CN104562145A - Method for preparing bioceramic membrane by composite oxidation - Google Patents
Method for preparing bioceramic membrane by composite oxidation Download PDFInfo
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- CN104562145A CN104562145A CN201410803384.0A CN201410803384A CN104562145A CN 104562145 A CN104562145 A CN 104562145A CN 201410803384 A CN201410803384 A CN 201410803384A CN 104562145 A CN104562145 A CN 104562145A
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- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 99
- 230000003647 oxidation Effects 0.000 title claims abstract description 85
- 238000000034 method Methods 0.000 title claims abstract description 36
- 239000003462 bioceramic Substances 0.000 title claims abstract description 17
- 239000012528 membrane Substances 0.000 title abstract description 7
- 239000002131 composite material Substances 0.000 title abstract description 5
- 239000000463 material Substances 0.000 claims abstract description 38
- 229910001069 Ti alloy Inorganic materials 0.000 claims abstract description 36
- 239000010935 stainless steel Substances 0.000 claims abstract description 17
- 229910001220 stainless steel Inorganic materials 0.000 claims abstract description 16
- 238000004140 cleaning Methods 0.000 claims abstract description 8
- 239000008367 deionised water Substances 0.000 claims abstract description 8
- 238000001035 drying Methods 0.000 claims abstract description 8
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 29
- 239000010936 titanium Substances 0.000 claims description 29
- 229910052719 titanium Inorganic materials 0.000 claims description 29
- 239000000919 ceramic Substances 0.000 claims description 21
- 239000008151 electrolyte solution Substances 0.000 claims description 21
- 239000007787 solid Substances 0.000 claims description 18
- 229910019142 PO4 Inorganic materials 0.000 claims description 12
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 12
- VSGNNIFQASZAOI-UHFFFAOYSA-L calcium acetate Chemical compound [Ca+2].CC([O-])=O.CC([O-])=O VSGNNIFQASZAOI-UHFFFAOYSA-L 0.000 claims description 12
- 239000010452 phosphate Substances 0.000 claims description 12
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 12
- 229910052700 potassium Inorganic materials 0.000 claims description 12
- 239000011591 potassium Substances 0.000 claims description 12
- 239000003513 alkali Substances 0.000 claims description 7
- 238000002242 deionisation method Methods 0.000 claims description 7
- 238000002203 pretreatment Methods 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 4
- 239000008139 complexing agent Substances 0.000 claims description 4
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 claims description 4
- 235000019832 sodium triphosphate Nutrition 0.000 claims description 4
- ZGTMUACCHSMWAC-UHFFFAOYSA-L EDTA disodium salt (anhydrous) Chemical group [Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O ZGTMUACCHSMWAC-UHFFFAOYSA-L 0.000 claims description 2
- 101001091385 Homo sapiens Kallikrein-6 Proteins 0.000 claims description 2
- 102100034866 Kallikrein-6 Human genes 0.000 claims description 2
- 101710194948 Protein phosphatase PhpP Proteins 0.000 claims description 2
- 235000011092 calcium acetate Nutrition 0.000 claims description 2
- 239000001639 calcium acetate Substances 0.000 claims description 2
- 229960005147 calcium acetate Drugs 0.000 claims description 2
- YYRMJZQKEFZXMX-UHFFFAOYSA-L calcium bis(dihydrogenphosphate) Chemical compound [Ca+2].OP(O)([O-])=O.OP(O)([O-])=O YYRMJZQKEFZXMX-UHFFFAOYSA-L 0.000 claims description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 2
- 235000010216 calcium carbonate Nutrition 0.000 claims description 2
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 2
- 239000000920 calcium hydroxide Substances 0.000 claims description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 2
- 235000011116 calcium hydroxide Nutrition 0.000 claims description 2
- 239000001506 calcium phosphate Substances 0.000 claims description 2
- 235000019691 monocalcium phosphate Nutrition 0.000 claims description 2
- 229910000150 monocalcium phosphate Inorganic materials 0.000 claims description 2
- HWGNBUXHKFFFIH-UHFFFAOYSA-I pentasodium;[oxido(phosphonatooxy)phosphoryl] phosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O HWGNBUXHKFFFIH-UHFFFAOYSA-I 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- 235000019982 sodium hexametaphosphate Nutrition 0.000 claims description 2
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 claims description 2
- 239000001488 sodium phosphate Substances 0.000 claims description 2
- 229910000162 sodium phosphate Inorganic materials 0.000 claims description 2
- 235000019830 sodium polyphosphate Nutrition 0.000 claims description 2
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 claims description 2
- UNXRWKVEANCORM-UHFFFAOYSA-I triphosphate(5-) Chemical compound [O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O UNXRWKVEANCORM-UHFFFAOYSA-I 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
- 229910052588 hydroxylapatite Inorganic materials 0.000 abstract description 13
- 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 abstract description 13
- 239000003792 electrolyte Substances 0.000 abstract description 12
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 abstract description 12
- 239000000126 substance Substances 0.000 abstract description 7
- 238000005260 corrosion Methods 0.000 abstract description 4
- 238000007745 plasma electrolytic oxidation reaction Methods 0.000 abstract description 3
- 230000007797 corrosion Effects 0.000 abstract description 2
- 238000004381 surface treatment Methods 0.000 abstract description 2
- 238000002513 implantation Methods 0.000 abstract 3
- 238000005868 electrolysis reaction Methods 0.000 abstract 2
- 230000002349 favourable effect Effects 0.000 abstract 2
- 229910021641 deionized water Inorganic materials 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract 1
- 239000007943 implant Substances 0.000 description 6
- 238000001556 precipitation Methods 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 238000004891 communication Methods 0.000 description 3
- 210000001519 tissue Anatomy 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 2
- 210000000988 bone and bone Anatomy 0.000 description 2
- 238000000280 densification Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 231100001261 hazardous Toxicity 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 230000001473 noxious effect Effects 0.000 description 2
- 231100000614 poison Toxicity 0.000 description 2
- 230000007096 poisonous effect Effects 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 206010061218 Inflammation Diseases 0.000 description 1
- 208000007536 Thrombosis Diseases 0.000 description 1
- 206010060872 Transplant failure Diseases 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 230000000975 bioactive effect Effects 0.000 description 1
- 230000004071 biological effect Effects 0.000 description 1
- 239000003519 biomedical and dental material Substances 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 238000005524 ceramic coating Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 230000035876 healing Effects 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000004054 inflammatory process Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000011164 ossification Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 229910001256 stainless steel alloy Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/26—Anodisation of refractory metals or alloys based thereon
Abstract
The invention discloses a method for preparing a bioceramic membrane by composite oxidation, belonging to a biological medical implantation material surface treatment technique. The method comprises the following steps: pretreating a titanium alloy sample, putting in an electrolyte as an anode, and carrying out anode oxidation by using a stainless steel electrolysis bath as a cathode; putting the titanium alloy sample subjected to anode oxidation treatment into the electrolyte as an anode, carrying out microarc oxidation by using the stainless steel electrolysis bath as a cathode, cleaning with deionized water, and drying to obtain the bioceramic membrane prepared by composite oxidation. The bioceramic membrane can form metallurgical bonding with the titanium alloy base surface, and has compact structure and high toughness. The outside contains the hydroxyapatite phase and more rutile phase, so the bioceramic membrane has the advantages of certain biocompatibility, favorable mechanical properties, favorable corrosion resistance and high chemical stability, conforms to the requirements for human implantation materials, and is one of primary materials for skeleton implantation and repair.
Description
Technical field
The present invention relates to a kind of method that combined oxidation prepares bioceramic film, belong to biological and medicinal implant material process for treating surface.
Background technology
Along with aging population aggravation and the unexpected increase causing injuring, the demand of people to bio-medical material and goods thereof is increasing.Widely used medical device is many by stainless steel and titanium alloy manufacture clinically at present.Titanium alloy is because having good biocompatibility and high specific tenacity and being used widely at biomedical sector, but industrial titanium is metal bio-inert material, longer with the healing time of wound; The abrasion resistance properties of titanium and titanium alloys is poor, and the abrasive dust rubbing due to long-term and other sclerous tissueses of human body and produce after implant into body can dissociate around implant, and cause inflammation even graft failure.So in order to carry out surface treatment to medical titanium alloy, improve it and implant performance and biocompatibility, strengthen itself and the biocompatibility of tissue and the precipitation of hazardous and noxious substances, reduce the formation of platelet adhesion reaction and thrombus, adopt composite oxidation technology, in electrolytic solution containing calcium phosphoric, first anodic oxidation treatment is carried out to titanium alloy, at the anode oxide film of the smooth densification of Surface Creation one deck, and then carry out differential arc oxidation process, surface regeneration one deck on the anode oxide film basis of smooth densification is made to contain hydroxyapatite and the porous ceramics rete of rough porous formation three-dimensional communication state.
By the thickness regulating the electrical parameter of anodic oxidation and differential arc oxidation to regulate surperficial ceramic film, the chemical constitution of porous bio-ceramic, thing phase composite and pore structure is controlled by regulating electrolytic solution composition, thus form the gradient-structure of titanium alloy biological ceramics rete, and form the hydroxyapatite with good biocompatibility on surface.Because anode oxide film is fine and close, high with substrate combinating strength, effectively can reduce the precipitation of hazardous and noxious substances in matrix, micro-arc oxidation films is coarse and form three-dimensional communication state, containing hydroxyapatite, have the advantages that tissue is grown into fast and healed with human body, thus realize good biocompatibility.
By the method to titanium alloy combined oxidation surface modification, the tight zone of its inside not only can effectively improve its use properties, reduce the precipitation of inner poisonous and harmful substances, its outside three-dimensional connected porous tectorium containing hydroxyapatite also can effectively make area of new bone be deposited directly to titanium alloy surface and promote osteogenesis, combined oxidation not only can improve stability and the wear resistance of titanium alloy implant surfaces, its surface bioactive can also be improved, thus make it better to serve medical field.
Summary of the invention
A kind of combined oxidation is the object of the present invention is to provide to prepare the method for bioceramic film, described method prepares one deck and the compact interior solid layer of titanium alloy substrate by anodic oxidation, on the basis of anode oxide film, prepare one deck by differential arc oxidation again and there is ceramic coating formed by micro-arc oxidation that is anti-corrosion, wear-resisting and good biological performance, specifically comprise the following steps:
(1) pre-treatment: surface finish process is carried out to specimen surface no marking to titanium alloy style, and then carry out oil removing, alkali cleaning and deionization washing, naturally dry;
(2) the titanium alloy style after pretreated is placed in electrolytic solution as anode, stainless steel electrolytic groove is negative electrode, carry out anodic oxidation, wherein the composition of electrolytic solution and content are: calcic ionogen 0.10mol/L ~ 0.20mol/L, phosphorous ionogen 0.10mol/L ~ 0.20mol/L, complexing agent 0.02mol/L ~ 0.06mol/L;
(3) step (2) is placed in the electrolytic solution identical with step (2) as anode again through anodic oxidation treatment titanium alloy style, stainless steel electrolytic groove is negative electrode, then carries out differential arc oxidation;
(4) the sample washed with de-ionized water post-drying after combined oxidation process is obtained the titanium material with the loose biological ceramics rete in interior solid outside.
Calcic ionogen described in step of the present invention (2) is that one or more materials in calcium acetate, calcium carbonate, monocalcium phosphate, calcium hydroxide, neurosin are mixed to get in any proportion.
Phosphorous ionogen described in step of the present invention (2) is that one or more materials in potassium primary phosphate, sodium phosphate, Sodium hexametaphosphate 99, tripoly phosphate sodium STPP, sodium polyphosphate are mixed to get in any proportion.
Described in step of the present invention (2), complexing agent selects EDTA-2Na or citric acid.
Described in step of the present invention (2), anodised power supply is the pulse power, and power parameter is: forward voltage 30 ~ 100V, and forward dutycycle is 10% ~ 50%, and frequency is 100Hz ~ 600Hz, and positive negative pulse stuffing number is 0 ~ 5, and oxidization time is 5 ~ 30min.
Described in step of the present invention (3), the power supply of differential arc oxidation is the pulse power, and power parameter is: forward voltage 400 ~ 500V, and forward dutycycle is 10% ~ 50%, and frequency is 100Hz ~ 600Hz, and positive negative pulse stuffing number is 0 ~ 5, and oxidization time is 20 ~ 80min.
The bioceramic film that the present invention prepares detects through XRD and SEM, combined oxidation rete can be obtained be made up of interior solid layer and outside tectorium, hardness value is between 307 ~ 330Hv, and thickness between 40 ~ 130 μm, and contains anatase octahedrite, rutile and hydroxyapatite phase.
Tool of the present invention has the following advantages:
(1) the loose biological ceramics rete in interior solid outside of the bioceramic film for preparing of the present invention forms metallurgical binding with titanium alloy-based surface, and the high and biocompatibility of bonding strength well, meets the requirement of body implanting material;
(2) the method for the invention first carries out anodic oxidation to titanium alloy, and then carry out differential arc oxidation process, metallurgical fine and close interior layer can be formed at titanium alloy surface and matrix, effectively can improve the solidity to corrosion of rete and stop the precipitation of inner poisonous and harmful substances, and then on anode oxide film basis, form the loose porous ceramic layer containing hydroxyapatite of one deck through differential arc oxidation, to raising titanium alloy biocompatibility, there is good effect;
(3) not containing the material to human body and bad environmental in the electrolytic solution that this combined oxidation uses, is green electrolytic solution;
(4) combined oxidation electrolytic solution raw material of the present invention is easy to get, and technique is easy to control, and not containing easily decomposing composition, stable components, is suitable for suitability for industrialized production;
(5) the outside loose porous ceramic film of the interior solid of gained of the present invention is titanium alloy in-situ preparation, interior solid, outside loose porous, there is ceramic outward appearance, good with basal body binding force, oxidation film layer thickness is 10 ~ 80 μm, has good anti-corrosion and biological property;
(6) the loose biological ceramics rete surface, interior solid outside that prepared by the method for the invention detects through XRD and SEM detected result shows, this rete hole three-dimensional communication and containing and hydroxyapatite composition like body bone inorganic substance constituent class, there is good biocompatibility, be conducive to the good fusion of implant and body.
Accompanying drawing explanation
Fig. 1 is combined oxidation schema;
Fig. 2 is the forming process schematic diagram of the fine and close outside loose biological ceramics rete of titanium alloy substrate interior surface.
In Fig. 2: figure (a) is titanium alloy substrate, figure (b) is formed for anode oxidation membrane, and scheming (c) is that anode oxidation membrane and differential arc oxidation film layer are formed, and (d) differential arc oxidation film layer surface forms hole.
Embodiment
Below in conjunction with the drawings and specific embodiments, the present invention is described in further detail, but protection scope of the present invention is not limited to described content.
embodiment 1
(1) pre-treatment: titanium alloy ti6al4v is cut into cylindrical titanium material, punches, carries out surface finish process to specimen surface no marking to titanium alloy above sample, and then carries out oil removing, alkali cleaning and deionization washing, naturally dries;
(2) anodic oxidation: the cylindrical titanium material of step (1) after pretreated is hung in electrolytic solution as anode, stainless steel electrolytic groove is negative electrode, carry out anodic oxidation, power supply used is the pulse power, power parameter is set as: forward voltage 30V, and forward dutycycle is 10%, and frequency is 200Hz, positive negative pulse stuffing number is 1, and oxidization time is 5min.Electrolyte quota is: lime acetate 0.05mol/L, EDTA-2Na0.10mol/L, potassium primary phosphate 0.01mol/L;
(3) differential arc oxidation: step (2) is hung in identical electrolytic solution as anode again through the cylindrical titanium material of anodic oxidation treatment with dense oxidation film, stainless steel electrolytic groove is negative electrode, carry out differential arc oxidation again, power supply used is the pulse power, power parameter is set as: forward voltage 400V, and forward dutycycle is 10%, and frequency is 200Hz, positive negative pulse stuffing number is 1, and oxidization time is 20min.Electrolyte quota is: lime acetate 0.05mol/L, EDTA-2Na0.10mol/L, potassium primary phosphate 0.01mol/L;
(4) the sample washed with de-ionized water post-drying after combined oxidation process is obtained the titanium material with the loose biological ceramics rete in interior solid outside.
The titanium material of the biological ceramics rete that the present embodiment prepares detects through XRD and SEM, this embodiment gained combined oxidation rete is made up of interior solid layer and outside tectorium, hardness can reach 310Hv, and thickness can reach 45 μm, and containing more anatase octahedrite and hydroxyapatite phase.
Embodiment 2
(1) pre-treatment: titanium alloy ti6al4v is cut into cylindrical titanium material, punches, carries out surface finish process to specimen surface without obvious cut to titanium alloy above sample, and then carries out oil removing, alkali cleaning and deionization washing, naturally dries;
(2) anodic oxidation: the cylindrical titanium material of step (1) after pretreated is hung in electrolytic solution as anode, stainless steel electrolytic groove is negative electrode, carry out anodic oxidation, power supply used is the pulse power, power parameter is set as: forward voltage 40V, and forward dutycycle is 20%, and frequency is 300Hz, positive negative pulse stuffing number is 1, and oxidization time is 10min.Electrolyte quota is: lime acetate 0.1mol/L, EDTA-2Na0.15mol/L, potassium primary phosphate 0.2mol/L;
(3) differential arc oxidation: step (2) is hung in identical electrolytic solution as anode again through the cylindrical titanium material of anodic oxidation treatment with dense oxidation film, stainless steel electrolytic groove is negative electrode, carry out differential arc oxidation again, power supply used is the pulse power, power parameter is set as: forward voltage 450V, and forward dutycycle is 20%, and frequency is 300Hz, positive negative pulse stuffing number is 1, and oxidization time is 40min.Electrolyte quota is: lime acetate 0.1mol/L, EDTA-2Na0.15mol/L, potassium primary phosphate 0.2mol/L;
(4) the sample washed with de-ionized water post-drying after combined oxidation process is obtained the titanium material with the loose biological ceramics rete in interior solid outside.
The titanium material of the biological ceramics rete that the present embodiment prepares detects through XRD and SEM, this embodiment gained combined oxidation rete is made up of interior solid layer and outside tectorium, hardness can reach 317Hv, and thickness can reach 56 μm, and containing more anatase octahedrite and hydroxyapatite phase.
Embodiment 3
(1) pre-treatment: titanium alloy ti6al4v is cut into cylindrical titanium material, punches, carries out surface finish process to specimen surface without obvious cut to titanium alloy above sample, and then carries out oil removing, alkali cleaning and deionization washing, naturally dries;
(2) anodic oxidation: the cylindrical titanium material of step (1) after pretreated is hung in electrolytic solution as anode, stainless steel electrolytic groove is negative electrode, carry out anodic oxidation, power supply used is the pulse power, power parameter is set as: forward voltage 60V, and forward dutycycle is 20%, and frequency is 400Hz, positive negative pulse stuffing number is 1, and oxidization time is 20min.Electrolyte quota is: lime acetate 0.1mol/L, EDTA-2Na0.15mol/L, potassium primary phosphate 0.2mol/L;
(3) differential arc oxidation: step (2) is hung in identical electrolytic solution as anode again through the cylindrical titanium material of anodic oxidation treatment with dense oxidation film, stainless steel electrolytic groove is negative electrode, carry out differential arc oxidation again, power supply used is the pulse power, power parameter is set as: forward voltage 450V, and forward dutycycle is 20%, and frequency is 400Hz, positive negative pulse stuffing number is 1, and oxidization time is 60min.Electrolyte quota is: lime acetate 0.1mol/L, EDTA-2Na0.15mol/L, potassium primary phosphate 0.2mol/L;
(4) the sample washed with de-ionized water post-drying after combined oxidation process is obtained the titanium material with the loose biological ceramics rete in interior solid outside.
The titanium material of the biological ceramics rete that the present embodiment prepares detects through XRD and SEM, this embodiment gained combined oxidation rete is made up of interior solid layer and outside tectorium, hardness can reach 319Hv, and thickness can reach 90 μm, and containing more anatase octahedrite and hydroxyapatite phase.
Embodiment 4
(1) pre-treatment: titanium alloy ti6al4v is cut into cylindrical titanium material, punches, carries out surface finish process to specimen surface without obvious cut to titanium alloy above sample, and then carries out oil removing, alkali cleaning and deionization washing, naturally dries;
(2) anodic oxidation: the cylindrical titanium material of step (1) after pretreated is hung in electrolytic solution as anode, stainless steel electrolytic groove is negative electrode, carry out anodic oxidation, power supply used is the pulse power, power parameter is set as: forward voltage 80V, and forward dutycycle is 40%, and frequency is 600Hz, positive negative pulse stuffing number is 1, and oxidization time is 30min.Electrolyte quota is: lime acetate 0.1mol/L, EDTA-2Na0.15mol/L, potassium primary phosphate 0.2mol/L;
(3) differential arc oxidation: step (2) is hung in identical electrolytic solution as anode again through the cylindrical titanium material of anodic oxidation treatment with dense oxidation film, stainless steel electrolytic groove is negative electrode, carry out differential arc oxidation again, power supply used is the pulse power, power parameter is set as: forward voltage 500V, and forward dutycycle is 40%, and frequency is 600Hz, positive negative pulse stuffing number is 1, and oxidization time is 80min.Electrolyte quota is: lime acetate 0.1mol/L, EDTA-2Na0.15mol/L, potassium primary phosphate 0.2mol/L;
(4) the sample washed with de-ionized water post-drying after combined oxidation process is obtained the titanium material with the loose biological ceramics rete in interior solid outside.
The titanium material of the biological ceramics rete that the present embodiment prepares detects through XRD and SEM, this embodiment gained combined oxidation rete is made up of interior solid layer and outside tectorium, hardness can reach 327Hv, and thickness can reach 110 μm, and containing more rutile and hydroxyapatite phase.
Embodiment 5
(1) pre-treatment: titanium alloy ti6al4v is cut into cylindrical titanium material, punches, carries out surface finish process to specimen surface without obvious cut to titanium alloy above sample, and then carries out oil removing, alkali cleaning and deionization washing, naturally dries;
(2) anodic oxidation: the cylindrical titanium material of step (1) after pretreated is hung in electrolytic solution as anode, stainless steel electrolytic groove is negative electrode, carry out anodic oxidation, power supply used is the pulse power, power parameter is set as: forward voltage 100V, and forward dutycycle is 40%, and frequency is 600Hz, positive negative pulse stuffing number is 1, and oxidization time is 30min.Electrolyte quota is: lime acetate 0.1mol/L, EDTA-2Na0.15mol/L, potassium primary phosphate 0.2mol/L;
(3) differential arc oxidation: step (2) is hung in identical electrolytic solution as anode again through the cylindrical titanium material of anodic oxidation treatment with dense oxidation film, stainless steel electrolytic groove is negative electrode, carry out differential arc oxidation again, power supply used is the pulse power, power parameter is set as: forward voltage 500V, and forward dutycycle is 40%, and frequency is 600Hz, positive negative pulse stuffing number is 1, and oxidization time is 80min.Electrolyte quota is: lime acetate 0.1mol/L, EDTA-2Na0.15mol/L, potassium primary phosphate 0.2mol/L;
(4) the sample washed with de-ionized water post-drying after combined oxidation process is obtained the titanium material with the loose biological ceramics rete in interior solid outside.
The titanium material of the biological ceramics rete that the present embodiment prepares detects through XRD and SEM, this embodiment gained combined oxidation rete is made up of interior solid layer and outside tectorium, hardness can reach 326Hv, and thickness can reach 128 μm, and containing more rutile and hydroxyapatite phase.
Claims (6)
1. combined oxidation prepares a method for bioceramic film, it is characterized in that, specifically comprises the following steps:
(1) pre-treatment: surface finish process is carried out to specimen surface no marking to titanium alloy style, and then carry out oil removing, alkali cleaning and deionization washing, naturally dry;
(2) the titanium alloy style after pretreated is placed in electrolytic solution as anode, stainless steel electrolytic groove is negative electrode, carry out anodic oxidation, wherein the composition of electrolytic solution and content are: calcic ionogen 0.10mol/L ~ 0.20mol/L, phosphorous ionogen 0.10mol/L ~ 0.20mol/L, complexing agent 0.02mol/L ~ 0.06mol/L;
(3) step (2) is placed in the electrolytic solution identical with step (2) as anode again through anodic oxidation treatment titanium alloy style, stainless steel electrolytic groove is negative electrode, then carries out differential arc oxidation;
(4) the sample washed with de-ionized water post-drying after combined oxidation process is obtained the titanium material with the loose biological ceramics rete in interior solid outside.
2. combined oxidation according to claim 1 prepares the method for bioceramic film, it is characterized in that: calcic ionogen described in step (2) is that one or more materials in calcium acetate, calcium carbonate, monocalcium phosphate, calcium hydroxide, neurosin are mixed to get in any proportion.
3. combined oxidation according to claim 1 prepares the method for bioceramic film, it is characterized in that: phosphorous ionogen described in step (2) is that one or more materials in potassium primary phosphate, sodium phosphate, Sodium hexametaphosphate 99, tripoly phosphate sodium STPP, sodium polyphosphate are mixed to get in any proportion.
4. combined oxidation according to claim 1 prepares the method for bioceramic film, it is characterized in that: described in step (2), complexing agent is EDTA-2Na or citric acid.
5. combined oxidation according to claim 1 prepares the method for bioceramic film, it is characterized in that: described in step (2), anodised power supply is the pulse power, power parameter is: forward voltage 30 ~ 100V, forward dutycycle is 10% ~ 50%, frequency is 100Hz ~ 600Hz, positive negative pulse stuffing number is 0 ~ 5, and oxidization time is 5 ~ 30min.
6. combined oxidation according to claim 1 prepares the method for bioceramic film, it is characterized in that: described in step (3), the power supply of differential arc oxidation is the pulse power, power parameter is: forward voltage 400 ~ 500V, forward dutycycle is 10% ~ 50%, frequency is 100Hz ~ 600Hz, positive negative pulse stuffing number is 0 ~ 5, and oxidization time is 20 ~ 80min.
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