradable of selecting absorbs high molecular polymer, and QE22 magnesium alloy silk material is as load BaTiO
3the carrier of piezoelectric ceramics function film and conductor, volume fraction is 30%, preparation process is as follows:
1) magnesium alloy is drawn into the silk material that diameter is 0.5mm;
2) preparation BaTiO
3sol solution and electrophoresis-differential arc oxidation is processed: under room temperature, take the Ba (OH) of 0.25mol
28H
2o is dissolved in the CH of 200mL
3in COOH, be heated to 70 ℃ and strong agitation, simultaneously cooling for reflux 2h, be cooled to room temperature, measure the butyl titanate of 100ml, then add 300ml dehydrated alcohol, after rapid stirring is cooling, dropwise add in cooling for reflux solution, vigorous stirring 30min, obtains BaTiO simultaneously
3sol solution.Measuring 300mL colloid solution joins in 5L differential arc oxidation electrolyte, bath composition is mainly 10g/L sodium silicate, 3g/L NaOH and 10g/L hydroxyapatite nanoparticle, magnesium alloy silk material is dipped in wherein, apply 380V voltage, the differential arc oxidation carrying out 15 minutes is processed, and makes its surface in situ generate one deck containing BaTiO
3the porous function film of piezoelectric ceramics, the average micropore size of porous function film is 25 μ m;
3) BaTiO
3the colloidal sol sealing of hole of piezoelectric ceramics function film applies film forming secondary load: the magnesium silk material above-mentioned electrophoresis-differential arc oxidation processing rear surface to porous function film is impregnated into BaTiO again
3in sol solution, carry out colloidal sol sealing of hole coating processing, dip time takes out dry after 4 hours, the BaTiO making
3the average bed thickness of piezoelectric ceramics function film is about 90 μ m;
4) sodium iodide, Graphene (volume fraction is 2%) are joined and in the chloroform soln that is dissolved with polymer P GA, make slurry and have BaTiO with above-mentioned area load again
3the magnesium alloy plate electrically conductive carrier material of piezoelectric ceramics function film mixes, after vacuum drying, by the processing of hot pull method, be prepared into bar, again in HVDC oil bath device to the bar the obtaining processing that polarizes, polarization temperature is 100 ℃, polarization time is 30min, polarizing voltage is 5000V, last, then the fixator for orthopedics department part such as machined one-tenth pin, screw, nail.
Above-mentioned embodiment is several example of the present invention, is not for limiting enforcement of the present invention and interest field, and all equivalences of making according to the content described in the present patent application scope of patent protection change and modify, and all should be included in the present patent application the scope of the claims.
Claims (4)
1. the adsorbable bone section device material that can promote bone growth, is characterized in that: described orthopedic instrument material is to be distributed in polymer and to be had BaTiO for improving Graphene, the area load of electric polarization effect by Medical absorbable high molecular polymer and disperse
3the electrically conductive carrier material that piezoelectric ceramics function film also can conduct piezoelectric signal forms, and be prepared from through thermal pressure molding and electric polarization processing, wherein, described electrically conductive carrier material is pure magnesium or magnesium alloy silk material or sheet material, its volume fraction is 10%～75%, adopt electrophoresis-micro-arc oxidation to apply in conjunction with colloidal sol sealing of hole the dual carrying method that embrane method is compounded to form, by BaTiO
3piezoelectric ceramics function film loads on electrically conductive carrier material, BaTiO
3piezoelectric ceramics function film bed thickness is 1～200 μ m, and the percent by volume of Graphene is 0.01%～5%, and all the other are Medical absorbable high molecular polymer.
2. the adsorbable bone section device material that can promote bone growth according to claim 1, is characterized in that: described Medical absorbable high molecular polymer is a kind of of absorbable polylactic acid, polyglycolic acid, polycaprolactone, Polyethylene Glycol, polyamide or wherein two or more their copolymer or blend.
3. the adsorbable bone section device material that can promote bone growth according to claim 1, is characterized in that: in described Medical absorbable high molecular polymer, can also add a small amount of graphite, CNT or conductive nano white carbon black to improve polarization effect.
4. the preparation method that can promote the adsorbable bone section device material of bone growth as claimed in claim 1, is characterized in that: the concrete preparation process of this orthopedic instrument material is as follows:
1) processing of electrically conductive carrier material: the pure magnesium of electrically conductive carrier material or magnesium alloy are made to a material or sheet material by drawing, rolling or pressing method;
2) BaTiO
3the first load of electrophoresis-micro-arc oxidation of piezoelectric ceramics function film: by the BaTiO preparing in advance
3colloid solution joins in differential arc oxidation alkaline electrolyte, with electrophoresis-differential arc oxidation treatment method, at the pure magnesium of electrically conductive carrier material or magnesium alloy silk material or plate surface, prepares containing BaTiO
3the porous function film of piezoelectric ceramics, electrophoresis-differential arc oxidation voltage is 100～600V, the processing time is 2～60min;
3) BaTiO
3the colloidal sol sealing of hole coating film forming secondary load of piezoelectric ceramics function film: in step 2), on basis, electrically conductive carrier material is impregnated into BaTiO again
30.5～10h in sol solution, carries out BaTiO
3the colloidal sol sealing of hole of piezoelectric ceramics function film applies film forming secondary load, takes out afterwards dry;
4) processing and forming of orthopedic instrument is processed with electric polarization: the polymer paste forming through organic solvent dissolution or high-temperature fusion is mixed homogeneously with Graphene and formed mixed slurry, then have BaTiO through dipping or coating processes and load
3the compound prefabricated blank of making of carrier material of piezoelectric ceramics function film, or first load is had to BaTiO
3the carrier material of piezoelectric ceramics function film is arranged in mold cavity, aforementioned mixed slurry reinjects, then, forming method processing by hot moulding, extruding, injection moulding or drawing is prepared into bar or sheet material, again in HVDC oil bath device to the processing that polarizes of prepared bar and sheet material, finally by the orthopedic instrument that is machined into desired structure.
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| CN105420796A (en) * | 2015-11-27 | 2016-03-23 | 福州大学 | Modified coating containing carbon nanotube-hydroxyapatite on magnesium-based surface and preparing method |
| CN110279895A (en) * | 2019-06-28 | 2019-09-27 | 江西理工大学 | A kind of l-lactic acid composite material and preparation method of barium titanate and graphene oxide collaboration enhancing |
| CN110797453A (en) * | 2019-11-14 | 2020-02-14 | 中国科学院长春应用化学研究所 | Piezoelectric nano composite material and preparation method thereof |
| CN112251790A (en) * | 2020-10-22 | 2021-01-22 | 中国船舶重工集团公司第七二五研究所 | Preparation method of rare earth magnesium alloy structural member surface composite film layer |
| CN112713234A (en) * | 2020-12-16 | 2021-04-27 | 昆山微电子技术研究院 | Piezoelectric body and preparation method thereof |
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1381276A (en) * | 2002-05-10 | 2002-11-27 | 清华大学 | Nano carbon tube reinforced plastics/ceramics-base composition for repairing bone |
| US20050100578A1 (en) * | 2003-11-06 | 2005-05-12 | Schmid Steven R. | Bone and tissue scaffolding and method for producing same |
| WO2008115883A1 (en) * | 2007-03-16 | 2008-09-25 | The Regents Of The University Of California | Nanostructure surface coated medical implants and methods of using the same |
| US20120271396A1 (en) * | 2007-01-19 | 2012-10-25 | Elixir Medical Corporation | Biodegradable endoprostheses and methods for their fabrication |
| CN103330959A (en) * | 2013-06-04 | 2013-10-02 | 东南大学 | Prestress-reinforced light high-strength controllable-degradation medical composite material and preparation method thereof |
| CN103420364A (en) * | 2013-07-13 | 2013-12-04 | 西南交通大学 | Preparation method of grapheme/hydroxyapatite composite material |
-
2014
- 2014-01-07 CN CN201410006749.7A patent/CN103721297B/en not_active Expired - Fee Related
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1381276A (en) * | 2002-05-10 | 2002-11-27 | 清华大学 | Nano carbon tube reinforced plastics/ceramics-base composition for repairing bone |
| US20050100578A1 (en) * | 2003-11-06 | 2005-05-12 | Schmid Steven R. | Bone and tissue scaffolding and method for producing same |
| US20120271396A1 (en) * | 2007-01-19 | 2012-10-25 | Elixir Medical Corporation | Biodegradable endoprostheses and methods for their fabrication |
| WO2008115883A1 (en) * | 2007-03-16 | 2008-09-25 | The Regents Of The University Of California | Nanostructure surface coated medical implants and methods of using the same |
| CN103330959A (en) * | 2013-06-04 | 2013-10-02 | 东南大学 | Prestress-reinforced light high-strength controllable-degradation medical composite material and preparation method thereof |
| CN103420364A (en) * | 2013-07-13 | 2013-12-04 | 西南交通大学 | Preparation method of grapheme/hydroxyapatite composite material |
Non-Patent Citations (4)
| Title |
|---|
| LAURA J ROMASANTA ET AL.: "Functionalised graphene sheets as effective high dielectric constant fillers", 《NANOSCALE RESEARCH LETTERS》 * |
| PALLAB BHATTACHARYA ET AL.: "Investigation on microwave absorption capacity of nanocomposites based on metal oxides and graphene", 《JOURNAL OF MATERIALS SCIENCE: MATERIALS IN ELECTRONICS》 * |
| 付春颖等: "生物压电陶瓷在骨修复材料的研究进展", 《求医问药》 * |
| 沈贺等: "石墨烯在生物医学领域的应用", 《东南大学学报（医学版）》 * |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105420796A (en) * | 2015-11-27 | 2016-03-23 | 福州大学 | Modified coating containing carbon nanotube-hydroxyapatite on magnesium-based surface and preparing method |
| CN105420796B (en) * | 2015-11-27 | 2018-06-12 | 福州大学 | The modified coating and preparation method of magnesium-based surface carbon nanotubes-hydroxyapatite |
| CN110279895A (en) * | 2019-06-28 | 2019-09-27 | 江西理工大学 | A kind of l-lactic acid composite material and preparation method of barium titanate and graphene oxide collaboration enhancing |
| CN110279895B (en) * | 2019-06-28 | 2022-03-11 | 江西理工大学 | Barium titanate and graphene oxide synergistically enhanced levorotatory polylactic acid composite material and preparation method thereof |
| CN110797453A (en) * | 2019-11-14 | 2020-02-14 | 中国科学院长春应用化学研究所 | Piezoelectric nano composite material and preparation method thereof |
| CN112251790A (en) * | 2020-10-22 | 2021-01-22 | 中国船舶重工集团公司第七二五研究所 | Preparation method of rare earth magnesium alloy structural member surface composite film layer |
| CN112251790B (en) * | 2020-10-22 | 2021-12-24 | 中国船舶重工集团公司第七二五研究所 | Preparation method of rare earth magnesium alloy structural member surface composite film layer |
| CN112713234A (en) * | 2020-12-16 | 2021-04-27 | 昆山微电子技术研究院 | Piezoelectric body and preparation method thereof |
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