CN106902391A - A kind of magnesium alloy is implanted into composite material and its preparation and application - Google Patents
A kind of magnesium alloy is implanted into composite material and its preparation and application Download PDFInfo
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- CN106902391A CN106902391A CN201611262987.XA CN201611262987A CN106902391A CN 106902391 A CN106902391 A CN 106902391A CN 201611262987 A CN201611262987 A CN 201611262987A CN 106902391 A CN106902391 A CN 106902391A
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- magnesium alloy
- implant
- arc oxidation
- layer
- abutment
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- 229910000861 Mg alloy Inorganic materials 0.000 title claims abstract description 181
- 239000002131 composite material Substances 0.000 title claims abstract description 53
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 229910052588 hydroxylapatite Inorganic materials 0.000 claims abstract description 110
- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical compound [OH-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 claims abstract description 110
- 239000007943 implant Substances 0.000 claims abstract description 85
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 80
- 230000003647 oxidation Effects 0.000 claims abstract description 75
- 229920000747 poly(lactic acid) Polymers 0.000 claims abstract description 40
- 239000004626 polylactic acid Substances 0.000 claims abstract description 40
- 238000004070 electrodeposition Methods 0.000 claims abstract description 39
- 239000000463 material Substances 0.000 claims abstract description 39
- 210000000988 bone and bone Anatomy 0.000 claims abstract description 38
- 239000011737 fluorine Substances 0.000 claims abstract description 37
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 37
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 36
- 238000000034 method Methods 0.000 claims abstract description 36
- 238000007745 plasma electrolytic oxidation reaction Methods 0.000 claims abstract description 30
- 238000002513 implantation Methods 0.000 claims abstract description 28
- 239000000843 powder Substances 0.000 claims abstract description 26
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- 230000001771 impaired effect Effects 0.000 claims abstract description 16
- 238000005470 impregnation Methods 0.000 claims abstract description 3
- 239000010410 layer Substances 0.000 claims description 165
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical group O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 40
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 39
- 239000007788 liquid Substances 0.000 claims description 37
- 239000008367 deionised water Substances 0.000 claims description 31
- 229910021641 deionized water Inorganic materials 0.000 claims description 31
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 20
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 20
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 20
- 230000007547 defect Effects 0.000 claims description 15
- 239000007789 gas Substances 0.000 claims description 15
- 239000000243 solution Substances 0.000 claims description 15
- 238000000498 ball milling Methods 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 13
- 210000001161 mammalian embryo Anatomy 0.000 claims description 13
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 12
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 12
- 239000011159 matrix material Substances 0.000 claims description 12
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 12
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 11
- 235000019441 ethanol Nutrition 0.000 claims description 11
- 125000005909 ethyl alcohol group Chemical group 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 11
- 239000002904 solvent Substances 0.000 claims description 11
- 238000011282 treatment Methods 0.000 claims description 11
- 229910052786 argon Inorganic materials 0.000 claims description 10
- 239000012298 atmosphere Substances 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 10
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims description 10
- 229910001220 stainless steel Inorganic materials 0.000 claims description 10
- 238000000547 structure data Methods 0.000 claims description 10
- 238000002591 computed tomography Methods 0.000 claims description 9
- 238000000151 deposition Methods 0.000 claims description 9
- 239000010935 stainless steel Substances 0.000 claims description 9
- 239000002253 acid Substances 0.000 claims description 8
- 230000011218 segmentation Effects 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 6
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 claims description 6
- 239000012530 fluid Substances 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 6
- 229910052697 platinum Inorganic materials 0.000 claims description 6
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 6
- 239000011435 rock Substances 0.000 claims description 6
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 6
- 239000001509 sodium citrate Substances 0.000 claims description 6
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 claims description 6
- HRXKRNGNAMMEHJ-UHFFFAOYSA-K trisodium citrate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 claims description 6
- 229960000281 trometamol Drugs 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 230000012010 growth Effects 0.000 claims description 5
- 238000002791 soaking Methods 0.000 claims description 5
- 238000007654 immersion Methods 0.000 claims description 4
- 238000005498 polishing Methods 0.000 claims description 4
- 230000001681 protective effect Effects 0.000 claims description 4
- 229940038773 trisodium citrate Drugs 0.000 claims description 4
- 238000010792 warming Methods 0.000 claims description 4
- 238000000137 annealing Methods 0.000 claims description 3
- -1 fluorine hydroxyl phosphorus Chemical compound 0.000 claims description 3
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 3
- 229910000406 trisodium phosphate Inorganic materials 0.000 claims description 2
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims 2
- DMGNFLJBACZMRM-UHFFFAOYSA-N O[P] Chemical compound O[P] DMGNFLJBACZMRM-UHFFFAOYSA-N 0.000 claims 1
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 claims 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims 1
- 229940075397 calomel Drugs 0.000 claims 1
- 150000002576 ketones Chemical class 0.000 claims 1
- 239000001301 oxygen Substances 0.000 claims 1
- 229910052760 oxygen Inorganic materials 0.000 claims 1
- 239000002356 single layer Substances 0.000 claims 1
- 230000007797 corrosion Effects 0.000 abstract description 18
- 238000005260 corrosion Methods 0.000 abstract description 18
- 230000010287 polarization Effects 0.000 abstract description 6
- 238000012360 testing method Methods 0.000 abstract description 6
- 238000010276 construction Methods 0.000 abstract description 4
- 210000000963 osteoblast Anatomy 0.000 abstract description 2
- 210000004409 osteocyte Anatomy 0.000 abstract description 2
- 210000004027 cell Anatomy 0.000 description 17
- 239000011248 coating agent Substances 0.000 description 15
- 238000000576 coating method Methods 0.000 description 15
- 239000011777 magnesium Substances 0.000 description 12
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 11
- 229910052749 magnesium Inorganic materials 0.000 description 11
- 230000008569 process Effects 0.000 description 11
- 239000000758 substrate Substances 0.000 description 10
- 229910001868 water Inorganic materials 0.000 description 9
- 239000000956 alloy Substances 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 6
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 6
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Natural products OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 5
- 229910045601 alloy Inorganic materials 0.000 description 5
- 239000011247 coating layer Substances 0.000 description 5
- 235000019263 trisodium citrate Nutrition 0.000 description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 4
- 230000004913 activation Effects 0.000 description 4
- 238000002242 deionisation method Methods 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 3
- 239000011575 calcium Substances 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 230000005518 electrochemistry Effects 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000011224 oxide ceramic Substances 0.000 description 3
- 229910052574 oxide ceramic Inorganic materials 0.000 description 3
- 239000008363 phosphate buffer Substances 0.000 description 3
- 238000005245 sintering Methods 0.000 description 3
- 239000011780 sodium chloride Substances 0.000 description 3
- 239000006144 Dulbecco’s modified Eagle's medium Substances 0.000 description 2
- 239000012981 Hank's balanced salt solution Substances 0.000 description 2
- 241001272567 Hominoidea Species 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 229910001069 Ti alloy Inorganic materials 0.000 description 2
- 229960000583 acetic acid Drugs 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 229910052586 apatite Inorganic materials 0.000 description 2
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- 239000012362 glacial acetic acid Substances 0.000 description 2
- 235000011187 glycerol Nutrition 0.000 description 2
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
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- 235000015097 nutrients Nutrition 0.000 description 2
- VSIIXMUUUJUKCM-UHFFFAOYSA-D pentacalcium;fluoride;triphosphate Chemical compound [F-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O VSIIXMUUUJUKCM-UHFFFAOYSA-D 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 238000004062 sedimentation Methods 0.000 description 2
- 239000012890 simulated body fluid Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
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- 238000004506 ultrasonic cleaning Methods 0.000 description 2
- 229910014497 Ca10(PO4)6(OH)2 Inorganic materials 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- 241000521257 Hydrops Species 0.000 description 1
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- 241000283973 Oryctolagus cuniculus Species 0.000 description 1
- 108010019160 Pancreatin Proteins 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- 206010060872 Transplant failure Diseases 0.000 description 1
- ZQBZAOZWBKABNC-UHFFFAOYSA-N [P].[Ca] Chemical group [P].[Ca] ZQBZAOZWBKABNC-UHFFFAOYSA-N 0.000 description 1
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- 239000003462 bioceramic Substances 0.000 description 1
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- 210000000481 breast Anatomy 0.000 description 1
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- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 159000000007 calcium salts Chemical class 0.000 description 1
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- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical class ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
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- 238000005137 deposition process Methods 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- CGMRCMMOCQYHAD-UHFFFAOYSA-J dicalcium hydroxide phosphate Chemical compound [OH-].[Ca++].[Ca++].[O-]P([O-])([O-])=O CGMRCMMOCQYHAD-UHFFFAOYSA-J 0.000 description 1
- 230000001079 digestive effect Effects 0.000 description 1
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 description 1
- 229910000397 disodium phosphate Inorganic materials 0.000 description 1
- 238000010891 electric arc Methods 0.000 description 1
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- 238000005868 electrolysis reaction Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000002389 environmental scanning electron microscopy Methods 0.000 description 1
- 229940088598 enzyme Drugs 0.000 description 1
- 229910052564 epsomite Inorganic materials 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 235000011389 fruit/vegetable juice Nutrition 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 230000035876 healing Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000001727 in vivo Methods 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
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- 210000000496 pancreas Anatomy 0.000 description 1
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- 238000011056 performance test Methods 0.000 description 1
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- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 description 1
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Classifications
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- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
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- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
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- A61L27/30—Inorganic materials
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- A61L27/28—Materials for coating prostheses
- A61L27/34—Macromolecular materials
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/50—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
- A61L27/54—Biologically active materials, e.g. therapeutic substances
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- A—HUMAN NECESSITIES
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- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/50—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
- A61L27/56—Porous materials, e.g. foams or sponges
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
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Abstract
The invention discloses a kind of magnesium alloy implantation composite material and its preparation and application, the magnesium alloy implantation composite material is magnesium alloy abutment of implant through the model that 3D printing makes with magnesium alloy powder, differential arc oxidation film layer is formed using micro-arc oxidation on magnesium alloy abutment of implant surface, then hydroxyapatite layer or fluorine hydroxyapatite layer are formed using electrochemical deposition method in micro-arc oxidation films layer surface again, finally forms polylactic acid layers in hydroxyapatite layer or fluorine hydroxyapatite layer surface impregnation；The present invention is from the data acquisition of original impaired bone structure to the preparation of final multicoat composite construction, realize the personalized exploitation of magnesium alloy implant material, obtain high-quality magnesium alloy implantation composite material, wherein polarization test shows that its corrosion resistance obtains 4 liftings of the order of magnitude, and there is the composite material of magnesium alloy after prepared by osteoblasts cultivation display more preferable osteocyte to promote ability.
Description
(1) technical field
The present invention relates to a kind of magnesium alloy multi-layer biological composite with good biocompatibility and preparation method thereof,
I.e. by carrying out the scanning of multi-layer spiral CT to the impaired bone structure of human body, initial data is then carried out into treatment reparation, then pass through
Prepared by the methods such as 3D printing, differential arc oxidation, electrochemical deposition have magnesium alloy/differential arc oxidation film layer/hydroxyapatite (or fluorine hydroxyl
Base apatite)/PLA boiomacromolecule Rotating fields implantation composite material.
(2) background technology
At present in clinical practice field, medical metal material mainly has stainless steel, cobalt-base alloys and titanium alloy etc. several big
Class material, but there are some drawbacks in this few class material, and such as 316L stainless steels produce gap rotten sometimes after human body is implanted into
The problems such as erosion, fretting corrosion and fatigue corrosion rupture.Titanium alloy and stainless steel material all have larger elastic mould value,
Stress-shielding effect can be caused in human body, causes bone tissue to heal slow, graft failure can be caused when serious.Additionally, stainless steel
Bio-inert material is with titanium-base alloy, it is necessary to operation taking-up again, increased pain and the doctor of patient after bone tissue reparation
Treatment expense is born.It is heavier and magnesium and magnesium alloy materials are widely paid close attention to its good biodegradability properties and biocompatibility
What is wanted is magnesium alloy close with the density and mechanical property of bone structure, can significantly avoid stress-shielding effect, improves implantation
Success rate.
The method for preparing biological medical magnesium alloy at present mainly includes：Smelting process, powder metallurgy and fused salt electrolysis process.But pass
System process has that technological operation degree-of-difficulty factor is big, power consumption is big in preparation process, high cost, automate it is low, from
And limit its extensive utilization in medical field；Powder metallurgic method sintering time in preparation process is short, is oxidized easily, difficult
To control setting rate and be difficult to obtain complex-shaped structure；The preparation process of discharge plasma sintering method it is relatively costly and
Must carry out under vacuum conditions.And new laser gain material manufacturing technology (3D printing), not only the advantage with high precision and
Real metallurgical binding can be reached in forming process, the shortcoming caused by magnesium alloy conventional fabrication processes is overcome.3D printing
Technology be based on mathematical model, with powdery metal or plastic or other material, by way of successively melting and piling up come
The technology of constructed object.Existing bioengineering field can carry out 3D printing in bone structure by multi-layer spiral CT three-dimensional rebuilding
The structure of aspect, the three-dimensional reconstruction based on multi-layer spiral CT improves modality conversion between entity world and digital world by common
Resolution ratio, can scan, edit and replication entity object, create accurate copy or optimization original paper.
The chemical property of magnesium is extremely active, cavernous oxide-film is easily generated in corrosive medium so that magnesium alloy
Mechanical performance reduction, influences the performance of implant.Zeng R C etc.【Zeng R C,Wolfgang D,Frank W,et
al.Progress and challenge formagnesium alloys as biomaterials[J]
.Adv.Eng.Mater.,2008,10(8):B3】Magnesium and its alloy be have studied in various simulated body fluids (simulated body
Fluid, SBF) in corrosive nature, its pH- potential diagram shows that magnesium alloy can occur Mg (s)+2H in aqueous2O(aq)→
H2(g)+Mg(OH)2S () is reacted and causes corrosion.Therefore, in order to improve the corrosion resistance of magnesium alloy, necessary surface is modified
The corrosion resistance of magnesium alloy can be significantly improved.Differential arc oxidization technique (Micro-arc oxidation, MAO) be it is a kind of recently
The process for modifying surface for growing up, the technology is that directly parent metal is become by micro-arc discharge area instantaneous high-temperature high-pressure sinter
Into oxide ceramics, and obtain thicker oxidation film.The activation of medical alloy surface oxide film is current tooth-planting material
A kind of most promising method in material surface active, can significantly improve stability of the magnesium alloy in human body.GUO Huixia
Deng【GUO Hui-xia,MA Ying,WANG Jing-song,et al.Corrosion behavior of micro-arc
oxidation coating onAZ91D magnesium alloy in NaCl solutions with different
concentrations[J].Trans.Nonferrous Met.Soc.China 22(2012)1786-1793.】Have studied micro-
The corrosion behavior of magnesium alloy AZ31 after arc oxidation processes in the NaCl solution of various concentrations, as a result shows, the corrosion of sample
Speed increases with the rising of chlorine ion concentration, but more untreated magnesium alloy, and sample etches performance is all obtained after differential of the arc treatment
To greatly being lifted.
Biomedical metallic material is poor in the presence of conductive, heat conductivility, contacts perishable with other metals, Metal ion release
The problems such as.In order to solve these problems, hydroxyapatite (HA:Ca10(PO4)6(OH)2) because its have good synosteosis performance,
Biocompatibility and widely paid close attention to.Hydroxyapatite has similar chemical composition and crystal structure with bone tissue, this
Just there is larger adhesive force in a short time after planting material implantation organism, material/bone interface can be made to form strong bonded, have
Beneficial to the initial maintenance of graft materials, can effectively suppress metal ion to the release in organism, hydroxyapatite may be used also in addition
To extend the service life of implant.But hydroxyapatite is easy to fatigue failure, for load implant, hydroxyapatite coat
Layer is even more and is easily come off from implant.Hydroxyapatite poor mechanical properties, its bending strength in itself is less than 100MPa.This
The success rate that implant is implanted into vivo can be substantially reduced.And by and the combination of magnesium alloy surface micro-arc oxidation can significantly carry
The binding ability of stability of the magnesium alloy high in human body, lifting hydroxyapatite layer and matrix.Current magnesium surface oxidation film
Activation it is important that how to form the oxidation film of surface hydroxyl apatite, usual way has two kinds：One is magnesium alloy
Surface active coating, i.e., processed by differential arc oxidation and directly generate the hydroxyapatite coat with bioactivity in Mg alloy surface
Layer；Another is magnesium surface activation modification, i.e., after processing metal surface, the oxide layer of magnesium is formed in magnesium surface, then by material
Material is placed in physiological environment or simulation physiological environment in the formation of its spatial induction HA.But both approaches are for preparing environment
With requirement higher.The activation modification of magnesium surface needs to be carried out in the environment of HTHP and has to operating environment among these
There is requirement higher, which has limited further applying for magnesium matrix hydroxyapatite coating layer.
The preparation of hydroxyapatite is carried out to the magnesium alloy substrate of differential arc oxidation pre-treatment using electrochemical deposition, more at present
Common hydro-thermal method prepares hydroxyapatite and compares with hot spray process, and the method can significantly reduce preparation temperature, improves experiment
Operability, is conducive to the popularization of magnesium alloy/hydroxyapatite composite.But the meeting in performance of simple electrodeposited coating
There is caducous tendency, causing the service life of coating reduces.Therefore, it is further to improve electro-deposition hydroxyapatite coating layer
Adhesion and composite biocompatibility, the hydroxyapatite layer to surface can carry out the system of boiomacromolecule coating
It is standby.The present invention carries out three-dimensional reconstruction by original impaired bone structure multi-slice Spiral CT, is carried out using 3D printing technique
The preparation of magnesium alloy materials, the differential arc oxidation for then carrying out surface to it is processed to improve the corrosion resistance of magnesium alloy substrate, and
Prepared for prepared by ensuing coating.It is prepared by the electrochemical deposition that hydroxyapatite coating layer is carried out in electrochemical deposition liquid,
And carry out boiomacromolecule layer film preparation, magnesium alloy multi-layer biological composite is realized by a series of PROCESS FOR TREATMENT
Preparation, obtain matching high, high performance composite construction.And so far, this systemic, high reproducibility, high-compatibility
The preparation of composite material of magnesium alloy have not been reported.
(3) content of the invention
It is an object of the present invention to provide a kind of magnesium alloy multi-layer biological composite with good biocompatibility and its system
Preparation Method, based on multi-layer spiral CT three-dimensional rebuilding, carries out the 3D printing of magnesium alloy abutment of implant and magnesium alloy is implanted into
Body matrix carries out a series of surface treatments such as differential arc oxidation, electrochemical deposition and boiomacromolecule layer preparation and prepares magnesium alloy plant
Enter body matrix/differential arc oxidation film layer/hydroxyapatite (HAP) or fluorine hydroxyapatite (FHAP) layer/PLA boiomacromolecule
The magnesium alloy implantation composite material of Rotating fields.The present invention solves magnesium alloy implant material poor corrosion resistance, degraded speed
Degree is fast, and the low problem of Gegenbaur's cell dependency improves the decay resistance and bioactivity of magnesium alloy substrate, is that magnesium alloy is planted
The further application for entering body material provides thinking.
The technical solution adopted by the present invention is：
The present invention provides a kind of magnesium alloy implantation composite material, and the magnesium alloy is implanted into composite material with magnesium alloy powder
The model made through 3D printing is magnesium alloy abutment of implant, is formed using micro-arc oxidation on magnesium alloy abutment of implant surface
Differential arc oxidation film layer (i.e. arc differential oxide ceramic layer), then forms hydroxyl in micro-arc oxidation films layer surface using electrochemical deposition method again
Base apatite layer or fluorine hydroxyapatite layer, finally form poly- breast in hydroxyapatite layer or fluorine hydroxyapatite layer surface impregnation
Acid layer (i.e. boiomacromolecule layer)；Differential arc oxidation liquid composition is used by the micro-arc oxidation：8~12g/L Na2SiO3, 8~
12g/L Na3PO4, 6~10g/L NaOH, 3~7g/L KF, 3~8g/L Na2CO3, 1~5g/L KOH, 50~100mL/L without
Water-ethanol, solvent is deionized water, pH value nature；Electrochemical deposition liquid composition is used by the hydroxyapatite layer：
0.042mol/L Ca(NO3)2、0.5mol/L NaNO3、0.025mol/L NH4H2PO4, 30-50mL/L absolute ethyl alcohols, 30-
50mL/L hydrogen peroxide, 0.004-0.006mol/L APES OP-21,0.1-0.2mol/L trisodium citrates, it is molten
Agent is deionized water, is 4.3-4.5 with trometamol and nitre acid for adjusting pH；The fluorine hydroxyapatite layer electrochemical deposition liquid is
To addition concentration 0.0008mol/L NaF in electrochemical deposition liquid used by hydroxyapatite layer.
Further, preferably differential arc oxidation liquid composition is：10g/L Na2SiO3、10g/L Na3PO4、8g/L NaOH、5g/L
KF、6g/L Na2CO3, 3g/L KOH, 75mL/L absolute ethyl alcohols, solvent is deionized water, pH value nature.It is preferred that electrochemical deposition
Liquid is constituted：0.042mol/L Ca(NO3)2、0.5mol/L NaNO3、0.025mol/L NH4H2PO4, 40mL/L absolute ethyl alcohols,
40mL/L hydrogen peroxide, 0.005mol/L APES OP-21,0.15mol/L trisodium citrates, solvent is deionization
Water, is 4.4 with trometamol and nitre acid for adjusting pH.The fluorine hydroxyapatite layer electrochemical deposition liquid is to hydroxyapatite layer
Concentration 0.0008mol/L NaF are added in electrochemical deposition liquid used.
Further, preferably described differential arc oxidation film layer thickness is 20 μm~30 μm, the hydroxyapatite layer or fluorine hydroxyl
Apatite layer thickness is 4 μm~6 μm.
Further, preferably described differential arc oxidation film layer is prepared as follows：It is with described magnesium alloy abutment of implant
Anode, stainless steel is negative electrode, is 550~650Hz in frequency in differential arc oxidation liquid, and the differential of the arc time is 15~30min, duty
Than being 15~30%, current density is 20A/cm2, operation temperature be room temperature (optimized frequency is 600Hz, differential of the arc time 20min,
Dutycycle is 20%, and current density is 20A/cm2, 23 DEG C of operation temperature) under the conditions of carry out differential arc oxidation reaction, after reaction terminates
Magnesium alloy abutment of implant is taken out, is cleaned by ultrasonic (preferably 15min) in deionized water, dried in 20-45 DEG C of baking oven, obtained
The magnesium alloy abutment of implant that surface forms micro-arc oxidation films Rotating fields is obtained, magnesium alloy abutment of implant/micro-arc oxidation films are designated as
Layer.
Further, preferably described hydroxyapatite layer or fluorine hydroxyapatite layer are prepared as follows：Formed with surface
The magnesium alloy abutment of implant of differential arc oxidation film layer is working electrode, and, used as to electrode, saturated calomel electrode is used as reference for platinized platinum
Electrode, in electrochemical deposition liquid, constant current mode, current density is 4-6mA/cm2(preferably 5mA/cm2), depositing temperature is 37 DEG C
Under conditions of carry out electrochemical deposition 90-150min (preferably 120min) after, described magnesium alloy abutment of implant is taken out, use
Deionized water is cleaned, and room temperature is dried；Immerse again in the NaOH aqueous solution of 1-2mol/L (preferably 2mol/L), 2- is soaked at 80 DEG C
4h (preferably 3h), is then cleaned repeatedly with deionized water, after room temperature is dried, in tube furnace under argon gas or vacuum protection atmosphere
In carry out the high temperature anneal, be warming up to 200 DEG C with the speed of 10 DEG C/min, be incubated 2h, obtain surface shape successively from outside to inside
Into hydroxyapatite layer or fluorine hydroxyapatite layer, the magnesium alloy abutment of implant of micro-arc oxidation films Rotating fields, magnesium alloy is designated as
Abutment of implant/differential arc oxidation film layer/hydroxyapatite layer or fluorine hydroxyapatite layer.The system of the fluorine hydroxyapatite layer
Standby is that electrochemical deposition liquid is changed to addition concentration 0.0008mol/L in electrochemical deposition liquid used by hydroxyapatite layer
NaF, other operations are identical.
Further, the thickness of preferably described polylactic acid layers is 5 μm~10 μm.
Further, preferably described polylactic acid layers are prepared as follows：Polylactic acid powder is added in dichloromethane, room
Warm uniform stirring 6 hours, obtains the PLA solution of mass concentration 2.5%；The PLA is 2.5 with dichloromethane mass ratio：
97.5；Surface is sequentially formed hydroxyapatite layer or fluorine hydroxyapatite layer, the magnesium alloy of differential arc oxidation film layer from outside to inside
In abutment of implant immersion PLA solution, after soaking at room temperature 20-30s, proposed with the constant speed of 15-25mm/min, logical
Room temperature is dried in wind kitchen, and then deionized water is cleaned, and room temperature is dried, that is, obtain and sequentially form from outside to inside polylactic acid layers, hydroxyl
Apatite layer or fluorine hydroxyapatite layer, the magnesium alloy implantation composite material of micro-arc oxidation films Rotating fields, are designated as magnesium alloy plant
Enter body matrix/differential arc oxidation film layer/hydroxyapatite layer or fluorine hydroxyapatite layer/polylactic acid layers.
Further, preferably described magnesium alloy abutment of implant is prepared as follows：(1) impaired bone structure is carried out into CT to sweep
Retouch, obtain the CT scan data of impaired bone structure, and be input to Materialise 3 d modeling softwares, carry out threshold value division, so
The noise for importing image is removed using region growth method afterwards, removal, the segmentation both injured bones structural region of redundant data is carried out；(2)
Segmentation is felt better behind damage bone structure region, further obtains impaired bone structure by Materialise 3 d modeling softwares opening operation
Three-dimensional structure data, realization initial data is switched into three-dimensional structure data, then will obtain three-dimensional structure data input UG
Software, obtains digitlization Cranial defect threedimensional model；(3) according to digitlization Cranial defect threedimensional model, design bone using CAD software and lack
Module is damaged, STL models are obtained；(4) by STL mode input 3D printing equipment, then by magnesium alloy powder in ball mill (XQM-0.4L
Planetary ball mill) in be well mixed, mill rotating speed be 250r/min, Ball-milling Time is 30min, employ nitrogen as be protect gas
Body, obtains the magnesium alloy powder after ball milling (preferable particle size is 40 μm~50 μm)；3D is added to beat the magnesium alloy powder after ball milling
Printing apparatus, are molded using laser 3D printing, and the power of laser is 100~200W (preferably 150W), sweep speed 20m/min, arteries and veins
1~3ms wide, frequency 0.0Hz, 2~3mm of defocusing amount, spot diameter 0.2mm, print, individual layer under argon gas or vacuum protection atmosphere
Print thickness 0.04mm, is printed according to STL models, obtains embryo material；The embryo material of acquisition is placed in electrochemical workstation
(IviumStat) in the electrolytic cell equipped with agitating device, polishing fluid is volume ratio 1 in electrolytic cell:1:20 perchloric acid, glycerine and
The mixed liquor of glacial acetic acid, in 30V constant voltage modes, liquid feeding nitrogen is cooled to -5 DEG C, and 100~200r/min of low whipping speed is (preferably
Carry out electrochemical polish operation under conditions of 150r/min), obtain the embryo material after electrochemical polish, then successively with absolute alcohol,
Acetone and deionized water are cleaned by ultrasonic, and dry at room temperature, obtain described magnesium alloy abutment of implant.
Further, preferably described magnesium alloy powder is AZ91D magnesium alloy powders, and particle diameter is 120 μm~150 μm.
The present invention also provides the preparation method that a kind of magnesium alloy is implanted into composite material, and methods described is：(1) will receive
Damaging bone structure carries out CT scan, obtains the CT scan data of impaired bone structure, and it is soft to be input to Materialise three-dimensional modelings
Part, carries out threshold value division, and the noise for importing image is then removed using region growth method, carries out removal, the segmentation of redundant data
Both injured bones structural region；(2) after damage bone structure region is felt better in segmentation, further opened by Materialise 3 d modeling softwares
Computing obtains the three-dimensional structure data of impaired bone structure, and initial data is switched to three-dimensional structure data by realization, then by acquisition
Three-dimensional structure data is input into UG softwares, obtains digitlization Cranial defect threedimensional model；(3) according to digitlization Cranial defect threedimensional model,
Cranial defect module is designed using CAD software, STL models are obtained；(4) by magnesium alloy powder, in ball mill, (XQM-0.4L is planetary
Ball mill) in be well mixed, mill rotating speed be 250r/min, Ball-milling Time is 30min, and it is protective gas to employ nitrogen as,
Obtain the magnesium alloy powder after ball milling (preferable particle size is 40 μm~50 μm)；By STL mode input 3D printer equipment, then by ball
Magnesium alloy powder after mill is placed in 3D printer equipment, is molded using laser 3D printing, and the power of laser is 100~200W
(preferably 150W), sweep speed 20m/min, 1~3ms of pulsewidth, frequency 0.0Hz, 2~3mm of defocusing amount, spot diameter 0.2mm, argon
Printed under gas or vacuum protection atmosphere, individual layer print thickness 0.04mm is printed according to STL models, obtain embryo material；To obtain
The embryo material for obtaining is placed in electrolytic cell of the electrochemical workstation (IviumStat) equipped with agitating device, and polishing fluid is body in electrolytic cell
Product compares 1:1:The mixed liquor of 20 perchloric acid, glycerine and glacial acetic acid, in 30V constant voltage modes, liquid feeding nitrogen is cooled to -5 DEG C, in stirring
Electrochemical polish operation is carried out under conditions of 100~200r/min of speed (preferably 150r/min), after obtaining electrochemical polish
Embryo material, then dried at room temperature with the ultrasonic cleaning of absolute alcohol, acetone and deionized water successively, obtain described magnesium alloy implantation
Body matrix；(5) with described magnesium alloy abutment of implant as anode, stainless steel is negative electrode, in differential arc oxidation liquid, is in frequency
550~650Hz, the differential of the arc time is 15~30min, and dutycycle is 15~30%, and current density is 20A/cm2, operation temperature is
(optimized frequency is 600Hz, differential of the arc time 20min to room temperature, and dutycycle is 20%, and current density is 20A/cm2, operation temperature 23
DEG C) under the conditions of carry out differential arc oxidation reaction, described magnesium alloy abutment of implant is taken out in reaction after terminating, surpass in deionized water
Sound cleans (preferably 15min), is dried in 20-45 DEG C of baking oven, obtains the magnesium alloy that surface forms micro-arc oxidation films Rotating fields
Abutment of implant, is designated as magnesium alloy abutment of implant/differential arc oxidation film layer；(6) the magnesium alloy implant base prepared with step (5)
Body/differential arc oxidation film layer is working electrode, and platinized platinum is used as to electrode, and saturated calomel electrode is heavy in electrochemistry as reference electrode
In hydrops, constant current mode, current density is 4-6mA/cm2(preferably 5mA/cm2), depositing temperature be 37 DEG C under conditions of carry out electricity
After chemical deposition 90-150min (preferably 120min), described magnesium alloy abutment of implant/differential arc oxidation film layer is taken out, used
Deionized water is cleaned, and room temperature is dried；Immerse again in the NaOH aqueous solution of 1-2mol/L (preferably 2mol/L), 2- is soaked at 80 DEG C
4h (preferably 3h), is then cleaned repeatedly with deionized water, after room temperature is dried, in tube furnace under argon gas or vacuum protection atmosphere
In carry out the high temperature anneal, be warming up to 200 DEG C with the speed of 10 DEG C/min, be incubated 2h, obtain surface shape successively from outside to inside
Into hydroxyapatite layer or fluorine hydroxyapatite layer, the magnesium alloy abutment of implant of micro-arc oxidation films Rotating fields, magnesium alloy is designated as
Abutment of implant/differential arc oxidation film layer/hydroxyapatite layer or fluorine hydroxyapatite layer；(7) polylactic acid powder is added to two
In chloromethanes, room temperature uniform stirring 6 hours obtains the PLA solution of mass concentration 2.5%；Magnesium alloy prepared by step (6)
In abutment of implant/differential arc oxidation film layer/hydroxyapatite layer or fluorine hydroxyapatite layer immersion PLA solution, soaking at room temperature
After 20-30s, propose that room temperature is dried in ventilating kitchen with the constant speed of 15-25mm/min, then deionized water is cleaned, room temperature
Dry, that is, obtain and sequentially form from outside to inside polylactic acid layers, hydroxyapatite layer or fluorine hydroxyapatite layer, differential arc oxidation film layer
The magnesium alloy implantation composite material of structure, is designated as magnesium alloy substrate/differential arc oxidation film layer/hydroxyapatite layer or fluorine hydroxyl
Apatite layer/polylactic acid layers.
Additionally, the present invention also provides a kind of magnesium alloy implantation composite material answering in bone renovating material is prepared
With.
Room temperature of the present invention refers to 25-30 DEG C.Differential arc oxidation film layer, hydroxyapatite layer or fluorine hydroxy-apatite in the present invention
Rock layers control the thickness of thickness, polylactic acid layers to be controlled by impregnating repeatedly, lifting by controlling the reaction time.
Compared with the existing technology for preparing magnesium alloy implant, the beneficial effects are mainly as follows：
(1) present invention is solved using the 3D printing technique based on multi-layer spiral CT three-dimensional rebuilding in the preparation of matrix
Complex process caused by the preparation methods such as conventional cast, sintering, oxidizable, the low problem of implant recovery accuracy, improves
The structure precision and biocompatibility of magnesium alloy implant；
(2) present invention prepares bio-ceramic coating and can in the coating introduce calcium using differential arc oxidization technique in Mg alloy surface
Deng the element favourable to bone growth, obtaining special micrometer level porous hole can strengthen the machinery knot of histocyte and implant
Conjunction ability, and excellent binding ability can meet magnesium alloy implant clinical manipulation wearability demand and film layer it is long-acting
Property；
(2) Mg alloy surface using electrochemical deposition technique after differential arc oxidation treatment prepares hydroxyapatite coating layer
The methods such as the more traditional plasma spraying of method have low-temperature operation, and process is simple can be in complex-shaped and porous surface base
The advantage of uniform coating is prepared on bottom, while the introducing of hydroxyapatite coating layer enhances the hydrophily of film surface, is conducive to
Albumen significantly improves the migration of cell and increases in the absorption on surface, the Integrated implant of material is improved, so as to be conducive to bone tissue
Healing；
(3) present invention carries out surface macromolecule layer using Best-Effort request machine to the magnesium alloy implant after electrodeposition process
Prepare, improve coating corrosion resistance in vivo, further promote the reparation of bone tissue.
The present invention realizes magnesium conjunction from the data acquisition of original impaired bone structure to the preparation of final multicoat composite construction
The personalized exploitation of golden implant material, obtains high-quality magnesium alloy implantation composite material, wherein polarization test display
Its corrosion resistance obtains 4 liftings of the order of magnitude, and the composite material of magnesium alloy after prepared by osteoblasts cultivation display has more
Good osteocyte promotes ability.
(4) illustrate
Fig. 1 is magnesium alloy abutment of implant/differential arc oxidation film layer/hydroxyapatite layer of the present invention (or fluorine hydroxy-apatite
Stone)/polylactic acid layers composite structural representation；
Fig. 2 is the scanning electron microscope (SEM) photograph of the magnesium alloy matrix surface after differential arc oxidation in embodiment 1, and wherein a is to amplify 2000
After times, after b is to amplify 5000 times；
Fig. 3 is the EDS energy spectrum diagrams that magnesium alloy substrate carries out surface after differential arc oxidation and electrochemical deposition in embodiment 1；
Fig. 4 is the scanning electron microscope (SEM) photograph of the magnesium alloy matrix surface after differential arc oxidation and electrochemical deposition in embodiment 2, its
After middle figure a is to amplify 1000 times, after b is to amplify 10000 times.
(5) specific embodiment
With reference to specific embodiment, the present invention is described further, but protection scope of the present invention is not limited in
This：
In following examples, magnesium alloy implantation composite material has sandwich construction (such as Fig. 1), including arc differential oxide ceramic
Layer, hydroxyapatite (or fluorine hydroxyapatite) layer and PLA boiomacromolecule layer.
Embodiment 1
1st, the preparation of magnesium alloy abutment of implant
(1) patient's bone structure is carried out into CT scan (slices spiral CTs of GE LightSpeed 16), carries out both injured bones structure number
According to collection, data save as DICOM format；
(2) CT scan data of acquisition is input to Materialise 3 d modeling softwares (Materialise
Magics20), threshold value division is carried out, the noise for importing image is then removed using region growth method, carry out going for redundant data
Except, segmentation both injured bones structural region；
(3) three-dimensional structure data of impaired bone structure is obtained by Materialise 3 d modeling softwares opening operation, then
The three-dimensional data that will be obtained is input into UG softwares (NX9.0) and obtains digitlization Cranial defect threedimensional model, and the reparation for carrying out Cranial defect sets
Meter；
(4) being designed according to Cranial defect and the limbs line of force using CASE(Computer Aided Software Engineering) (CAD) (AutoCAD2010) carries out bone
The design of defect module, obtains high-quality digital model.
(5) the digital model data that will be obtained are with the object STL mode inputs of standard to 3D printer (Focus-
MD300 pulse lasers) in, AZ91D magnesium alloy powders (120 μm~150 μm of particle diameter) are well mixed in mixed powder machine,
Mill rotating speed is 250r/min, and Ball-milling Time is 30min, and it is protective gas to employ nitrogen as, and obtains the magnesium alloy after ball milling
Powder, particle diameter is 40 μm~50 μm.Magnesium alloy powder after ball milling is added into 3D printer, is molded using laser 3D printing, swashed
The power of light is 200W, sweep speed 20m/min, pulsewidth 2ms, frequency 0.0Hz, defocusing amount 2.5mm, spot diameter 0.2mm, argon
Printed under gas or vacuum protection atmosphere, individual layer print thickness 0.04mm, the embryo material of acquisition carries out electrochemical polish, and polishing fluid is
Volume ratio 1:The mixed liquor of 9 perchloric acid, positive absolute ethyl alcohol, using electrochemical workstation (IviumStat) and be provided with stirring dress
The electrolytic cell put is in constant current mode, current density 3A/dm2, -5 degrees Celsius of temperature (plus liquid nitrogen cooling), mixing speed 150r/min
Under conditions of be polished operation, obtain embryo material of the surface roughness at 70 μm or so；Absolute alcohol, acetone is respectively adopted, goes
Ionized water each ultrasonic cleaning of 15 minutes, carries out the de-oiling degreasing on embryo material surface, dries at room temperature, after obtaining electrochemical polish
Magnesium alloy abutment of implant.
(6) with the dried magnesium alloy abutment of implant of step (5) as anode, stainless steel is negative electrode, in differential arc oxidation liquid
In, it is 600Hz, differential of the arc time 20min in frequency, dutycycle is 20%, and current density is 20A/cm2, operation temperature is 23 DEG C
Under the conditions of carry out differential arc oxidation treatment, magnesium alloy abutment of implant surface formed 20 μm of differential arc oxidation film layers, take out, go from
It is cleaned by ultrasonic 15min in sub- water, is dried in 45 DEG C of baking oven, obtains surface and form 20 μm of magnesium conjunctions of micro-arc oxidation films Rotating fields
Golden abutment of implant, is designated as magnesium alloy abutment of implant/differential arc oxidation film layer.Differential arc oxidation liquid is constituted：10g/L Na2SiO3、
10g/L Na3PO4、8g/L NaOH、5g/L KF、6g/L Na2CO3, 3g/L KOH, 75mL/L absolute ethyl alcohols, solvent for go from
Sub- water, pH value nature.
(7) electro-deposition is carried out under three-electrode system.It is with step (6) magnesium alloy abutment of implant/differential arc oxidation film layer
Working electrode, used as to electrode, used as reference electrode, in electrochemical deposition liquid, constant current mode is electric for saturated calomel electrode for platinized platinum
Current density is 5mA/cm2, after depositing temperature under conditions of 37 DEG C to carry out electrochemical deposition 120min, by magnesium alloy implant base
Body is taken out, and is washed with deionized water only, and room temperature is dried；Immerse again in the NaOH aqueous solution of 2mol/L, 3h is soaked at 80 DEG C, by phosphorus
Acid calcium salt is fully converted to hydroxyapatite, is then cleaned repeatedly with deionized water, after room temperature is dried, is protected in argon gas or vacuum
The high temperature anneal is carried out under shield atmosphere, the adhesion of hydroxyapatite layer and differential arc oxidation layer is improved, annealing temperature is 200
DEG C, 2h is incubated, wherein diamond heating speed is 10 DEG C/min, obtains magnesium alloy abutment of implant surface shape successively from the inside to the outside
Into 20 μm of differential arc oxidation film layers, 5 μm of structures of hydroxyapatite (HAP) layer are designated as magnesium alloy abutment of implant/micro-arc oxidation films
Layer/hydroxyapatite layer, scanning electron microscope (SEM) photograph is as shown in Figure 2；Electrochemical deposition liquid is constituted：0.042mol/L Ca(NO3)2、
0.5mol/L NaNO3、0.025mol/L NH4H2PO4, 40mL/L absolute ethyl alcohols, 40mL/L hydrogen peroxide, 0.005mol/L alkyl
Phenol polyethenoxy ether OP-21,0.15mol/L trisodium citrate, solvent is deionized water, is with trometamol and nitre acid for adjusting pH
4.4。
(8) PLA powder (weight average molecular weight 150,000) is added to dichloromethane (DCM:Dichloromethane in), room
Warm uniform stirring 6 hours, it is 2.5 that both add mass ratio:97.5, the PLA solution of 2.5wt.% is obtained, it is then immersed in step
(7) magnesium alloy abutment of implant/differential arc oxidation film layer/hydroxyapatite layer, after soaking at room temperature 25s, in Best-Effort request machine (Shanghai
Three grind science and technology produces SYDC-100 type Best-Effort requests coating machine) in the presence of, proposed with the constant speed of 20mm/min, in ventilation
Room temperature is dried in kitchen.Then deionized water is cleaned, and room temperature is dried, you can obtain magnesium alloy abutment of implant surface from the inside to the outside according to
25 μm of differential arc oxidation film layers of secondary formation, 5 μm of hydroxyapatite layers, 8 μm of structures of polylactic acid layers are designated as magnesium alloy implant base
The magnesium alloy implantation composite material of body/differential arc oxidation film layer/hydroxyapatite layer/polylactic acid layers structure, structural representation is shown in
Shown in Fig. 1, EDS energy spectrum diagrams are as shown in Figure 3.
From figure 2 it can be seen that hydroxyapatite product is in bar sheet (a in Fig. 2), further amplify it can be seen that (Fig. 2
There is certain interval between middle b) hydroxyapatite, and differential of the arc hole is completely covered, coating uniform has cause, and this is conducive to surface biological
The preparation of macromolecule layer, while also further enhancing the biocompatibility of magnesium alloy implant.
As seen from Figure 3, calcium phosphorus atoms ratio reaches 2.39, and more than theoretical value 1.67, this is due to deposition process and heat
During treatment caused by the loss of phosphorus.
2nd, the performance test of magnesium alloy abutment of implant
(1) the dynamic polarization test of electrochemistry
By the present embodiment obtain magnesium alloy abutment of implant composite Hank solution (component be 8g/L NaCl,
0.4g/L KCl, 0.25g/L NaH2PO4·H2O, 0.35g/L NaHCO3, 0.06g/L Na2HPO4·2H2O, 0.19g/L
MgCl2, 0.19g/L CaCl2·2H2O, 0.06g/L MgSO4·7H2O and 1g/L glucose, deionized water is prepared, pH 7.8)
In carry out the dynamic polarization test of electrochemistry, it is electrochemical workstation (IviumStat) to use equipment, and its specific test parameter is：Sweep
Speed is retouched for 1mVs-1, sweep limits is -2.0V to 1.0V, magnesium alloy implantation composite material (AZ91D/ obtained in step 1
MAO/HAP/PLA) as working electrode, platinum electrode make to electrode, saturated calomel electrode as reference electrode, at a temperature of 37 DEG C
Tested, be control, the experimental data for measuring such as table 1 below with the magnesium alloy abutment of implant (magnesium alloy AZ31) of step (5)
It is shown：
The analysis result of polarization curve in table 1.Hank solution
| Sample | Ecorr(V) | |
| Magnesium alloy AZ31 | -1.73 | |
| AZ91D/MAO/HAP/PLA | -1.22 |
Can be obtained by table 1, the corrosion potential of magnesium alloy implantation composite material prepared by present case is from being not handled by
- 1.22V is arrived in preceding -1.73V liftings.In general, a corrosion potential higher shows that it has more preferable decay resistance,
Therefore, the magnesium alloy implantation composite material that prepared by present case has been obviously improved the decay resistance of magnesium alloy substrate.From corrosion
Current density can be seen that the corrosion electric current density of the matrix after treatment reduces 4 orders of magnitude, and this shows prepared by present case
Magnesium alloy composite coating material significantly reduces the corrosion rate of magnesium alloy substrate.Dynamic polarization test results can be illustrated, made
Standby magnesium alloy composite coating material can effectively improve the decay resistance of magnesium alloy substrate.
(2) attachment Gegenbaur's cell experiment
The magnesium alloy implantation composite material obtained to step 1 carries out cell culture experiments：To be obtained from adult rabbits body
Gegenbaur's cell cleaned twice with pH=7.5 phosphate buffers, be then collected by centrifugation, take cell precipitation be seeded to DMEM training
In nutrient solution, in 5%CO2, to be cultivated 1 week at 37 DEG C, the cell of acquisition is configured to 5 × 10 with pH=7.5 phosphate buffers5/ ml cells
Suspension.
Magnesium alloy implantation prepared by magnesium alloy abutment of implant (magnesium alloy AZ31) and step (8) prepared by step (5)
Composite material (AZ91D/MAO/HAP/PLA) is sterilized 40 minutes in 110 DEG C of water vapours respectively, and 5mm × 5mm is then taken respectively
The sample of × 1mm sizes is added in six orifice plates, then is separately added into 5 × 105/ ml Gegenbaur's cell suspension 1ml, add 10ml and contain
The DMEM nutrient solutions of 10% hyclone (FBS), 5%CO2, 37 DEG C are cultivated 24h, are washed with pH=7.5 phosphate buffer solutions afterwards
Three removal non-adhering cells of plate, are subsequently adding 0.5ml digestive juices (pancreas enzyme -EDTA) digestion, and the standard for adding 0.5ml disappears
Change liquid (pancreatin inhibitor) and terminate digestion, be made cell suspension, cell count is carried out with Z2 type cellular granularity calculating instruments.It is counted
Result is as shown in table 2 below：
The cell count of each group after the culture in 24 hours of 2. Gegenbaur's cell of table
| Sample | Attached cell number |
| Magnesium alloy AZ31 | 62000±2000 |
| AZ91D/MAO/HAP/PLA | 71000±2000 |
The Ti/MAO/HAP/PLC composite coating materials as obtained in table 2 can obtain present case have more attachment skeletonization thin
Born of the same parents, this Ti/MAO/HAP/PLC composite coating material for showing to prepare has preferably promotion bone cell growth ability, effectively
Improve the bioactivity of magnesium alloy substrate material.
Embodiment 2
Step (1)~(5) are identical with the condition in embodiment 1；
Be changed to for differential arc oxidation treatment fluid composition in the step of embodiment 1 (6) by step (6)：8g/L Na2SiO3、10g/L
Na3PO4、8g/L NaOH、3g/L KF、3g/L Na2CO3, 1g/L KOH, 50mL/L absolute ethyl alcohols, solvent is deionized water, pH
Value nature.The control parameter of differential arc oxidation is changed to：Frequency is 550Hz, and the differential of the arc time is 15min, and dutycycle is 15%, and electric current is close
It is 15A/cm to spend2, remaining condition is constant；Obtain magnesium alloy abutment of implant/differential arc oxidation film layer.
Be changed to for electrochemical deposition liquid composition in the step of embodiment 1 (7) by step (7)：0.042mol/L Ca(NO3)2、
0.5mol/L NaNO3、0.025mol/L NH4H2PO4, 30mL/L absolute ethyl alcohols, 30mL/L hydrogen peroxide, 0.004mol/L alkyl
In phenol polyethenoxy ether OP-21,0.1mol/L trisodium citrate, the deposition liquid of 0.0008mol/L NaF, solvent is deionization
Water, is 4.3 with trometamol and nitre acid for adjusting pH.Electrochemical deposition condition is changed to：Constant current mode, current density is 4mA/cm2,
Depositing temperature is 37 DEG C, and sedimentation time is 90min.The concentration of NaOH is changed to 1mol/L, and soak time is changed to 2h, and remaining condition is not
Become, remaining condition is constant；ESEM is as shown in Figure 4.Obtain magnesium alloy abutment of implant/differential arc oxidation film layer/hydroxy-apatite
Rock layers.SEM photograph is shown in Fig. 4,.
(soak time in the step of embodiment 1 (8) is changed to 20s to step by 8, and lifting speed is changed to the perseverance of 15mm/min
Constant speed degree, remaining condition is constant.Magnesium alloy implantation composite material is obtained ,/differential arc oxidation film layer thickness is 20 μm, hydroxy-apatite
Rock layers thickness is 4 μm, and polylactic acid layers thickness is 5 μm.
Fig. 4 is that the present embodiment gained magnesium alloy substrate carries out the SEM after differential arc oxidation and electrochemical fluorine hydroxyapatite
Photo, it can be seen that fluorine hydroxyapatite product prepared by electro-deposition is in nanoscale acicular texture, can be seen after amplification
Obvious flower-like structure, this is, because differential arc oxidation hole increases surface area, to promote the nucleation rate of matrix surface, is caused
One lower crystallite dimension, and low crystallite dimension is more beneficial for improving the bioactivity of material, enhances magnesium alloy
Biocompatibility.Meanwhile, it can clearly be seen that differential arc oxidation hole is covered very well after deposit, obtain covering uniform table
Face.
Embodiment 3
Step (1)~(5) are identical with the condition in embodiment 1；
Be changed to for differential arc oxidation treatment fluid composition in the step of embodiment 1 (6) by step (6)：12g/L Na2SiO3、12g/
L Na3PO4、10g/L NaOH、7g/L KF、8g/L Na2CO3, 5g/L KOH, 100mL/L absolute ethyl alcohols, solvent is deionization
Water, pH value nature.The control parameter of differential arc oxidation is changed to：Frequency is 650Hz, and the differential of the arc time is 30min, and dutycycle is 30%,
Current density is 20A/cm2, remaining condition is constant；Obtain magnesium alloy abutment of implant/differential arc oxidation film layer.
Be changed to for electrochemical deposition liquid composition in the step of embodiment 1 (7) by step (7)：0.042mol/L Ca(NO3)2、
0.5mol/L NaNO3、0.025mol/L NH4H2PO4, 50mL/L absolute ethyl alcohols, 50mL/L hydrogen peroxide, 0.006mol/L alkyl
In phenol polyethenoxy ether OP-21,0.2mol/L trisodium citrate, the deposition liquid of 0.0008mol/L NaF, solvent is deionization
Water, is 4.5 with trometamol and nitre acid for adjusting pH, and electrochemical deposition condition is changed to：Constant current mode, current density is 6mA/cm2,
Depositing temperature is 37 DEG C, and sedimentation time is 150min.The concentration of NaOH is changed to 2mol/L, and soak time is changed to 4h, remaining condition
Constant, remaining condition is constant；Obtain magnesium alloy abutment of implant/differential arc oxidation film layer/hydroxyapatite layer.
Soak time in the step of embodiment 1 (8) is changed to 30s by step (8), and lifting speed is changed to the perseverance of 25mm/min
Constant speed degree, remaining condition is constant.Magnesium alloy implantation composite material is obtained, differential arc oxidation film layer thickness is 30 μm, hydroxy-apatite
Rock layers thickness is 6 μm, and polylactic acid layers thickness is 10 μm.
Claims (10)
1. a kind of magnesium alloy is implanted into composite material, it is characterised in that the magnesium alloy implantation composite material is passed through with magnesium alloy powder
The model that 3D printing makes is magnesium alloy abutment of implant, forms micro- using micro-arc oxidation on magnesium alloy abutment of implant surface
Arc oxidation film layer, then forms hydroxyapatite layer or fluorine hydroxyl phosphorus in micro-arc oxidation films layer surface using electrochemical deposition method again
Grey rock layers, finally form polylactic acid layers in hydroxyapatite layer or fluorine hydroxyapatite layer surface impregnation；The micro-arc oxidation
Differential arc oxidation liquid used is constituted：8~12g/L Na2SiO3, 8~12g/L Na3PO4, 6~10g/L NaOH, 3~7g/L
KF, 3~8g/L Na2CO3, 1~5g/L KOH, 50~100mL/L absolute ethyl alcohols, solvent is deionized water, pH value nature；It is described
Electrochemical deposition liquid composition is used by hydroxyapatite layer：0.042mol/L Ca(NO3)2、0.5mol/L NaNO3、
0.025mol/L NH4H2PO4, 30-50mL/L absolute ethyl alcohols, 30-50mL/L hydrogen peroxide, 0.004-0.006mol/L alkyl phenols gather
Oxygen vinethene OP-21,0.1-0.2mol/L trisodium citrate, solvent is deionized water, is with trometamol and nitre acid for adjusting pH
4.3-4.5；The fluorine hydroxyapatite layer electrochemical deposition liquid is to be added in electrochemical deposition liquid used by hydroxyapatite layer
Concentration 0.0008mol/L NaF.
2. magnesium alloy as claimed in claim 1 is implanted into composite material, it is characterised in that the differential arc oxidation film layer thickness is 20 μ
M~30 μm, the hydroxyapatite layer or fluorine hydroxyapatite layer thickness are 4 μm~6 μm.
3. magnesium alloy as claimed in claim 1 is implanted into composite material, it is characterised in that the differential arc oxidation film layer is by such as lower section
It is prepared by method：With described magnesium alloy abutment of implant as anode, stainless steel is negative electrode, is 550 in frequency in differential arc oxidation liquid
~650Hz, the differential of the arc time is 15~30min, and dutycycle is 15~30%, and current density is 20A/cm2, operation temperature is room temperature
Under the conditions of carry out differential arc oxidation reaction, reaction takes out magnesium alloy abutment of implant after terminating, and is cleaned by ultrasonic in deionized water,
Dried in 20-45 DEG C of baking oven, obtain the magnesium alloy abutment of implant that surface forms differential arc oxidation film layer.
4. magnesium alloy as claimed in claim 1 is implanted into composite material, it is characterised in that the hydroxyapatite layer or fluorine hydroxyl
Apatite layer is prepared as follows：The magnesium alloy abutment of implant of differential arc oxidation film layer is formed as working electrode with surface, platinum
Used as to electrode, used as reference electrode, in electrochemical deposition liquid, constant current mode, current density is 4- to saturated calomel electrode to piece
6mA/cm2, after depositing temperature under conditions of 37 DEG C to carry out electrochemical deposition 90-150min, by described magnesium alloy implant
Matrix is taken out, and is washed with deionized water only, and room temperature is dried；Immerse again in the NaOH aqueous solution of 1-2mol/L, 2- is soaked at 80 DEG C
4h, is then cleaned repeatedly with deionized water, after room temperature is dried, carries out height in tube furnace under argon gas or vacuum protection atmosphere
Temperature annealing, 200 DEG C are warming up to the speed of 10 DEG C/min, are incubated 2h, are obtained surface and are sequentially formed hydroxyl phosphorus from outside to inside
Grey rock layers or fluorine hydroxyapatite layer, the magnesium alloy abutment of implant of micro-arc oxidation films Rotating fields.
5. magnesium alloy as claimed in claim 1 implantation composite material, it is characterised in that the thickness of the polylactic acid layers is 5 μm~
10μm。
6. magnesium alloy as claimed in claim 1 is implanted into composite material, it is characterised in that the polylactic acid layers are made as follows
It is standby：PLA is added in dichloromethane, room temperature uniform stirring 6 hours, obtains the PLA solution of mass concentration 2.5%；Will
Surface sequentially forms hydroxyapatite layer or fluorine hydroxyapatite layer, the magnesium alloy implant base of differential arc oxidation film layer from outside to inside
In body immersion PLA solution, after soaking at room temperature 20-30s, proposed with the constant speed of 15-25mm/min, in ventilating kitchen interior room
Temperature is dried, and then deionized water is cleaned, and room temperature is dried, that is, obtain and sequentially form from outside to inside polylactic acid layers, hydroxyapatite layer
Or the magnesium alloy implantation composite material of fluorine hydroxyapatite layer, micro-arc oxidation films Rotating fields.
7. magnesium alloy as claimed in claim 1 is implanted into composite material, it is characterised in that the magnesium alloy abutment of implant is by such as
It is prepared by lower section method：(1) impaired bone structure is carried out into CT scan, obtains the CT scan data of impaired bone structure, and be input to
Materialise 3 d modeling softwares, carry out threshold value division, and the noise for importing image is then removed using region growth method, enter
The removal of row redundant data, segmentation both injured bones structural region；(2) obtained by Materialise 3 d modeling softwares opening operation
The three-dimensional structure data of impaired bone structure, the three-dimensional structure data that then will be obtained is input into UG softwares, obtains digitlization Cranial defect
Threedimensional model；(3) according to digitlization Cranial defect threedimensional model, Cranial defect module is designed using CAD software, obtains STL models；
(4) by STL mode input 3D printing equipment, then magnesium alloy powder is well mixed in ball mill, mill rotating speed is 250r/min,
Ball-milling Time is 30min, and it is protective gas to employ nitrogen as, and obtains the magnesium alloy powder after ball milling；By the magnesium alloy after ball milling
Powder adds 3D printing equipment, is molded using laser 3D printing, and the power of laser is 100~200W, sweep speed 20m/min,
1~3ms of pulsewidth, frequency 0.0Hz, 2~3mm of defocusing amount, spot diameter 0.2mm, print under argon gas or vacuum protection atmosphere, single
Layer print thickness 0.04mm, the embryo material of acquisition is placed in electrolytic cell of the electrochemical workstation equipped with agitating device, is thrown in electrolytic cell
Light liquid is volume ratio 1:9 perchloric acid, the mixed liquor of absolute ethyl alcohol, in 30V constant voltage modes, liquid feeding nitrogen is cooled to -5 DEG C, is stirring
Mix and carry out under conditions of 100~200r/min of speed electrochemical polish operation, obtain the embryo material after electrochemical polish, then use successively
Absolute alcohol, acetone and deionized water are cleaned by ultrasonic, and dry at room temperature, obtain described magnesium alloy abutment of implant.
8. magnesium alloy as claimed in claim 1 is implanted into composite material, it is characterised in that the magnesium alloy powder is AZ91D magnesium alloys
Powder, particle diameter is 120 μm~150 μm.
9. magnesium alloy described in a kind of claim 1 is implanted into the preparation method of composite material, it is characterised in that methods described is：
(1) impaired bone structure is carried out into CT scan, obtains the CT scan data of impaired bone structure, and it is three-dimensional to be input to Materialise
Modeling software, carries out threshold value division, and the noise for importing image is then removed using region growth method, carries out going for redundant data
Except, segmentation both injured bones structural region；(2) the three of impaired bone structure are obtained by Materialise 3 d modeling softwares opening operation
Dimension structured data, the three-dimensional structure data that then will be obtained is input into UG softwares, obtains digitlization Cranial defect threedimensional model；(3) root
According to digitlization Cranial defect threedimensional model, Cranial defect module is designed using CAD software, obtain STL models；(4) by powder of stainless steel
It is well mixed in ball mill, mill rotating speed is 250r/min, and Ball-milling Time is 30min, and it is protective gas to employ nitrogen as,
Obtain the magnesium alloy powder after ball milling；By STL mode input 3D printing equipment, the magnesium alloy powder after ball milling is added into 3D printing
Equipment, is molded using laser 3D printing, and the power of laser is 100~200W, sweep speed 20m/min, 1~3ms of pulsewidth, frequency
0.0Hz, 2~3mm of defocusing amount, spot diameter 0.2mm, print, individual layer print thickness under argon gas or vacuum protection atmosphere
0.04mm, the embryo material of acquisition is placed in electrolytic cell of the electrochemical workstation equipped with agitating device, and polishing fluid is volume in electrolytic cell
Than 1:9 perchloric acid, the mixed liquor of absolute ethyl alcohol, in 30V constant voltage modes, liquid feeding nitrogen is cooled to -5 DEG C, low whipping speed 100~
Electrochemical polish operation is carried out under conditions of 200r/min, the embryo material after electrochemical polish is obtained, then uses absolute alcohol, third successively
Ketone and deionized water are cleaned by ultrasonic, and dry at room temperature, obtain described magnesium alloy abutment of implant；(5) with described magnesium alloy
Abutment of implant is anode, and stainless steel is negative electrode, in differential arc oxidation liquid, frequency be 550~650Hz, the differential of the arc time be 15~
30min, dutycycle is 15~30%, and current density is 20A/cm2, operation temperature is that to carry out differential arc oxidation anti-under room temperature condition
Should, reaction takes out magnesium alloy abutment of implant after terminating, and is cleaned by ultrasonic in deionized water, is dried in 20-45 DEG C of baking oven,
The magnesium alloy abutment of implant that surface forms micro-arc oxidation films Rotating fields is obtained, magnesium alloy abutment of implant/differential arc oxidation is designated as
Film layer；(6) with step (5) magnesium alloy abutment of implant/differential arc oxidation film layer as working electrode, platinized platinum is used as to electrode, saturation
Used as reference electrode, in electrochemical deposition liquid, constant current mode, current density is 4-6mA/cm to calomel electrode2, depositing temperature is
After carrying out electrochemical deposition 90-150min under conditions of 37 DEG C, described magnesium alloy abutment of implant/differential arc oxidation film layer is taken
Go out, be washed with deionized water only, room temperature is dried；Immerse again in the NaOH aqueous solution of 1-2mol/L, 2-4h is soaked at 80 DEG C, then
Cleaned repeatedly with deionized water, after room temperature is dried, carry out high annealing in tube furnace under argon gas or vacuum protection atmosphere
Treatment, 200 DEG C are warming up to the speed of 10 DEG C/min, are incubated 2h, obtain surface sequentially form from outside to inside differential arc oxidation film layer,
The magnesium alloy abutment of implant of hydroxyapatite layer or fluorine hydroxyapatite Rotating fields, is designated as magnesium alloy abutment of implant/differential of the arc
Oxidation film layer/hydroxyapatite layer or fluorine hydroxyapatite layer；(7) PLA is added in dichloromethane, room temperature is uniformly stirred
Mix 6 hours, obtain the PLA solution of mass concentration 2.5%；Magnesium alloy abutment of implant/differential arc oxidation prepared by step (6)
In film layer/hydroxyapatite layer or fluorine hydroxyapatite layer immersion PLA solution, after soaking at room temperature 20-30s, with 15-25mm/
The constant speed of min proposes that room temperature is dried in ventilating kitchen, and then deionized water is cleaned, and room temperature is dried, that is, obtain from outside to inside
Sequentially form the magnesium alloy implant of polylactic acid layers, hydroxyapatite layer or fluorine hydroxyapatite layer, micro-arc oxidation films Rotating fields
Composite.
10. application of the magnesium alloy implantation composite material in bone renovating material is prepared described in a kind of claim 1.
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| CN109266980A (en) * | 2018-11-05 | 2019-01-25 | 淮阴工学院 | In the method that Mg alloy surface prepares bulk material amorphous layer |
| CN109881238A (en) * | 2019-03-21 | 2019-06-14 | 西安交通大学 | Magnesium-based surface has the active coating and preparation method thereof of self-healing function |
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| CN110528048A (en) * | 2019-08-30 | 2019-12-03 | 广东省新材料研究所 | A kind of titanium alloy implant Bio-surface active coating and preparation method thereof |
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| CN113549977A (en) * | 2020-04-26 | 2021-10-26 | 巨腾国际控股有限公司 | Magnesium alloy article surface treatment method and structure thereof |
| CN112077308A (en) * | 2020-08-27 | 2020-12-15 | 西安理工大学 | Preparation method of 3D printing porous lattice structure with corrosion resistance and high strength |
| CN112675362A (en) * | 2020-12-24 | 2021-04-20 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of personalized magnesium alloy bracket for bone repair and product thereof |
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