CN103751858B - Absorbable orthopedic instrument material capable of promoting revascularization and preparation method thereof - Google Patents
Absorbable orthopedic instrument material capable of promoting revascularization and preparation method thereof Download PDFInfo
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- CN103751858B CN103751858B CN201410007096.4A CN201410007096A CN103751858B CN 103751858 B CN103751858 B CN 103751858B CN 201410007096 A CN201410007096 A CN 201410007096A CN 103751858 B CN103751858 B CN 103751858B
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Abstract
The invention discloses an absorbable instrument material capable of promoting revascularization for department of orthopaedics and a preparation method thereof. The instrument material for department of orthopaedics comprises an absorbable high-molecular polymer, graphene dispersed and distributed in the polymer and used for reinforcing and toughening, and a degradable carrier material loaded with copper ions, wherein the copper ions capable of promoting collagen deposition and revascularization can be slowly released in a use process, wherein the copper ions are effectively loaded on a degradable carrier material used as a pure magnesium or magnesium alloy wire or plate containing a hydroxyapatite porous ceramic layer on the surface by using a dual-compound loading technology of a special electrophoresis-micro-arc oxidation method and a chemical immersion ion exchange reaction method. A rod or plate is firstly produced by adopting methods such as hot mould pressing, extruding or drawing, and then mechanically processed into various absorbable functional bone repair and fixation instruments such as bone nails and bone lamellas, thus the absorbable instrument material is wide in application prospect.
Description
Technical field
The present invention relates to a kind of Absorbable rod orthopaedics internal fixation device with specific function and preparation method thereof, the copper ion that can promote revascularization can be slowly released in use degradation process, there is the function promoting collagen deposition and revascularization, belong to orthopedic instrument technical field, be specially a kind of Absorbable rod orthopedic instrument that can promote revascularization and preparation method thereof.
Background technology
In the last few years, increasing concern was received by the advantages such as the orthopedic fixation device such as absorbable bone peg, hone lamella tool takes out without the need to second operation because of degradable, stress-shielding effect is little of degradable high polymer material as the processing such as polylactic acid, polyglycolic acid preparation.But with being orthopedic instrument, also there is the problems such as X-ray absorbability is weak, development effect is poor in them.All sterilizing process will be carried out before orthopedic instrument implant into body, but wound still can inevitably bacterial infection in operation and postoperative healing process, serious words can cause inflammation, implant is caused to lose efficacy, the more important thing is, the acid degradation products that Absorbable rod orthopedic instrument discharges gradually in degradation process and particulate matter all can cause surrounding body to produce inflammation, therefore, in the whole process of union of fracture, how Absorbable rod macromolecule orthopedic instrument effectively reduces the probability of bacterial infection, can promote that again the growth of surrounding bone tissue and other body tissue is one of key element of its implantation success simultaneously.
Nearest research shows: copper ion can promote collagen deposition and revascularization (Catherine Gerard, et al.Biomaterials, 31 (2010): 824-831), therefore, if copper ion is loaded in absorbable polymer orthopedic instrument, the regeneration of fracture area blood vessel can be promoted, accelerate the healing of fracture.In addition, copper ion is the indispensable micronutrient of health, it is the component of blood in human body in azurin, and for blood, nervus centralis and immune system, growth and the function of the internal organs such as hair, skin and skeletal tissue and brain regulating liver-QI, the heart have material impact.Copper ion also has bactericidal action, mainly through firmly adsorbing with electronegative microbial film, make protein coagulating, destroy the activity of cell synzyme, cause cell loss division growth ability and dead, 317L rustless steel as cupric shows good anti-microbial property (Ling Ren, et al.Materials Science and Engineering C, 32 (2012): 1204-1209) to staphylococcus aureus and escherichia coli.
Therefore, copper ion or copper ion are introduced in the absorbable polymer nail, hone lamella etc. of current Clinical practice, slow release copper ion in degradation process is used by Absorbable rod orthopaedics fixed apparatus, the regeneration of fracture area blood vessel can be promoted, accelerate the healing of fracture, meanwhile, the antimicrobial effect of copper effectively can reduce the probability of postoperative infection antibacterial, thus realizes high performance, the multifunction of Absorbable rod orthopedic instrument.
The Absorbable rod macromolecule orthopedic instrument of current Clinical practice does not have sterilization, promotes revascularization and developing function, and easily cause inflammation, healing cycle is long, and cannot carry out X-ray periodic diagnosis and monitoring to its degraded and absorbed behavior in implantation process in vivo.Copper ion is introduced in such orthopedic instrument, slow release copper ion in degradation process is used by Absorbable rod orthopaedics fixed apparatus, the regeneration of fracture area blood vessel can be promoted, accelerate the healing of fracture, simultaneously, the antimicrobial effect of copper effectively can reduce the probability of postoperative infection antibacterial, thus realizes high performance, the multifunction of Absorbable rod orthopedic instrument.But due to the salt of cupric or ceramic particle and polymer wellability poor, interface cohesion is undesirable, and it adds membership and worsens the inherently undesirable mechanical property of such orthopedic instrument.
Summary of the invention
Technical problem: the object of this invention is to provide and a kind of there is Absorbable rod orthopedic instrument promoting revascularization function and preparation method thereof, namely by selecting desirable degradable carrier material and load technology, promote that the copper ion payload of revascularization biological effect is in Absorbable rod high molecular polymer orthopedic instrument by having, make in this Absorbable rod high molecular polymer orthopedic instrument use procedure in Operation body, by the degraded of self, initiatively discharge appropriate copper ion, reach and promote fracture site revascularization, the object of healing acceleration.Desirable copper ion carrier material self should also have degradable characteristic, meanwhile, should improve the loading content of copper ion in Absorbable rod high molecular polymer orthopedic instrument as far as possible, to promote the promotion revascularization performance of orthopedic instrument.Therefore, the key technical problem that the present invention solves further comprises the strengthening and toughening technology etc. of the selection of degradable carrier material, the load technology that can improve copper ion load capacity, degradable polymer.
Technical scheme: for achieving the above object, of the present inventionly a kind ofly can promote that the absorbable orthopedic instrument material of revascularization is in the polymer for the Graphene of strengthening and toughening by Absorbable rod high molecular polymer and Dispersed precipitate, load is made up of the degradable carrier material of copper ion, and be prepared from through thermal pressure molding, the copper ion that can promote revascularization can be slowly released in use degradation process, wherein, carrier material is that surface has the pure magnesium of the porous ceramic layer of hydroxyl apatite phase or magnesium alloy silk material or sheet material, adopt the dual carrying method that electrophoresis-micro-arc oxidation and chemical impregnation ion-exchange reactions method are compounded to form, by copper ion load on a support material, the volume fraction of described carrier material is 10% ~ 75%, the micropore size of its porous surface ceramic layer is 1 ~ 50 μm, thickness is 1 ~ 100 μm, the percent by volume of Graphene is 0.01% ~ 5%.
Absorbable rod high molecular polymer is absorbable polylactic acid, polyglycolic acid, polycaprolactone, Polyethylene Glycol, polyamide a kind of or wherein two or more their copolymer or blend.
Of the present inventionly can promote that the concrete preparation process of the preparation method of the absorbable orthopedic instrument material of revascularization is as follows:
1) processing of degradable carrier material: the pure magnesium or magnesium alloy that are used as carrier material are made a material or sheet material by drawing, rolling or pressing method;
2) the first load of electrophoresis-micro-arc oxidation of copper ion: by the Cu (OH) prepared in advance
2colloid solution joins in the alkaline electrolyte containing Hydroxyapatite nanoparticles end, the first supported copper ion processing of electrophoresis-differential arc oxidation is carried out to the pure magnesium of carrier material or magnesium alloy silk material or sheet material, electrophoresis-differential arc oxidation voltage is 100 ~ 600V, and the processing time is 2 ~ 60min;
3) the chemical impregnation ion-exchange reactions secondary load of copper ion: in step 2) basis on, it is 1 × 10 that the pure magnesium of first for electrophoresis-differential arc oxidization surface supported copper ion or magnesium alloy silk material or sheet material carrier material are impregnated into concentration again
-5~ 1 × 10
-3the CuSO of mol/L
4in solution, water bath with thermostatic control temperature is 20 ~ 90 DEG C, and dip time 2 ~ 12 hours carries out the load of second time copper ion by chemical impregnation ion-exchange reactions;
4) processing and forming of orthopedic instrument: the polymer paste formed through organic solvent dissolution or high-temperature fusion is mixed homogeneously with Graphene and forms mixed slurry, passing through dipping or coating processes and load again has the carrier material compound of copper ion to make prefabricated blank, or first load had the carrier material of copper ion to be arranged in mold cavity, reinject aforementioned mixed slurry, then, bar or sheet material is prepared into by forming method processing such as hot moulding, extruding, injection moulding or drawings, then the orthopedic instrument of machined one-tenth desired structure.
Beneficial effect: beneficial effect of the present invention is as follows:
1) this Absorbable rod orthopedic instrument has promotion revascularization function, by selecting desirable carrier material and load technology, promote that the copper ion payload of revascularization biological effect is in Absorbable rod high molecular polymer orthopedic instrument by having, make in this Absorbable rod high molecular polymer orthopedic instrument use procedure in Operation body, by the degraded of self, initiatively discharge appropriate copper ion, reach and promote fracture site revascularization, the object of healing acceleration, and copper ion is loaded in the oxide ceramic layer slower than magnesium alloy degradation speed, there is the ability of long-acting promotion fracture site revascularization.
2) the dual composite load method that special electrophoresis-micro-arc oxidation and chemical impregnation ion-exchange reactions method are formed is employed, related between two kinds of carrying methods, it not simple combination, the load capacity of copper ion can be improved, thus promote the promotion revascularization performance of Absorbable rod orthopedic instrument.Traditional, single micro-arc oxidation or chemical conversion embrane method etc. can prepare the oxide ceramic layer of cupric on magnesium alloy materials surface, if but the salt of solubility cupric is directly dissolved in differential arc oxidation electrolyte solution goes, the efficiency that copper ion participates in film forming is very low, cause copper ion load capacity not enough, thus do not have the effect promoting revascularization.In order to overcome this difficulty, present invention employs the two step composite load technology that electrophoresis-micro-arc oxidation and chemical impregnation ion-exchange reactions method are formed, the first step is at the preliminary supported copper ion of carrier material Mg alloy surface with electrophoresis-micro-arc oxidation, the salt of solubility cupric is not directly directly dissolved in electrolyte solution and goes by the method, but be prepared into the colloid solution of cupric, add again in alkaline electrolyte, colloidal solid can adsorb anion thus electronegative, according to colloidal theory, electrophoresis directed movement can be there is in charged colloidal particle under electric field action, based on this principle, under electric field action, containing copper colloid particle anode electrophoresis motion, the oxidation ceramic layer containing copper ion is generated at the pure magnesium of anode or magnesium alloy surfaces of carrier materials.Meanwhile, magnesium alloy surfaces of carrier materials arc differential oxide ceramic layer has microcellular structure, and cupric colloidal particle can enter micropore inside by electrophoresis motion, increases the load capacity of copper ion further.Second step is that the carrier material that the surface first step obtained has a copper ions porous ceramic layer of hydroxyapatite is immersed in the solution containing copper ion again, to give full play to the ion-exchange reactions ability of the powerful load capacity of micropore in porous ceramic layer and hydroxyapatite phase, thus, significantly increase saturation and the load capacity of copper ion further.Above-mentioned two step composite load technical schemes can improve the loading content of copper ion in Absorbable rod high molecular polymer orthopedic instrument, the function of the promotion revascularization of General Promotion orthopedic instrument to greatest extent.
3) there is long-acting bactericidal effect.In Absorbable rod orthopedic instrument of the present invention, the copper ion of load has antibacterial functions, in Absorbable rod orthopedic instrument degradation process, can slowly release copper ion, thus ensures long-acting bactericidal effect.
4) there is developing function.In Absorbable rod orthopedic instrument of the present invention, the copper ion of load has excellent absorption of x-rays ability, is conducive to the degraded and absorbed behavior of Post operation to implant devices and carries out X-ray periodic diagnosis and monitoring.
5) there is good biocompatibility, Absorbable rod performance and mechanical property.Absorbable rod high molecular polymer selected by Absorbable rod orthopedic instrument of the present invention and copper ion carrier material are the bio-medical material with good biocompatibility and degradability, can be absorbed by organism degrades or be excreted by blood circulation, and take out without the need to second operation, in addition, Graphene and copper ion carrier material-magnesium alloy silk material or sheet material form certain strengthening and toughening effect to Absorbable rod high molecular polymer orthopedic instrument.
Detailed description of the invention
In a kind of Absorbable rod orthopedic instrument that can promote revascularization of the present invention and preparation method thereof, described orthopedic instrument material is by Absorbable rod high molecular polymer, Dispersed precipitate is in the polymer for the Graphene of strengthening and toughening, load is made up of the degradable carrier material of copper ion, the copper ion that can promote revascularization can be slowly released in use procedure, wherein, the dual composite load technology that copper ion is formed by special electrophoresis-micro-arc oxidation and chemical impregnation ion-exchange reactions method is contained on the pure magnesium of hydroxyapatite porous ceramic layer or magnesium alloy silk material or sheet material carrier material by payload on surface, the volume fraction of described pure magnesium or magnesium alloy silk material or sheet material carrier material is 10% ~ 75%, the micropore size of its porous surface ceramic layer is 1 ~ 50 μm, thickness is 1 ~ 100 μm, the percent by volume of Graphene is 0.01% ~ 5%, the concrete preparation process of this orthopedic instrument is as follows:
1) processing of degradable carrier material: pure for carrier material magnesium or magnesium alloy are made a material or sheet material by drawing, rolling or pressing method.Because pure magnesium or magnesium alloy self are exactly a kind of degradable medical metal, having good biocompatibility, is a kind of degradable carrier material of desirable copper ion; Simultaneously, carrier material is processed filamentation material or sheet material, the directed potentiation of silk material or sheet material can be utilized, effectively make up the deterioration effect of the mechanical property may brought after general carrier material enters polymer, while the payload of copper ion can be realized, do not reduce again the mechanical property of polymer.
2) the first load of electrophoresis-micro-arc oxidation of copper ion: by the Cu (OH) prepared in advance
2colloid solution joins in the differential arc oxidation alkaline electrolyte containing Hydroxyapatite nanoparticles end, the pure magnesium of antianode carrier material or magnesium alloy silk material or sheet material carry out the first supported copper ion processing of electrophoresis-differential arc oxidization surface, electrophoresis-differential arc oxidation voltage is 100 ~ 600V, and the time is 2 ~ 60min.According to colloidal theory; electrophoresis directed movement can be there is in charged colloidal particle under electric field action; based on this principle; cupric colloid is added in alkaline electrolyte; colloidal solid can adsorb anion thus electronegative; afterwards under electric field action, containing copper colloid particle anode electrophoresis motion, generate the oxidation ceramic layer containing copper ion at pure magnesium or magnesium alloy surfaces of carrier materials.Meanwhile, magnesium alloy surfaces of carrier materials arc differential oxide ceramic layer has microcellular structure, and cupric colloidal particle can enter micropore inside by electrophoresis motion, increases the load capacity of copper ion further.Meanwhile, also add Hydroxyapatite nanoparticles end in electrolyte, therefore, after this process, surfaces of carrier materials can form the copper ions porous ceramic layer containing hydroxyapatite.
3) the chemical impregnation ion-exchange reactions secondary load of copper ion: in step 2) basis on, it is 1 × 10 that the pure magnesium of first for electrophoresis-differential arc oxidization surface supported copper ion or magnesium alloy silk material or sheet material carrier material are impregnated into concentration again
-5~ 1 × 10
-3the CuSO of mol/L
4in solution, water bath with thermostatic control temperature is 20 ~ 90 DEG C, and dip time 2 ~ 12 hours carries out the load of second time copper ion by chemical impregnation ion-exchange reactions.The special crystal structure that hydroxyapatite has makes it have very strong ion-exchange capacity, and meanwhile, the pore structure of porous ceramic layer also can improve the load capacity of copper ion further.Therefore, by step 2) surface that the obtains carrier material with the copper ions porous ceramic layer of hydroxyapatite is immersed in the solution containing copper ion again, the load capacity of micropore in porous ceramic layer and the ion-exchange reactions ability of hydroxyapatite phase can be given full play to, thus, significantly increase saturation and the load capacity of copper ion.
4) processing and forming of orthopedic instrument: after the polymer paste formed through organic solvent dissolution or high-temperature fusion is mixed homogeneously with Graphene, passing through dipping or coating processes and load again has the carrier material compound of copper ion to make prefabricated blank, or first load had the carrier material of copper ion to be arranged in mold cavity, reinject mixed slurry, then, bar or sheet material is prepared into by forming method processing such as hot moulding, extruding, injection moulding or drawings, then the orthopedic instrument of machined one-tenth desired structure.Graphene has good biocompatibility and excellent specific strength, specific stiffness, has good strengthening and toughening effect to degradable polymer.
Described Absorbable rod orthopedic instrument that can promote revascularization and preparation method thereof, is characterized in that: Absorbable rod high molecular polymer is absorbable polylactic acid, polyglycolic acid, polycaprolactone, Polyethylene Glycol, polyamide a kind of or wherein two or more their copolymer or blend.
Embodiment 1
It is polylactic acid that the degradable selected absorbs high molecular polymer, and the load carriers of copper ion is pure magnesium, and volume fraction is 25%, and preparation process is as follows:
1) the pre-pure magnesium as carrier is drawn into the silk material that diameter is 0.3mm;
2) Cu (OH) is prepared
2colloid solution, carries out electrophoresis-differential arc oxidation process: get 0.0005mol/L CuSO
4solution and each 1L of 0.0005mol/L NaOH solution are mixed to get Cu (OH)
2colloid solution.Measuring 500mL colloid solution joins in 5L micro-arc oxidation electrolyte, and electrolyte main component is 10g/L sodium silicate, 2g/LNaOH and 8g/L hydroxyapatite nanoparticle.Be dipped in wherein by magnesium silk material, apply 420V voltage, carry out the electrophoresis-differential arc oxidation process of 20 minutes, make its surface in situ generate the hydroxylapatite ceramic protective layer of one deck supported copper ion, the mean pore size of ceramic layer is 25 μm, and average thickness is 70 μm;
3) the magnesium silk material after differential arc oxidation being impregnated into concentration is 1 × 10
-4the CuSO of mol/L
4solution, water bath with thermostatic control temperature is 50 DEG C, and the chemical impregnation response time is 4 hours;
4) mix with the magnesium silk material of above-mentioned process, Graphene (volume fraction is 0.05%) after PLLA polymer being heated to 190 DEG C of meltings, be prepared into bar, the fixator for orthopedics department parts such as machined one-tenth pin, screw, nail by hot-extrusion method processing.
Embodiment 2
The degradable selected absorbs the polymer P GLA that high molecular polymer is polylactic acid and polyglycolic acid, and the carrier of supported copper ion is AZ31B magnesium alloy, and volume fraction is 40%, and preparation process is as follows:
1) magnesium alloy is rolled into the sheet material of 0.5mm;
2) Cu (OH) is prepared
2colloid solution, carries out electrophoresis-differential arc oxidation process: get 0.001mol/L CuSO
4solution and each 1L of 0.001mol/L NaOH solution are mixed to get Cu (OH)
2colloid solution.Getting 1L colloid solution joins in 10L micro-arc oxidation electrolyte, electrolyte main component is 8g/L sodium silicate, 2g/L NaOH, 10g/L hydroxyapatite nanoparticle, magnesium alloy plate is dipped in wherein, apply 380V voltage, carry out the electrophoresis-differential arc oxidation process of 20 minutes, make its surface in situ generate the ceramic protective layer of supported copper ion, the mean pore size of ceramic layer is 30 μm, and average thickness is 80 μm;
3) magnesium alloy plate after differential arc oxidation being impregnated into concentration is 4 × 10
-4the CuSO of mol/L
4in solution, water bath with thermostatic control temperature is 60 DEG C, and the chemical impregnation response time is 3 hours;
4) by magnesium sheet material, Graphene (volume fraction the is 0.5%) compound of the chloroform soln and above-mentioned process that are dissolved with polymer P GLA, after vacuum drying, sheet material is prepared into by the processing of hot moulding method, more machined one-tenth hone lamella.
Embodiment 3
It is polyglycolic acid (PGA) that the degradable selected absorbs high molecular polymer matrix, and the carrier of supported copper ion is QE22 magnesium alloy, and volume fraction is 30%, and preparation process is as follows:
1) magnesium alloy is drawn into the silk material that diameter is 0.5mm;
2) Cu (OH) is prepared
2colloid solution, carries out electrophoresis-differential arc oxidation process: get 0.0005mol/L CuSO
4solution and each 1L of 0.0006mol/L NaOH solution are mixed to get Cu (OH)
2colloid solution.Measuring 500mL colloid solution joins in 5L micro-arc oxidation electrolyte, bath composition is mainly 10g/L sodium silicate, 3g/LNaOH and 10g/L hydroxyapatite nanoparticle, magnesium alloy silk material is dipped in wherein, apply 380V voltage, carry out the electrophoresis-differential arc oxidation process of 15 minutes, make its surface in situ generate the hydroxylapatite ceramic protective layer of one deck supported copper ion, the mean pore size of ceramic layer is 25 μm, and average thickness is 90 μm;
3) magnesium alloy silk material after differential arc oxidation being impregnated into concentration is 5 × 10
-4the CuSO of mol/L
4in solution, water bath with thermostatic control temperature is 80 DEG C, and the chemical impregnation response time is 5 hours;
4) with the magnesium silk material of above-mentioned process, Graphene (volume fraction is 2%) compound after PGA polymer being heated to 180 DEG C of meltings, bar is prepared into by the processing of hot pull method, 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 used to limit enforcement of the present invention and interest field, and all equivalences made 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 (3)
1. one kind can promote the absorbable orthopedic instrument material of revascularization, it is characterized in that: described orthopedic instrument material is in the polymer for the Graphene of strengthening and toughening by Absorbable rod high molecular polymer and Dispersed precipitate, load is made up of the degradable carrier material of copper ion, and be prepared from through thermal pressure molding, the copper ion that can promote revascularization can be slowly released in use degradation process, wherein, carrier material is that surface has the pure magnesium of the porous ceramic layer of hydroxyl apatite phase or the silk material of magnesium alloy or sheet material, adopt the dual carrying method that electrophoresis-micro-arc oxidation and chemical impregnation ion-exchange reactions method are compounded to form, by copper ion load on a support material, the volume fraction of described carrier material is 10% ~ 75%, the micropore size of its porous surface ceramic layer is 1 ~ 50 μm, thickness is 1 ~ 100 μm, the percent by volume of Graphene is 0.01% ~ 5%, all the other are Medical absorbable high molecular polymer.
2. the absorbable orthopedic instrument material that can promote revascularization according to claim 1, is characterized in that: Absorbable rod high molecular polymer is absorbable polylactic acid, polyglycolic acid, polycaprolactone, Polyethylene Glycol, polyamide a kind of or wherein two or more their copolymer or blend.
3. can promote a preparation method for the absorbable orthopedic instrument material of revascularization as claimed in claim 1, it is characterized in that: the concrete preparation process of this orthopedic instrument is as follows:
1) processing of degradable carrier material: the pure magnesium or magnesium alloy that are used as carrier material are made a material or sheet material by drawing, rolling or pressing method;
2) the first load of electrophoresis-micro-arc oxidation of copper ion: by the Cu (OH) prepared in advance
2colloid solution joins in the alkaline electrolyte containing Hydroxyapatite nanoparticles end, the first supported copper ion processing of electrophoresis-differential arc oxidation is carried out to the silk material of the pure magnesium of carrier material or magnesium alloy or sheet material, electrophoresis-differential arc oxidation voltage is 100 ~ 600V, and the processing time is 2 ~ 60min;
3) the chemical impregnation ion-exchange reactions secondary load of copper ion: in step 2) basis on, it is 1 × 10 that the pure magnesium of first for electrophoresis-differential arc oxidization surface supported copper ion or the silk material of magnesium alloy or sheet material carrier material are impregnated into concentration again
-5~ 1 × 10
-3the CuSO of mol/L
4in solution, water bath with thermostatic control temperature is 20 ~ 90 DEG C, and dip time 2 ~ 12 hours carries out the load of second time copper ion by chemical impregnation ion-exchange reactions;
4) processing and forming of orthopedic instrument: the polymer paste formed through organic solvent dissolution or high-temperature fusion is mixed homogeneously with Graphene and forms mixed slurry, passing through dipping or coating processes and load again has the carrier material compound of copper ion to make prefabricated blank, or first load had the carrier material of copper ion to be arranged in mold cavity, reinject aforementioned mixed slurry, then, bar or sheet material is prepared into by hot moulding, extruding, injection moulding or the processing of drawing forming method, then the orthopedic instrument of machined one-tenth desired structure.
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| CN104127916B (en) * | 2014-07-15 | 2015-11-18 | 东南大学 | Have antibacterial and promote osteogenesis function absorbable orthopedic instrument material and preparation method |
| CN108379658B (en) * | 2018-02-06 | 2021-03-02 | 中国科学院金属研究所 | Orthopedic implant device with copper-containing coating and method of making the same |
| CN108950654A (en) * | 2018-08-30 | 2018-12-07 | 齐昊 | A kind of antibacterial applications of copper sulphate in painting dressing automobiles cathode electrodip painting |
| CN112723500B (en) * | 2019-10-28 | 2023-10-27 | 华东理工大学 | Environment-friendly high-efficiency nano copper ion compound and preparation method and application thereof |
| CN110950333B (en) * | 2019-12-16 | 2021-09-14 | 天新福（北京）医疗器材股份有限公司 | Method for preparing graphene oxide material |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101337090A (en) * | 2008-08-29 | 2009-01-07 | 乐普（北京）医疗器械股份有限公司 | Composite coating magnesium/magnesium alloy biology device and preparation method thereof |
| CN102526804A (en) * | 2012-03-06 | 2012-07-04 | 四川大学华西医院 | Coloboma repairing material |
| 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 |
Family Cites Families (2)
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| WO2011096402A1 (en) * | 2010-02-03 | 2011-08-11 | 独立行政法人物質・材料研究機構 | Biocompatible device |
-
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101337090A (en) * | 2008-08-29 | 2009-01-07 | 乐普（北京）医疗器械股份有限公司 | Composite coating magnesium/magnesium alloy biology device and preparation method thereof |
| CN102526804A (en) * | 2012-03-06 | 2012-07-04 | 四川大学华西医院 | Coloboma repairing material |
| 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 |
Non-Patent Citations (2)
| Title |
|---|
| "In-vitro assessments of micro arc oxidized ceramic films on AZ31 magnesium implant:Degradation and cell-surface response";A. Seyfooria 等;《Progress in Natural Science:Materials International》;20130719;第23卷(第4期);第425-433页 * |
| 逯平 等."不同镁合金支架材料MAO/PLLA复合膜研究".《稀有金属材料与工程》.2011,第40卷(第12期),第2232-2235页. * |
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