CN100572610C - The plasma micro-arc oxidation legal system is equipped with the method for hydroxyl apatite bioceramic film - Google Patents
The plasma micro-arc oxidation legal system is equipped with the method for hydroxyl apatite bioceramic film Download PDFInfo
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- CN100572610C CN100572610C CNB2007100135850A CN200710013585A CN100572610C CN 100572610 C CN100572610 C CN 100572610C CN B2007100135850 A CNB2007100135850 A CN B2007100135850A CN 200710013585 A CN200710013585 A CN 200710013585A CN 100572610 C CN100572610 C CN 100572610C
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- 229910052588 hydroxylapatite Inorganic materials 0.000 title claims abstract description 27
- 238000000034 method Methods 0.000 title claims abstract description 27
- 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 title claims abstract description 23
- 239000003462 bioceramic Substances 0.000 title claims abstract description 14
- 238000007745 plasma electrolytic oxidation reaction Methods 0.000 title claims abstract description 10
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 40
- 239000008151 electrolyte solution Substances 0.000 claims abstract description 40
- 239000010936 titanium Substances 0.000 claims abstract description 40
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 39
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 31
- 229910001069 Ti alloy Inorganic materials 0.000 claims abstract description 16
- 238000002360 preparation method Methods 0.000 claims abstract description 14
- 239000010935 stainless steel Substances 0.000 claims abstract description 10
- 229910001220 stainless steel Inorganic materials 0.000 claims abstract description 10
- -1 argent ion Chemical class 0.000 claims abstract description 7
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 5
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910001424 calcium ion Inorganic materials 0.000 claims abstract description 4
- 239000010703 silicon Substances 0.000 claims abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 25
- 239000008367 deionised water Substances 0.000 claims description 19
- 229910021641 deionized water Inorganic materials 0.000 claims description 19
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 9
- 239000002105 nanoparticle Substances 0.000 claims description 7
- 239000000919 ceramic Substances 0.000 claims description 6
- 229910019142 PO4 Inorganic materials 0.000 claims description 3
- 239000010452 phosphate Substances 0.000 claims description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 2
- 239000012153 distilled water Substances 0.000 claims description 2
- 239000003792 electrolyte Substances 0.000 claims description 2
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 2
- 229910000108 silver(I,III) oxide Inorganic materials 0.000 claims description 2
- 230000003647 oxidation Effects 0.000 abstract description 22
- 239000011159 matrix material Substances 0.000 abstract description 10
- 239000007943 implant Substances 0.000 abstract description 8
- 229910052751 metal Inorganic materials 0.000 abstract description 7
- 239000002184 metal Substances 0.000 abstract description 7
- 229910052698 phosphorus Inorganic materials 0.000 abstract description 6
- 230000004071 biological effect Effects 0.000 abstract description 5
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 abstract description 4
- 239000011574 phosphorus Substances 0.000 abstract description 4
- 150000002500 ions Chemical class 0.000 abstract description 2
- 238000001356 surgical procedure Methods 0.000 abstract description 2
- 150000003839 salts Chemical class 0.000 abstract 2
- 239000002253 acid Substances 0.000 abstract 1
- 239000011575 calcium Substances 0.000 description 9
- 230000010355 oscillation Effects 0.000 description 9
- 239000004576 sand Substances 0.000 description 7
- 239000011248 coating agent Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- 239000002826 coolant Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 3
- 210000000988 bone and bone Anatomy 0.000 description 3
- VSGNNIFQASZAOI-UHFFFAOYSA-L calcium acetate Chemical compound [Ca+2].CC([O-])=O.CC([O-])=O VSGNNIFQASZAOI-UHFFFAOYSA-L 0.000 description 3
- 238000004070 electrodeposition Methods 0.000 description 3
- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 description 3
- 230000012010 growth Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000012890 simulated body fluid Substances 0.000 description 3
- 229910010413 TiO 2 Inorganic materials 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000001639 calcium acetate Substances 0.000 description 2
- 235000011092 calcium acetate Nutrition 0.000 description 2
- 229960005147 calcium acetate Drugs 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229940045641 monobasic sodium phosphate Drugs 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000007750 plasma spraying Methods 0.000 description 2
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 description 2
- 238000003980 solgel method Methods 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000012620 biological material Substances 0.000 description 1
- 239000010839 body fluid Substances 0.000 description 1
- 210000001124 body fluid Anatomy 0.000 description 1
- 230000008468 bone growth Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000001962 electrophoresis Methods 0.000 description 1
- 235000021321 essential mineral Nutrition 0.000 description 1
- 210000004394 hip joint Anatomy 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000010335 hydrothermal treatment Methods 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-N phosphoric acid Substances OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000007669 thermal treatment Methods 0.000 description 1
- 210000001519 tissue Anatomy 0.000 description 1
- 230000008467 tissue growth Effects 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- 229910000406 trisodium phosphate Inorganic materials 0.000 description 1
- 235000019801 trisodium phosphate Nutrition 0.000 description 1
- 210000000689 upper leg Anatomy 0.000 description 1
Abstract
The present invention relates to a kind of method of utilizing the differential arc oxidation method to prepare hydroxyl apatite bioceramic film at titanium or titanium alloy surface.At first be mixed with electrolytic solution A, or in electrolytic solution A, add the argent ion, be mixed with electrolytic solution B with the salt of calcium ions and the salt of phosphorus-containing acid ion; Or in electrolytic solution A, add silicon ion, be mixed with electrolytic solution C; Then, with titanium or titanium alloy is that anode places electrolytic solution A, B, C respectively, the metal stainless steel vessel of containing electrolytic solution is a negative electrode, conditions such as the positive phase voltage of setting pulse power supply, frequency are carried out plasma micro-arc oxidation to titanium or titanium alloy, i.e. preparation generates the hydroxyl apatite bioceramic film layer with different performance.The titanium base bioceramic matrix material of this method preparation had not only had the intensity of titanium metal and toughness but also had had the biological activity of hydroxyapatite, can be applicable to fields such as Orthopeadic Surgery implant and tooth implant.
Description
Technical field:
The present invention relates to a kind of technology that metal surface modification is handled, promptly utilize the differential arc oxidation method directly to prepare the method for hydroxyl apatite bioceramic film at titanium or titanium alloy surface.Can be applicable to the fields such as tooth implant of femur, hip joint implant and the Oral Repair of Orthopeadic Surgery with the titanium base bioceramic matrix material of this method preparation.
Background technology:
Titanium or titanium alloy are the biomaterial for medical purpose of using always, and it has good biocompatibility and higher intensity and toughness, but it lacks biological activity, can not combine well with people's bone behind the implant into body, easily causes the implant loose or dislocation.(Hydroxyapatite is the essential mineral composition of bone HA) to hydroxyapatite, has excellent biological compatibility and biological activity, and is safe behind the implant into body, nontoxic, and the energy induction of bone growth is good substitute material for human hard tissues.But the hydroxyapatite physical strength is low, its application in medical science of toughness official post is very limited.
Generate one deck hydroxyapatite films at titanium or titanium alloy surface and make it become metal matrix ceramic composites, it had not only had the intensity of titanium metal and toughness but also had had the good biological activity of hydroxyapatite, thereby it has become people's goal in research.
At present, the method for preparing the hydroxylapatite biology rete at the titanium matrix surface has plasma spraying method, electrochemical deposition method, sol-gel method and differential arc oxidation (Micro-arc Oxidation, MAO) method etc.Plasma spraying method can be given birth to hydroxyapatite in the material surface spraying, but there is some shortcoming in it, biological ceramics bonding strength as material surface and spraying is relatively poor, for some complex-shaped implants, the The Nomenclature Composition and Structure of Complexes of the relatively poor and at high temperature restive hydroxyapatite of its homogeneity (HA).The hydroxyapatite and the substrate combinating strength of electrochemical deposition preparation are lower.The top coat and the high base strength of sol-gel and electrodeposition technology for preparing are lower, and the follow-up high thermal treatment of sol-gel method, and the phase structure of coating is changed.
At present, though have employing differential arc oxidation (MAO) technology to prepare the report of HA both at home and abroad, but they adopt the initial oxidation technology by aftertreatment growth HA again, as: employing differential arc oxidation-hydrothermal synthesis methods such as Japanese H.Ishizawa have prepared HA, they by the titanium dioxide film of MAO at the synthetic calcic phosphorus of titanium alloy surface, have synthesized HA through 300 ℃ of following hydrothermal treatment consists of 4 hours earlier then.The Englishman adopts the titanium alloy differential arc oxidation to generate TiO
2, prepared the HA coating with HA powder electrophoretic method again.The Korean generates the TiO of calcic phosphorus on the titanium matrix by differential arc oxidation in the electrolytic solution that lime acetate and β-Phosphoric acid glycerol esters are received
2Coating was soaked 7-14 days in simulated body fluid (SBF) or longer time induced growth HA again.
Xi'an Communications University generates hydroxyapatite by optically catalytic TiO 2 in simulated body fluid under ultraviolet condition behind titanium matrix differential arc oxidation.Tsing-Hua University generates TiO with anodic oxidation at the titanium matrix surface earlier
2Coating uses differential arc oxidation at TiO again
2The porous TiO of growth calcic phosphorus on the coating
2Coating is beneficial to the osseous tissue growth.Aforesaid method is for earlier carrying out anodic oxidation to the titanium matrix or differential arc oxidation is handled, and then through the body fluid mineralising hydro-thermal is synthetic or alkaline purification after form HA.
Summary of the invention:
Main purpose of the present invention is to overcome the deficiencies in the prior art, and a kind of simple method is provided, and adopts differential arc oxidation method to make titanium or one step of titanium alloy surface directly generate the hydroxyl apatite bioceramic film layer in electrolytic solution; Another object of the present invention is to adopt differential arc oxidation method to make titanium or titanium alloy surface directly generate the hydroxyl apatite bioceramic film layer with germ resistance in electrolytic solution; A further object of the present invention is to adopt differential arc oxidation method to make titanium or titanium alloy surface directly generate siliceous hydroxyl apatite bioceramic film layer in electrolytic solution.
In order to realize the foregoing invention purpose, operation steps of the present invention is as follows:
The first step, contain 0.010-0.040mol/L calcium ion and the electrolytic solution A that contains the 0.05-0.20mol/L phosphate anion with distilled water or deionized water preparation earlier, wherein calcium ion is provided by calcium acetate, caoxalate etc., and phosphate anion is provided by SODIUM PHOSPHATE, MONOBASIC, tri-sodium phosphate, ammonium di-hydrogen phosphate etc.; Or in electrolytic solution A, adding the argent ion of 0.01-0.05mol/L, addition manner is the nanoparticle or the silver suboxide nanoparticle of argent, is mixed with electrolytic solution B; Or in electrolytic solution A, adding the silicon ion of 0.02-0.10mol/L, addition manner is the nanoparticle or the silicon oxide nanoparticle of silicon, is mixed with electrolytic solution C;
Second step was that anode places electrolytic solution A, B, C respectively with titanium or titanium alloy, and the metal stainless steel vessel of containing electrolytic solution A, B, C is respectively negative electrode, is 200-600V in the positive phase voltage of the pulse power, and current density is 10-60A/dm
2Frequency is 20-500Hz, stacking factor is under the condition of 10-80% titanium or titanium alloy to be carried out plasma micro-arc oxidation, oxidization time is 5-30min, electrolyte temperature is 20-80 ℃, and promptly preparation generates the hydroxyl apatite bioceramic film layer, has the nano-hydroxyapatite biological ceramic film of germ resistance, siliceous nano-hydroxyapatite biological ceramic film respectively.
Experimental result is through energy dispersive x ray analysis (EDX) and X-ray diffraction (XRD) observation analysis, and the rete of generation contains Ca, P element, and has the obvious characteristic diffraction peak of HA.In mixing Ag ion and Si ionic HA rete, detect, except containing Ca and P element, also have Ag and Si element to exist through EDX.
The hydroxyl apatite bioceramic film of the inventive method preparation is formed and Stability Analysis of Structures, is evenly distributed, and is tight with the titanium matrix bond.Not only had the intensity of titanium metal and toughness but also had the good biological activity of hydroxyapatite with the titanium base bioceramic matrix material of this method preparation, had broad application prospects.
Embodiment:
Embodiment 1: with the SODIUM PHOSPHATE, MONOBASIC (NaH of deionized water preparation 0.06mol/L
2PO
4.2H
2O) solution adds 0.13mol/L calcium acetate ((CH again
3COO)
2Ca.H
2O), fully stir, be mixed with electrolytic solution.With pure titanium is the anode of differential arc oxidation, is negative electrode with the stainless steel electrolytic groove.Pure titanium sheet is earlier through #200, #400, and #600, #800, the #1000 sand papering is rinsed well with deionized water and to be placed in the electrolytic solution, adopts the pulse power, and current density is 10-16A/dm
2, dutycycle is 75%, and oxidization time is 10min, and final value voltage is 400V, and what can form thickness and be 10-15 μ m contains the HA rete.Feed water coolant in the oxidising process and cool off, temperature remains on below 50 ℃.
Embodiment 2: with the NaH of deionized water preparation 0.12mol/L
2PO
4.2H
2O solution adds 0.26mol/L (CH again
3COO)
2Ca.H
2O fully stirs, and is mixed with electrolytic solution.With pure titanium is the anode of differential arc oxidation, is negative electrode with the stainless steel electrolytic groove.Pure titanium sheet is earlier through #200, #400, and #600, #800, the #1000 sand papering is rinsed well with deionized water and to be placed in the electrolytic solution, adopts the pulse power, and current density is 10-16A/dm
2, dutycycle is 50%, and oxidization time is 10min, and final value voltage is 400V, and what can form thickness and be 10-15 μ m contains the HA rete.Feed water coolant in the oxidising process and cool off, temperature remains on below 50 ℃.
Embodiment 3: with the NaH of deionized water preparation 0.18mol/L
2PO
4.2H
2O solution adds 0.39mol/L (CH again
3COO)
2Ca.H
2O fully stirs, and is mixed with electrolytic solution.With pure titanium is the anode of differential arc oxidation, is negative electrode with the stainless steel electrolytic groove.Pure titanium sheet is earlier through #200, #400, and #600, #800, the #1000 sand papering is rinsed well with deionized water and to be placed in the electrolytic solution, adopts the pulse power, and current density is 10-16A/dm
2, dutycycle is 25%, and oxidization time is 10min, and final value voltage is 400V, and what can form thickness and be 10-15 μ m contains the HA rete.Feed water coolant in the oxidising process and cool off, temperature remains on below 50 ℃.
Embodiment 4: with the NaH of deionized water preparation 0.12mol/L
2PO
4.2H
2O solution adds 0.26mol/L (CH again
3COO)
2Ca.H
2O fully stirs, and is mixed with electrolytic solution.With pure titanium is the anode of differential arc oxidation, is negative electrode with the stainless steel electrolytic groove.Pure titanium sheet is earlier through #200, #400, and #600, #800, the #1000 sand papering is rinsed well with deionized water and to be placed in the electrolytic solution, adopts the pulse power, and current density is 10-16A/dm
2, dutycycle is 50%, and oxidization time is 30min, and final value voltage is 450V, and what can form thickness and be 20-25 μ m contains the HA rete.Feed water coolant in the oxidising process and cool off, temperature remains on below 50 ℃.
Embodiment 5: with 0.12molNaH
2PO
4.2H
2O is dissolved in the 500mL deionized water with ultra-sonic oscillation, again with 0.26mol (CH
3COO)
2Ca.H
2O is dissolved in the 500mL deionized water with ultra-sonic oscillation, then two aqueous solution is mixed, and adopts ultra-sonic oscillation to be mixed with electrolytic solution.With pure titanium is the anode of differential arc oxidation, is negative electrode with the stainless steel electrolytic groove.Pure titanium sheet is process #200 earlier, #400, and the #600 sand papering is rinsed well with deionized water, and is standby.Pure titanium sheet is placed electrolytic solution, adopt dual-pulse power supply, current density is 22-25A/dm
2, dutycycle is 15%, and oxidization time is 20min, and final value voltage is 500V, and outlet temperature is about 70 ℃, what can form thickness and be 25-30 μ m contains the HA rete.
Embodiment 6: with 0.12mol NaH
2PO
4.2H
2O is dissolved in the 500mL deionized water with ultra-sonic oscillation, again with 0.26mol (CH
3COO)
2Ca.H
2O is dissolved in the 500mL deionized water with ultra-sonic oscillation, then two aqueous solution is mixed, and adds the nano level Ag of 0.025mol
2The O particle, and adopt ultra-sonic oscillation to be mixed with electrolytic solution.With pure titanium is the anode of differential arc oxidation, is negative electrode with the stainless steel electrolytic groove.Pure titanium sheet is earlier through #200, #400, and the #600 sand papering is rinsed well with deionized water and to be placed in the electrolytic solution, adopts the pulse power, and current density is 22-25A/dm
2, dutycycle is 15%, and oxidization time is 20min, and final value voltage is 500V, and outlet temperature is about 70 ℃, can form thickness is the HA rete that contains Ag1.67at.%, has germ resistance of 30-35 μ m.
Embodiment 7: with 0.12molNaH
2PO
4.2H
2O is dissolved in the 500mL deionized water with ultra-sonic oscillation, again with 0.26mol (CH
3COO)
2Ca.H
2O is dissolved in the 500mL deionized water with ultra-sonic oscillation, then two aqueous solution is mixed, and adds the nano level SiO of 0.06mol
2Particle, and adopt ultra-sonic oscillation to be mixed with electrolytic solution.With pure titanium is the anode of differential arc oxidation, is negative electrode with the stainless steel electrolytic groove.Pure titanium sheet is earlier through #200, #400, and the #600 sand papering is rinsed well with deionized water and to be placed in the electrolytic solution, adopts the pulse power, and current density is 22-25A/dm
2, dutycycle is 15%, and oxidization time is 20min, and final value voltage is 500V, and outlet temperature is about about 70 ℃, and can form thickness is the HA rete of the siliceous 1.31at.% of 40-45 μ m.
Claims (1)
1, a kind of plasma micro-arc oxidation legal system is equipped with the method for hydroxyl apatite bioceramic film, it is characterized in that: at first contain 0.010-0.040mol/L calcium ion and the electrolytic solution A that contains the 0.05-0.20mol/L phosphate anion with distilled water or deionized water preparation, the nanoparticle or the silver suboxide nanoparticle that in electrolytic solution A, add the argent of 0.01-0.05mol/L again, be mixed with electrolytic solution B, or in electrolytic solution A, add silicon nano or the silicon oxide nanoparticle of 0.02-0.10mol/L, be mixed with electrolytic solution C; Then, be that anode places electrolytic solution B and C respectively with titanium or titanium alloy, the stainless steel vessel of containing electrolytic solution is a negative electrode, is 200-600V in the positive phase voltage of the pulse power, current density is 10-60A/dm
2Frequency is 20-500Hz, stacking factor is under the condition of 10-80% titanium or titanium alloy to be carried out plasma micro-arc oxidation, oxidization time is 5-30min, electrolyte temperature is 20-80 ℃, has promptly generated the nano-hydroxyapatite biological ceramic film with germ resistance, siliceous nano-hydroxyapatite biological ceramic film with electrolytic solution B and C preparation respectively.
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|---|---|---|---|
| CNB2007100135850A CN100572610C (en) | 2007-02-10 | 2007-02-10 | The plasma micro-arc oxidation legal system is equipped with the method for hydroxyl apatite bioceramic film |
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|---|---|---|---|
| CNB2007100135850A CN100572610C (en) | 2007-02-10 | 2007-02-10 | The plasma micro-arc oxidation legal system is equipped with the method for hydroxyl apatite bioceramic film |
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| CN102560596A (en) * | 2012-01-05 | 2012-07-11 | 哈尔滨工业大学 | Method for coating micro-arc oxidation titanium implant with cefazolin sodium and chitosan composite drug membrane |
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