CN104911671A - Preparation method for titanium alloy surface composite oxidation biological ceramic film - Google Patents
Preparation method for titanium alloy surface composite oxidation biological ceramic film Download PDFInfo
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- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 94
- 230000003647 oxidation Effects 0.000 title claims abstract description 80
- 229910001069 Ti alloy Inorganic materials 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000000919 ceramic Substances 0.000 title abstract description 16
- 239000002131 composite material Substances 0.000 title abstract description 7
- 238000000034 method Methods 0.000 claims abstract description 32
- 239000008151 electrolyte solution Substances 0.000 claims description 35
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- 239000003462 bioceramic Substances 0.000 claims description 18
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 claims description 14
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 12
- 239000010935 stainless steel Substances 0.000 claims description 12
- 229910001220 stainless steel Inorganic materials 0.000 claims description 12
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 10
- 238000004140 cleaning Methods 0.000 claims description 10
- VSGNNIFQASZAOI-UHFFFAOYSA-L calcium acetate Chemical compound [Ca+2].CC([O-])=O.CC([O-])=O VSGNNIFQASZAOI-UHFFFAOYSA-L 0.000 claims description 7
- JEGUKCSWCFPDGT-UHFFFAOYSA-N h2o hydrate Chemical compound O.O JEGUKCSWCFPDGT-UHFFFAOYSA-N 0.000 claims description 7
- 229940045641 monobasic sodium phosphate Drugs 0.000 claims description 7
- 229910000160 potassium phosphate Inorganic materials 0.000 claims description 7
- 229940093916 potassium phosphate Drugs 0.000 claims description 7
- 235000011009 potassium phosphates Nutrition 0.000 claims description 7
- 235000019353 potassium silicate Nutrition 0.000 claims description 7
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 claims description 7
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 6
- ZNCPFRVNHGOPAG-UHFFFAOYSA-L sodium oxalate Chemical compound [Na+].[Na+].[O-]C(=O)C([O-])=O ZNCPFRVNHGOPAG-UHFFFAOYSA-L 0.000 claims description 6
- 229940039790 sodium oxalate Drugs 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 3
- 238000005868 electrolysis reaction Methods 0.000 claims description 2
- 235000011194 food seasoning agent Nutrition 0.000 claims description 2
- OJGLOFBKLCHJFP-UHFFFAOYSA-L disodium;2-oxopropanedioate Chemical compound [Na+].[Na+].[O-]C(=O)C(=O)C([O-])=O OJGLOFBKLCHJFP-UHFFFAOYSA-L 0.000 claims 1
- 238000007745 plasma electrolytic oxidation reaction Methods 0.000 abstract description 8
- 238000005516 engineering process Methods 0.000 abstract description 4
- 239000012528 membrane Substances 0.000 abstract description 4
- 239000007769 metal material Substances 0.000 abstract description 3
- 230000007547 defect Effects 0.000 abstract description 2
- 239000011148 porous material Substances 0.000 abstract 3
- 238000004381 surface treatment Methods 0.000 abstract 1
- 230000010148 water-pollination Effects 0.000 abstract 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 15
- 239000000463 material Substances 0.000 description 15
- 239000010936 titanium Substances 0.000 description 15
- 229910052719 titanium Inorganic materials 0.000 description 15
- 210000000988 bone and bone Anatomy 0.000 description 14
- 239000003792 electrolyte Substances 0.000 description 12
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 11
- 238000002203 pretreatment Methods 0.000 description 7
- 239000003086 colorant Substances 0.000 description 6
- 210000001519 tissue Anatomy 0.000 description 5
- 239000007943 implant Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 239000003513 alkali Substances 0.000 description 3
- 238000002316 cosmetic surgery Methods 0.000 description 3
- 238000002242 deionisation method Methods 0.000 description 3
- 238000002513 implantation Methods 0.000 description 3
- 208000015181 infectious disease Diseases 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 229910021645 metal ion Inorganic materials 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 238000009736 wetting Methods 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229910010413 TiO 2 Inorganic materials 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 230000003796 beauty Effects 0.000 description 2
- 230000000975 bioactive effect Effects 0.000 description 2
- 210000001124 body fluid Anatomy 0.000 description 2
- 239000010839 body fluid Substances 0.000 description 2
- 238000004891 communication Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- 208000006386 Bone Resorption Diseases 0.000 description 1
- 206010020843 Hyperthermia Diseases 0.000 description 1
- 241001104043 Syringa Species 0.000 description 1
- 235000004338 Syringa vulgaris Nutrition 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 238000002048 anodisation reaction Methods 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000004071 biological effect Effects 0.000 description 1
- 230000024279 bone resorption Effects 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
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- 238000011161 development Methods 0.000 description 1
- 230000029087 digestion Effects 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 229910052588 hydroxylapatite Inorganic materials 0.000 description 1
- 230000036031 hyperthermia Effects 0.000 description 1
- 238000001727 in vivo Methods 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 150000001455 metallic ions Chemical class 0.000 description 1
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- 230000001590 oxidative effect Effects 0.000 description 1
- 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 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 230000029663 wound healing Effects 0.000 description 1
Abstract
The invention discloses a preparation method for a titanium alloy surface composite oxidation biological ceramic film and belongs to the orthopaedic metal material surface treatment technology field. An internal compact layer is prepared through an anodic oxidation method, a surface porous biological ceramic film layer is prepared based on an anodic oxidation membrane layer directly through a micro-arc oxidation method, finally, long-time oxidation is carried out in a low voltage or a small current based on the micro-arc oxidation film layer through an anodic oxidation method, thus a combination layer of the film layer is thick, pores in a compact layer are few, and the holes in a rough layer are communicated with each other. In the prepared composite oxidation biological ceramic film, the inner layer is a combination layer which has a compact structure, the interface layer is a compact layer which has a compact structure and has a lot of tiny pores with uniform pore size distribution, and the outer layer is a porous and loose layer which has a rough and porous surface and has good hydrophily. The defects of thin thickness, low hardness and the like of an anode oxide film are overcome, and the problem of single color of a micro-arc oxidation film layer is solved.
Description
Technical field
The present invention relates to a kind of preparation method of titanium alloy surface combined oxidation bioceramic film, belong to the technical field of surface of orthopaedics metallic substance.
Background technology
After bone substitution material implants, to be bone substitution material with osseous tissue ask desirable combination is combined with bone bonding pattern, make the continuity presented by the continuity of interface structure between implant and bone functionally, and interface bond strength can meet or exceed the bonding strength of bone self, implant self.Bone bonding process comprises mechanical interlock effect and chemical bonding effect, only has bioactive material and could form this bone bonding.Because the structures and characteristics of medical metal material and osseous tissue differ greatly, chemical key can not be there is with osseous tissue and be combined.In addition, titanium and osseous tissue Young's modulus differ greatly, and easily produce the adverse consequences such as stress concentration and bone resorption after implanting.Thus Young's modulus low (avoiding material fracture in vivo) is found, to osseous tissue " stress shielding is little ", more mate with skeleton mechanical compatibility, good biocompatibility and the emphasis of medical titanium alloy developing material can be become with the titanium alloy material of bone forming bone bonding.
In order to give medical titanium good biological activity, activation treatment need be carried out to medical titanium surface.The activation method of medical titanium roughly has plasma spray method, anonizing, colloidal sol. gel method, spatial induction mineralising method and micro-arc oxidation etc.
The oxidation film layer that medical titanium and titanium alloy anode oxidation obtain is bright in colour, and form compact structure with Titanium base surface energy, one deck hydrophobic silica rete that bonding force is strong, not only can improve wear resistance and the solidity to corrosion of material, and digestion of metallic ion problem can be solved to a great extent, reduce cytotoxicity, greatly improve the biocompatibility of implant.In addition, a kind of means that can also distinguish as different implantation piece of the oxide film of different colours.Meanwhile, along with plastic surgery dummy increases gradually in clinical application, the requirement of people has been not limited only to the recovery of its basic function, also day by day improves the requirement of aesthetic property, and such as, the chromatic beauty of artificial tooth can give visual sense of beauty and enjoy.Anode oxidation process is as a kind of method of surface modification, and its technique is simple, opens the functional new way with aesthetic property harmony of a strip material.
But the titanium dioxide film that independent conventional anodization technology can only exist with amorphous form in titanium alloy surface preparation, although oxide film various colors, but rete is often too thin, the hardness of anode oxide film is generally between 300-500HV, the maximum ga(u)ge of anode oxide film is only 3 ~ 10 μm, and wear resistance is poor.And film surface easily produces sharp limit defect, and the anodised scope of application is narrower.
Differential arc oxidization technique directly can form one deck hydrophilic film on titanium or titanium alloy surface, and the impact due to localized hyperthermia in rete exists rutile TiO
2with Detitanium-ore-type TiO
2phase structure.Owing to there is the high-temperature-phase rutile TiO of titanium dioxide in rete
2existence, the hardness of micro-arc oxidation films can reach more than 600HV, can reach 2500HV, thickness aspect, and differential arc oxidation can obtain the uniform oxidation film layer of surfaces externally and internally, and its maximum ga(u)ge can reach 200-300 μm.And can electrolyte prescription be regulated, by using the electrolytic solution being rich in Ca, P, the rete that differential arc oxidation is obtained exists and has bioactive hydroxyapatite phase, allows titanium or titanium alloy more easily be combined with matrix in implanting tissue, prevents the generation of " foreign material repulsion " phenomenon.But differential arc oxidation film layer short texture, the amorphous film Rotating fields not having anodic oxidation to be formed is fine and close, obtains bonding force not strong between rete and matrix.
To sum up, combined oxidation technology, namely be first at the dense oxidation film that the pre-anodic oxidation treatment in titanium or titanium alloy surface obtains, then on this basis, adopt micro-arc oxidation to prepare the method for the ceramic film of one deck porosity and looseness again on surface, finally carry out once anodised method (i.e. AO+MAO+AO) again.Ceramic film prepared by the method has three layers of gradient-structure, inner compact layer, outer rough porous, and there is the little aperture layer of one deck in the middle layer between skin and internal layer.This have the ceramic film of gradient effectively to stop free metal ion is separated out in body fluid, thus cause the infection of body tissue.This membrane structure is fine and close, and bonding force is good, has important Research Significance and DEVELOPMENT PROSPECT.
Summary of the invention
The technical problem to be solved in the present invention is the shortcomings such as anode oxidation membrane is thin, and hardness is low; And the key coat of differential arc oxidation film layer has hole, when in the medical titanium alloy implanting tissue processed, matrix metal ion can be free out from these holes, thus cause tissue infection, is unfavorable for the shortcoming of wound healing.
The object of the present invention is to provide a kind of preparation method of titanium alloy surface combined oxidation bioceramic film, adopt the biological ceramics rete of MULTIPLE COMPOSITE mode of oxidizing preparation in notch cuttype, namely interior solid layer is prepared by anonizing, on anode oxidation membrane basis, directly surperficial porous bio-ceramic rete is prepared again by micro-arc oxidation, finally adopt anonizing when on the basis of differential arc oxidation film layer in low voltage or small area analysis be oxidized for a long time, make the key coat of rete thicker, hole on tight zone is less, hole in rough layer is interconnected, specifically comprise the steps:
(1) titanium alloy is carried out polish, oil removing, cleaning, for subsequent use after seasoning;
(2) sample step (1) handled well hangs in the electrolytic solution as anode, and stainless steel electrolytic groove is negative electrode, carries out anodic oxidation, for subsequent use after cleaning, drying; Wherein, electrolytic solution is the one of phosphoric acid and sulfuric acid.
(3) change the electrolytic solution in electrolyzer, again hang in step (2) in the electrolytic solution as anode through the pretreated sample of anodic oxidation, stainless steel, as negative electrode, carries out differential arc oxidation, for subsequent use after cleaning, oven dry; Wherein said electrolytic solution is lime acetate, one or both materials of potassiumphosphate mix in any proportion;
(4) electrolytic solution in electrolyzer is changed, the anodised sample obtained in step (3) is hung in the electrolytic solution as anode again, stainless steel carries out anodic oxidation as negative electrode, wherein, electrolytic solution is sodium oxalate, one or more in nine water water glass, SODIUM PHOSPHATE, MONOBASIC, sodium hydroxide are mixed to get in any proportion.
(5) combined oxidation bioceramic film is just obtained at titanium alloy surface after the anodised sample washed with de-ionized water obtained in step (4) being dried.
In electrolytic solution described in step of the present invention (2), the concentration of phosphoric acid is 15 ~ 50g/L, and the concentration of sulfuric acid is 300 ~ 390g/L.
In step of the present invention (2) and the electrolytic process described in (4), electrolytic parameter is set as: forward voltage is 10 ~ 120V, and forward dutycycle is 10 ~ 60%, and frequency is 100 ~ 800Hz, and positive negative pulse stuffing number is 1 ~ 6, and oxidization time is 10 ~ 100min.
Described in step of the present invention (3), the formula of electrolytic solution is: lime acetate concentration is 15 ~ 40g/L, the concentration of potassiumphosphate is 10 ~ 30g/L.
Described in step of the present invention (3), the parameter of electrolysis is: forward voltage 220 ~ 600V, and forward dutycycle is 10% ~ 60%, and frequency is 100Hz ~ 800Hz, and positive negative pulse stuffing number is 1 ~ 6, and oxidization time is 10 ~ 30min.
Described in step of the present invention (4), the formula of electrolytic solution is: the concentration of sodium oxalate is 10 ~ 25g/L, the concentration of nine water water glass 10 ~ 15g/L, SODIUM PHOSPHATE, MONOBASIC is 10 ~ 15g/L, the concentration of sodium hydroxide is 1 ~ 7g/L.
Ceramic film prepared by the method for the invention has three layers of gradient-structure, inner compact layer, outer rough porous, and there is the little aperture layer of one deck in the middle layer between skin and internal layer; This have the ceramic film of gradient effectively to stop free metal ion is separated out in body fluid, thus cause the infection of body tissue; And, due to the anode oxidation process finally carried out, film surface prepared by this process can present distinct colors by control electrolyte prescription and power parameter, therefore, a kind of means that the oxide film of different colours can also be distinguished as different implantation piece, along with plastic surgery dummy increases gradually in clinical application, the requirement of people has been not limited only to the recovery of its basic function, also day by day improve the requirement of aesthetic property, the rete that therefore prepared by the present invention also can meet the requirement of popular aesthetic property.
Beneficial effect of the present invention:
(1) anode oxidation process owing to finally carrying out, film surface prepared by this process can present distinct colors by control electrolyte prescription and power parameter, therefore, a kind of means that the oxide film of different colours can also be distinguished as different implantation piece, along with plastic surgery dummy increases gradually in clinical application, the requirement of people has been not limited only to the recovery of its basic function, also day by day improve the requirement of aesthetic property, the rete that therefore prepared by the present invention also can meet the requirement of popular aesthetic property.
(2) controllability of the present invention is high, is conducive to controlling, and cost is low, and range of application is comparatively wide, can produce in batches.
Accompanying drawing explanation
Fig. 1 is process flow sheet of the present invention;
Fig. 2 is the SEM collection of illustrative plates of the combined oxidation bioceramic film that embodiment 1 prepares;
Fig. 3 is the XRD figure spectrum of the combined oxidation bioceramic film that embodiment 1 prepares;
Fig. 4 is the SEM collection of illustrative plates of the combined oxidation bioceramic film that embodiment 2 prepares;
Fig. 5 is the XRD figure spectrum of the combined oxidation bioceramic film that embodiment 2 prepares;
Fig. 6 is the SEM collection of illustrative plates of the combined oxidation bioceramic film that embodiment 3 prepares;
Fig. 7 is the XRD figure spectrum of the combined oxidation bioceramic film that embodiment 4 prepares.
Embodiment
Below in conjunction with drawings and Examples, the present invention is described further, but protection scope of the present invention is not limited to described content.
Embodiment 1
Method described in the present embodiment, for the preparation of the biological ceramics rete of notch cuttype, as shown in Figure 1, specifically comprises the following steps:
(1) pre-treatment: titanium alloy TC 4 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: hung in the electrolytic solution as anode by sample good for pre-treatment, stainless steel electrolytic groove is negative electrode, carries out anodic oxidation, for subsequent use after cleaning, drying; Power parameter is set as: forward voltage is 10V, and forward dutycycle is 10%, and frequency is 100Hz, and positive negative pulse stuffing number is 1, and oxidization time is 10; Electrolyte prescription is: phosphoric acid concentration is 15g/L.
(3) differential arc oxidation: change the electrolytic solution in electrolyzer, electrolyte prescription is: lime acetate concentration is 15g/L, and the concentration of potassiumphosphate is 10g/L; (2) step 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 220V, and forward dutycycle is 10%, and frequency is 100Hz, positive negative pulse stuffing number is 1, and oxidization time is 10min.
(4) anodic oxidation: by (3) step through differential arc oxidation process sample again carry out anodic oxidation, change electrolytic solution, electrolyte prescription is: the concentration of sodium oxalate is 10g/L, the concentration of nine water water glass 10g/L, SODIUM PHOSPHATE, MONOBASIC is 10g/L, the concentration of sodium hydroxide is 1g/L.Power parameter is set as: forward voltage is 10V, and forward dutycycle is 10%, and frequency is 100Hz, and positive negative pulse stuffing number is 1, and oxidization time is 10min.
(5) oven dry of the sample washed with de-ionized water of MULTIPLE COMPOSITE oxide treatment is just obtained the biological ceramics rete that film layer structure is notch cuttype, there is good wetting ability.
(6) as shown in Figure 2,3, detect through XRD and SEM, this embodiment gained combined oxidation rete is made up of interior solid layer and outside tectorium, the hole of tectorium is connected with there being a little said minuscule hole between hole, and microhardness can reach 394Hv, thicknesses of layers can reach 80 μm, and containing more Anatase; Rete presents lilac.
Embodiment 2
Method described in the present embodiment, for the preparation of the biological ceramics rete of notch cuttype, as shown in Figure 1, specifically comprises the following steps:
(1) pre-treatment: titanium alloy TC 4 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: hung in the electrolytic solution as anode by sample good for pre-treatment, stainless steel electrolytic groove is negative electrode, carries out anodic oxidation; Power parameter is set as: forward voltage is 60V, and forward dutycycle is 30%, and frequency is 500Hz, and positive negative pulse stuffing number is 3, and oxidization time is 50min; Electrolyte prescription is: sulfuric acid concentration is 300g/L.
(3) differential arc oxidation: change the electrolytic solution in electrolyzer, electrolyte prescription is: lime acetate concentration is 30g/L, and the concentration of potassiumphosphate is 15g/L.(2) step is hung in identical electrolytic solution as anode again through the cylindrical titanium material of anodic oxidation pre-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 30%, and frequency is 500Hz, positive negative pulse stuffing number is 3, and oxidization time is 20min.
(4) anodic oxidation: by (3) step through differential arc oxidation process sample again carry out anodic oxidation, change electrolytic solution, electrolyte prescription is: the concentration of sodium oxalate is 15g/L, the concentration of nine water water glass 12g/L, SODIUM PHOSPHATE, MONOBASIC is 12g/L, the concentration of sodium hydroxide is 2g/L; Power parameter is set as: forward voltage is 60V, and forward dutycycle is 30%, and frequency is 500Hz, and positive negative pulse stuffing number is 3, and oxidization time is 50min.
(5) oven dry of the sample washed with de-ionized water of MULTIPLE COMPOSITE oxide treatment is just obtained the biological ceramics rete that film layer structure is notch cuttype, there is good wetting ability.
(6) this embodiment gained combined oxidation rete as shown in Figure 4,5, detect through XRD and SEM, rete interior solid layer and outside tectorium are formed, the hole of tectorium is connected with there being many said minuscule hole between hole, in three-dimensional communication structure, and microhardness can reach 450Hv, and thicknesses of layers can reach 100 μm, containing Rutile Type and Anatase in rete, rete presents nattierblue.
Embodiment 3
Method described in the present embodiment, for the preparation of the biological ceramics rete of notch cuttype, as shown in Figure 1, specifically comprises the following steps:
(1) pre-treatment: titanium alloy TC 4 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: hung in the electrolytic solution as anode by sample good for pre-treatment, stainless steel electrolytic groove is negative electrode, carries out anodic oxidation; Power parameter is set as: forward voltage is 120V, and forward dutycycle is 60%, and frequency is 800Hz, and positive negative pulse stuffing number is 6, and oxidization time is 100min; Electrolyte prescription is: the concentration of phosphoric acid is 50g/L.
(3) differential arc oxidation: change the electrolytic solution in electrolyzer, electrolyte prescription is: lime acetate concentration is 40g/L, and the concentration of potassiumphosphate is 30g/L.(2) step 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 425V, and forward dutycycle is 60%, and frequency is 800Hz, positive negative pulse stuffing number is 6, and oxidization time is 30min.
(4) anodic oxidation: by (3) step through differential arc oxidation process sample again carry out anodic oxidation, change electrolytic solution, electrolyte prescription is: the concentration of sodium oxalate is 25g/L, the concentration of nine water water glass 15g/L, SODIUM PHOSPHATE, MONOBASIC is 15g/L, the concentration of sodium hydroxide is 7g/L; Power parameter is set as: forward voltage is 120V, and forward dutycycle is 60%, and frequency is 800Hz, and positive negative pulse stuffing number is 6, and oxidization time is 100min.
(5) oven dry of the sample washed with de-ionized water of MULTIPLE COMPOSITE oxide treatment is just obtained the biological ceramics rete that film layer structure is notch cuttype, there is good wetting ability.
(6) this embodiment gained combined oxidation rete as shown in Figure 6,7, detect through XRD and SEM, combined oxidation rete interior solid layer and outside tectorium are formed, the hole of tectorium is connected with there being the hole of many even size distribution between hole, in three-dimensional communication structure, and microhardness can reach 475Hv, and thicknesses of layers can reach 120 μm, containing a large amount of Rutile Type and a small amount of Anatase in rete, rete presents darkcyan.
Claims (6)
1. a preparation method for titanium alloy surface combined oxidation bioceramic film, is characterized in that, specifically comprises the steps:
(1) titanium alloy is carried out polish, oil removing, cleaning, for subsequent use after seasoning;
(2) sample step (1) handled well hangs in the electrolytic solution as anode, and stainless steel electrolytic groove is negative electrode, carries out anodic oxidation, for subsequent use after cleaning, drying; Wherein, electrolytic solution is the one of phosphoric acid or sulfuric acid;
(3) change the electrolytic solution in electrolyzer, again hang in step (2) in the electrolytic solution as anode through the pretreated sample of anodic oxidation, stainless steel, as negative electrode, carries out differential arc oxidation, for subsequent use after cleaning, oven dry; Wherein said electrolytic solution is lime acetate, potassiumphosphate mixes in any proportion;
(4) electrolytic solution in electrolyzer is changed, the anodised sample obtained in step (3) is hung in the electrolytic solution as anode again, stainless steel carries out anodic oxidation as negative electrode, and wherein electrolytic solution is sodium oxalate, one or more in nine water water glass, SODIUM PHOSPHATE, MONOBASIC, sodium hydroxide are mixed to get in any proportion;
(5) combined oxidation bioceramic film is just obtained at titanium alloy surface after the anodised sample washed with de-ionized water obtained in step (4) being dried.
2. the preparation method of titanium alloy surface combined oxidation bioceramic film according to claim 1, is characterized in that: in the electrolytic solution described in step (2), the concentration of phosphoric acid is 15 ~ 50g/L, the concentration of sulfuric acid is 300 ~ 390g/L.
3. the preparation method of titanium alloy surface combined oxidation bioceramic film according to claim 1, it is characterized in that: in step (2) and the electrolytic process described in (4), electrolytic parameter is set as: forward voltage is 10 ~ 120V, forward dutycycle is 10 ~ 60%, frequency is 100 ~ 800Hz, positive negative pulse stuffing number is 1 ~ 6, and oxidization time is 10 ~ 100min.
4. the preparation method of titanium alloy surface combined oxidation bioceramic film according to claim 1, is characterized in that: described in step (3), the formula of electrolytic solution is: lime acetate concentration is 15 ~ 40g/L, the concentration of potassiumphosphate is 10 ~ 30g/L.
5. the preparation method of titanium alloy surface combined oxidation bioceramic film according to claim 1, it is characterized in that: described in step (3), the parameter of electrolysis is: forward voltage 220 ~ 600V, forward dutycycle is 10% ~ 60%, frequency is 100Hz ~ 800Hz, positive negative pulse stuffing number is 1 ~ 6, and oxidization time is 10 ~ 30min.
6. the preparation method of titanium alloy surface combined oxidation bioceramic film according to claim 1, is characterized in that: the concentration of the electrolytic solution mesoxalic acid sodium described in step (4) is 10 ~ 25g/L, the concentration of nine water water glass 10 ~ 15g/L, SODIUM PHOSPHATE, MONOBASIC is 10 ~ 15g/L, the concentration of sodium hydroxide is 1 ~ 7g/L.
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| CN106676604A (en) * | 2015-11-05 | 2017-05-17 | 中国科学院金属研究所 | Preparation method and application of bacteriostatic bio-active ceramic membrane for porous titanium or titanium alloy surface of lattice structure |
| CN106725928A (en) * | 2016-12-12 | 2017-05-31 | 同济大学 | A kind of dental implant abutment and preparation method thereof |
| CN106676605B (en) * | 2015-11-05 | 2018-07-13 | 中国科学院金属研究所 | Preparation method and applications with the porous pure titanium of lattice structure or titanium alloy surface multiporous biological active ceramic film |
| CN112301399A (en) * | 2020-07-20 | 2021-02-02 | 江苏燕园精英医疗科技有限公司 | Surface treatment method for dental implant |
| CN112779583A (en) * | 2020-12-26 | 2021-05-11 | 常州市钛宇新材料科技有限公司 | Color and thick film combined titanium alloy surface treatment method |
| CN113089047A (en) * | 2021-04-12 | 2021-07-09 | 四川九洲电器集团有限责任公司 | Aluminum alloy component and preparation method and application thereof |
| CN114540911A (en) * | 2020-11-25 | 2022-05-27 | 比亚迪股份有限公司 | Metal part and preparation method thereof |
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| CN113089047A (en) * | 2021-04-12 | 2021-07-09 | 四川九洲电器集团有限责任公司 | Aluminum alloy component and preparation method and application thereof |
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