CN104674320B - A kind of titanium or the wear-resisting antibacterial bioactive ceramics membrane preparation method of titanium alloy surface and application - Google Patents
A kind of titanium or the wear-resisting antibacterial bioactive ceramics membrane preparation method of titanium alloy surface and application Download PDFInfo
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- CN104674320B CN104674320B CN201310635158.1A CN201310635158A CN104674320B CN 104674320 B CN104674320 B CN 104674320B CN 201310635158 A CN201310635158 A CN 201310635158A CN 104674320 B CN104674320 B CN 104674320B
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- titanium alloy
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- 239000000919 ceramic Substances 0.000 title claims abstract description 90
- 229910001069 Ti alloy Inorganic materials 0.000 title claims abstract description 64
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 55
- 239000010936 titanium Substances 0.000 title claims abstract description 55
- 229910052719 titanium Inorganic materials 0.000 title claims abstract description 50
- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 41
- 230000000975 bioactive effect Effects 0.000 title claims abstract description 39
- 239000012528 membrane Substances 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 32
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 28
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 21
- 239000007943 implant Substances 0.000 claims abstract description 20
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 16
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 9
- 210000000214 mouth Anatomy 0.000 claims abstract description 4
- 238000002604 ultrasonography Methods 0.000 claims abstract description 3
- 239000011575 calcium Substances 0.000 claims description 29
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 27
- 239000000243 solution Substances 0.000 claims description 26
- 239000011701 zinc Substances 0.000 claims description 25
- 238000007254 oxidation reaction Methods 0.000 claims description 23
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 19
- 229960005069 calcium Drugs 0.000 claims description 19
- 239000007864 aqueous solution Substances 0.000 claims description 18
- 239000003792 electrolyte Substances 0.000 claims description 17
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 16
- 239000000463 material Substances 0.000 claims description 16
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 15
- 229910017604 nitric acid Inorganic materials 0.000 claims description 15
- 230000003647 oxidation Effects 0.000 claims description 15
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 14
- 238000005422 blasting Methods 0.000 claims description 11
- 238000002161 passivation Methods 0.000 claims description 11
- 239000004576 sand Substances 0.000 claims description 10
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 10
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 8
- 229940038879 chelated zinc Drugs 0.000 claims description 8
- 238000006388 chemical passivation reaction Methods 0.000 claims description 8
- 238000003825 pressing Methods 0.000 claims description 8
- 230000008569 process Effects 0.000 claims description 8
- 229910052710 silicon Inorganic materials 0.000 claims description 8
- 239000010703 silicon Substances 0.000 claims description 8
- 238000002791 soaking Methods 0.000 claims description 8
- 239000003921 oil Substances 0.000 claims description 7
- 239000000758 substrate Substances 0.000 claims description 7
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 6
- 239000002738 chelating agent Substances 0.000 claims description 6
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 6
- 239000011734 sodium Substances 0.000 claims description 5
- 159000000007 calcium salts Chemical class 0.000 claims description 4
- 150000003751 zinc Chemical class 0.000 claims description 4
- MOMKYJPSVWEWPM-UHFFFAOYSA-N 4-(chloromethyl)-2-(4-methylphenyl)-1,3-thiazole Chemical compound C1=CC(C)=CC=C1C1=NC(CCl)=CS1 MOMKYJPSVWEWPM-UHFFFAOYSA-N 0.000 claims description 3
- 239000001736 Calcium glycerylphosphate Substances 0.000 claims description 3
- 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 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 3
- 229920000388 Polyphosphate Polymers 0.000 claims description 3
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 3
- VSGNNIFQASZAOI-UHFFFAOYSA-L calcium acetate Chemical group [Ca+2].CC([O-])=O.CC([O-])=O VSGNNIFQASZAOI-UHFFFAOYSA-L 0.000 claims description 3
- 235000011092 calcium acetate Nutrition 0.000 claims description 3
- 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 3
- FNAQSUUGMSOBHW-UHFFFAOYSA-H calcium citrate Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O FNAQSUUGMSOBHW-UHFFFAOYSA-H 0.000 claims description 3
- 239000001354 calcium citrate Substances 0.000 claims description 3
- 229940062672 calcium dihydrogen phosphate Drugs 0.000 claims description 3
- UHHRFSOMMCWGSO-UHFFFAOYSA-L calcium glycerophosphate Chemical compound [Ca+2].OCC(CO)OP([O-])([O-])=O UHHRFSOMMCWGSO-UHFFFAOYSA-L 0.000 claims description 3
- 229940095618 calcium glycerophosphate Drugs 0.000 claims description 3
- 235000019299 calcium glycerylphosphate Nutrition 0.000 claims description 3
- MKJXYGKVIBWPFZ-UHFFFAOYSA-L calcium lactate Chemical compound [Ca+2].CC(O)C([O-])=O.CC(O)C([O-])=O MKJXYGKVIBWPFZ-UHFFFAOYSA-L 0.000 claims description 3
- 239000001527 calcium lactate Substances 0.000 claims description 3
- 235000011086 calcium lactate Nutrition 0.000 claims description 3
- 229960002401 calcium lactate Drugs 0.000 claims description 3
- 229910000389 calcium phosphate Inorganic materials 0.000 claims description 3
- 238000010335 hydrothermal treatment Methods 0.000 claims description 3
- 235000019691 monocalcium phosphate Nutrition 0.000 claims description 3
- 229910000403 monosodium phosphate Inorganic materials 0.000 claims description 3
- 235000019799 monosodium phosphate Nutrition 0.000 claims description 3
- 239000001205 polyphosphate Substances 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 claims description 3
- 235000019983 sodium metaphosphate Nutrition 0.000 claims description 3
- 235000013337 tricalcium citrate Nutrition 0.000 claims description 3
- 239000004246 zinc acetate Substances 0.000 claims description 3
- 239000011592 zinc chloride Substances 0.000 claims description 3
- 235000005074 zinc chloride Nutrition 0.000 claims description 3
- 235000001465 calcium Nutrition 0.000 claims description 2
- 229960004256 calcium citrate Drugs 0.000 claims description 2
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 2
- 239000000292 calcium oxide Substances 0.000 claims description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 2
- 229940087373 calcium oxide Drugs 0.000 claims description 2
- 235000012255 calcium oxide Nutrition 0.000 claims description 2
- 238000004140 cleaning Methods 0.000 claims description 2
- 238000005520 cutting process Methods 0.000 claims description 2
- 238000007493 shaping process Methods 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 239000001488 sodium phosphate Substances 0.000 claims description 2
- 229910000162 sodium phosphate Inorganic materials 0.000 claims description 2
- 235000011008 sodium phosphates Nutrition 0.000 claims description 2
- 235000019830 sodium polyphosphate Nutrition 0.000 claims description 2
- 239000007921 spray Substances 0.000 claims description 2
- 230000003746 surface roughness Effects 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
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 2
- 229960001763 zinc sulfate Drugs 0.000 claims description 2
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical group OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims 2
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- 239000010452 phosphate Substances 0.000 claims 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims 1
- 238000000576 coating method Methods 0.000 abstract description 28
- 239000011248 coating agent Substances 0.000 abstract description 19
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- 239000007769 metal material Substances 0.000 abstract description 5
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- 238000004381 surface treatment Methods 0.000 abstract description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 21
- 238000005488 sandblasting Methods 0.000 description 19
- 238000005260 corrosion Methods 0.000 description 16
- 229910052588 hydroxylapatite Inorganic materials 0.000 description 15
- 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 15
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 13
- 210000000988 bone and bone Anatomy 0.000 description 12
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- 238000007745 plasma electrolytic oxidation reaction Methods 0.000 description 7
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- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 6
- 230000008901 benefit Effects 0.000 description 6
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- 239000000470 constituent Substances 0.000 description 6
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- 238000004519 manufacturing process Methods 0.000 description 5
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
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- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229960002901 sodium glycerophosphate Drugs 0.000 description 3
- REULQIKBNNDNDX-UHFFFAOYSA-M sodium;2,3-dihydroxypropyl hydrogen phosphate Chemical compound [Na+].OCC(O)COP(O)([O-])=O REULQIKBNNDNDX-UHFFFAOYSA-M 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000011787 zinc oxide Substances 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Natural products CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 2
- 102000002260 Alkaline Phosphatase Human genes 0.000 description 2
- 108020004774 Alkaline Phosphatase Proteins 0.000 description 2
- 102000004190 Enzymes Human genes 0.000 description 2
- 108090000790 Enzymes Proteins 0.000 description 2
- 241001465754 Metazoa Species 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 229910000883 Ti6Al4V Inorganic materials 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
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- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
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- 241000588724 Escherichia coli Species 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
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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
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61C—DENTISTRY; APPARATUS OR METHODS FOR ORAL OR DENTAL HYGIENE
- A61C8/00—Means to be fixed to the jaw-bone for consolidating natural teeth or for fixing dental prostheses thereon; Dental implants; Implanting tools
- A61C8/0012—Means to be fixed to the jaw-bone for consolidating natural teeth or for fixing dental prostheses thereon; Dental implants; Implanting tools characterised by the material or composition, e.g. ceramics, surface layer, metal alloy
- A61C8/0013—Means to be fixed to the jaw-bone for consolidating natural teeth or for fixing dental prostheses thereon; Dental implants; Implanting tools characterised by the material or composition, e.g. ceramics, surface layer, metal alloy with a surface layer, coating
- A61C8/0015—Means to be fixed to the jaw-bone for consolidating natural teeth or for fixing dental prostheses thereon; Dental implants; Implanting tools characterised by the material or composition, e.g. ceramics, surface layer, metal alloy with a surface layer, coating being a conversion layer, e.g. oxide layer
-
- 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
- C25D11/024—Anodisation under pulsed or modulated current or potential
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Health & Medical Sciences (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Electrochemistry (AREA)
- Orthopedic Medicine & Surgery (AREA)
- Oral & Maxillofacial Surgery (AREA)
- Ceramic Engineering (AREA)
- Dentistry (AREA)
- Epidemiology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Animal Behavior & Ethology (AREA)
- General Health & Medical Sciences (AREA)
- Public Health (AREA)
- Veterinary Medicine (AREA)
- Materials For Medical Uses (AREA)
Abstract
The invention discloses a kind of preparation method and application of the wear-resisting antibacterial bioactive ceramics film of titanium or titanium alloy surface, belong to technical field of metal material surface treatment.The method prepares bottom passivating film first, then under the conditions of combination of ultrasound forward direction square wave pulse voltage, prepares the porous hard ceramic membrane containing Zn, Ca and P, then is carried out hydro-thermal process, finally obtains wear-resisting antibacterial bioactive ceramics film.The inventive method, with being firmly combined with matrix, shows preferable wear-resisting and decay resistance compared with the coating with bioactivity that other methods are obtained, and has fungistatic effect because of the introducing of Zn again while bioactivity is realized.Based on the tooth implant for oral cavity field produced by the present invention, the time of traditional tooth implant and synosteosis is shortened.
Description
Technical field
The present invention relates to field of metal surface treatment technology, and in particular to a kind of titanium or the wear-resisting antibacterial biology of titanium alloy surface
Active ceramic membrane preparation method and application.
Background technology
In biomedical metallic material, titanium or titanium alloy have become tooth implant, bone wound by its excellent performance
Injured labour product and joint prosthesis preferred material.Mainly there is advantages below relative to other medical metal materials：
（1）Compared with stainless steel, the elastic modelling quantity of titanium or titanium alloy with people's bone more closely, biocompatibility more preferably.
（2）The corrosion resisting property and anti-fatigue performance of titanium or titanium alloy are better than stainless steel and cobalt-base alloys, are organized after implantation
Reaction is slight, and surface property is good.
（3）Titanium or titanium alloy influence smaller relative to other medical metal materials on bone growth, and in its tissue
Without nickel composition, allergy is smaller.After testing, titanium alloy implant can be with longer-term persistence body, it is to avoid second operation.
Although titanium or titanium alloy have many advantages compared with other medical metal materials, there is also simultaneously following
Weak point：
（1）Although titanium or titanium alloy have the elastic modelling quantity closest with bone, but still the significantly larger than springform of bone
Amount, so easily causes mechanical performance on interface and mismatches.
（2）From composition, titanium or titanium alloy are entirely different with bone tissue, although they have good life and bone between
Thing compatibility, bone regeneration around implant is formed without fibers encapsulation after implantation, but is a kind of Integrated implant of the embedding even property of machinery between them
Rather than strong chemical synostosis.
（3）Titanium or titanium alloy have good corrosion resisting property because its surface can be formed one layer it is very firm and continuous
Oxide passivation film.But because human body fluid is complicated, surface passivated membrane is implanted with possible damaged, dissolving for a long time so that
Harmful substance is discharged into tissue, causes graft failure.
For these problems, domestic and international researcher has done numerous studies to the synosteosis of planting body, and by different tables
Face processing method prepares different types of coating to improve its anti-corrosion, anti-wear performance in titanium or titanium alloy surface, and improves simultaneously
Its bioactivity.
（1）Dip coating：So-called dip coating is that the mixed solution of P element prepares hydroxyapatite with containing Ca（HA）Colloidal sol.
Hydroxyapatite is the main inorganic composition for constituting human body hard tissue, artificial synthesized hydroxyapatite and internal hydroxy-apatite
Stone is very much like.The dip-coating in HA colloidal sols by titanium or titanium alloy, is obtained HA coatings, for increasing surface-active.Although this side
Method is fairly simple, it is easy to operate, but coating performance is more sensitive to HA colloidal sols composition, pH value, temperature conditionss.Additionally, coating
It is also not high with basal body binding force, it is difficult to meet practical application.
（2）Plasma spraying method：Plasma spraying be clinically study it is more ripe, using more method.This method
It is to make, by the gas ionization between electrode, to form higher temperature plasma using the electric arc produced between two DC electrodes,
Melting is heated during dusty material is sent into flame passes, and is ejected into rapid solidification on metal body at a high speed and form coating.Deng from
Sub- spraying process has the advantages that production efficiency is high, Repeatability is good, coating uniform and suitable industrialized production.But, it is this
The equipment that method and other physics heat spraying methods are required for complexity, cost is of a relatively high, and technological parameter is regulated and controled to require
Compare strict.And the composition and structure of coating are inconsistent with HA in natural bone, and can not obtain equal in surfaces of complex shape
Even coating.These shortcomings limit its clinical practice.
（3）Vapour deposition process：Vapour deposition is the material that will be evaporated or sputter（Metal, alloy or compound）Deposit to
The surface of matrix forms film layer, for changing matrix friction and wear behavior.The titanium alloy coating obtained with vapour deposition process has
Hardness higher, wear-resisting and its resistance to corrosion, and low cost, are widely used.But the universal prepares coating of vapour deposition is relatively thin, with
The adhesion of substrate is not strong enough, it is difficult to meets and requires.
It will be apparent that the studies above work achieves result highly significant in some aspects, but prepared coating is deposited
In not enough problem, it is difficult to meet needs of production.Therefore, have in titanium alloy surface exploitation strong with matrix combination higher
Degree, good wear-resisting, corrosion resisting property and there is the coating of preferable bioactivity simultaneously, the scientific worker that still needs proceeds depth
Enter and the exploration of system.
The content of the invention
It is an object of the invention to overcome the deficiencies in the prior art, there is provided a kind of titanium or the wear-resisting antibacterial biology of titanium alloy surface
The preparation method and application of active ceramic film.Using the method prepare wear-resisting antibacterial bioactive ceramics film, not only with
The advantage that matrix is firmly combined with, also with good wear-resisting and corrosion resistance.Simultaneously as the addition of Zn makes it also have in coating
There is good biocidal property, so as to realize the feature of titanium or titanium alloy implant.Zinc is the important trace element of human body, is body
It is middle to participate in one of most trace element of physiological function.This element all plays important work in terms of DNA synthesis, protein metabolism
With while contributing to cell proliferation and differentiation and relevant enzyme system to play its functional activity；Zinc also has good biocidal property simultaneously.
So the ceramic layer containing Zn, HA can improve titanium or the bioactivity of titanium alloy substrate and have fungistatic effect again.And, should
Ceramic membrane not only can individually be used as biological coating, and can be processed by following process, be further converted to more resistance to
Erosion, wear-resisting and high bioactivity composite ceramic layer, to improve the combination property of titanium or titanium alloy surface.
The technical solution adopted in the present invention is as follows：
The preparation method of a kind of titanium or the wear-resisting antibacterial bioactive ceramics film of titanium alloy surface, comprises the following steps：
（1）Chemical passivation is processed：After titanium or titanium alloy surface are through blasting treatment, it is passivated in passivating solution.
（2）The preparation of the porous hard ceramic membrane containing Zn, Ca and P：Titanium or titanium alloy after Passivation Treatment is tied in ultrasound
Differential arc oxidation is carried out under the conditions of the positive square-wave pulse of conjunction, the porous hard ceramic containing Zn, Ca and P is prepared in titanium or titanium alloy surface
Film；Its composition of the electrolyte of the differential arc oxidation use is as follows：
Containing in the porous hard ceramic membrane preparation process of Zn, Ca and P, ultrasonic power is 20~90W, electrolyte temperature 20~50
DEG C, electric source modes are positive square-wave pulse, oxide termination 250~450V of voltage, oxidization time 5~30 minutes, current density 1~
5A/dm2, 100~1000Hz of frequency, dutycycle 30%~90%.
（3）Hydro-thermal process：Titanium or titanium alloy that surface prepares porous hard ceramic membrane are put into and contain alkaline aqueous solution
Heated in enclosed high pressure reactor, cooled down in atmosphere after taking out drying, obtained in titanium or titanium alloy surface and contain HA
With the wear-resisting antibacterial bioactive ceramics film of Zn.
In hydrothermal treatment process, alkaline aqueous solution used is the NaOH aqueous solution, and its pH value is 10-12, and heating-up temperature is
150~250 DEG C, 8~12h of soaking time, pressing force is 5~15MPa.
The blasting treatment：Material spray is silica sand, 0.2~1mm of silicon sand size, 0.2~0.5MPa of compressed air intensity；Sandblasting
Substrate Surface Roughness Ra3.0~6.5 μm after treatment.
The passivating solution is mixed by hydrofluoric acid and nitric acid, and the volume ratio of hydrofluoric acid and nitric acid is 1:3~1:5；Hydrogen
Fluoric acid is the hydrofluoric acid that volumetric concentration is 40%, and nitric acid is the nitric acid that volumetric concentration is 70%.1~5min of passivation time, gained
Thickness to passivating film is 1~5 μm.
Described chelating calcium is to use complexometry, obtained by calcium salt and chelating agent are chelated；The calcium salt is acetic acid
One or more of calcium, calcium chloride, calcium dihydrogen phosphate, calcium glycerophosphate, calcium citrate, calcium lactate and calcium oxide.The phosphoric acid
Salt is one or more in sodium glycero-phosphate, sodium dihydrogen phosphate, sodium metaphosphate and polyphosphate sodium.Described chelated zinc is to use
Obtained by complexometry is chelated zinc salt and chelating agent；The zinc salt is in zinc acetate, zinc chloride, zinc nitrate and zinc sulfate
One or more.The chelating calcium is negatively charged with chelated zinc, in the solution with preferable stability.Described chelating agent is
Na2EDTA or EDTA.Described nano granular of zinc oxide average-size is 20~60nm.
In step（1）It is preceding by titanium or titanium alloy substrate material cutting polishing after, in acetone ultrasonic wave cleaning removal surface
Grease, ultrasonic time is 10~20min.
Titanium or wear-resisting antibacterial its thickness of bioactive ceramics film of titanium alloy surface prepared by method described above is 10~30 μm,
Porosity is 30~60%.Can be used for the tooth implant in Medical oral cavity field.The ceramic membrane is put on the tooth kind of machined shaping
Implant makes its surface produce one layer of wear-resisting antibacterial bioactive ceramics film.The planting body is tested by zoopery, its synosteosis
Time is 15~20 days.
Differential arc oxidation（MAO）：Micro-plasma oxidation is also called, in the application oxidizing process, due to puncturing what is formed
Discharge channel can be such that hard tissue implanting material grows inwardly, therefore, it can preferably improve and area of new bone mechanical engagement.Using
Ceramic layer prepared by differential arc oxidation not only has wear-resistant and corrosion resistance higher, also maintains ceramics and titanium alloy substrate
Adhesion.Meanwhile, the process is simple of the technology, low cost, pollution are small, variously-shaped element can be processed, with extensive
Application prospect.
Hydroxyapatite（HA）：The natural composite wood that people's bone tissue is inherently constituted into bone fibres and hydroxyapatite
Material.Hydroxyapatite is referred to as HA, and its element composition is Ca, P, O and H element, is closed containing that bond can occur with tissue
Hydroxyl, its chemical composition, crystal structure to constitute tissue hydroxyapatite wear it is brilliant and its similar.Implantation human body hard tissue
It is bonded very well with bone afterwards, and bone growth can be induced, and tissue reaction is slight, in has turned into bioactive ceramics now
Preferred material.
Zinc：As one of micro elements needed by human, all physiological metabolism processes are almost participated in body, zinc has urges
Change and adjustment effect, be the confactor of internal more than 300 kinds of enzymes.There is important physiological function just because of zinc, body is required
Maintain enough zinc to promote cell growth, maintain cell function.Research shows that zinc take part in Gegenbaur's cell alkaline phosphatase
Formed, and play catalysis, joint activation and enclosed structure effect, so that alkaline phosphatase activities increases.Can also be in acceleration bodies
The synthesis of DNA and RNA, increased the aggregate velocity of protein, enhance the vitality of osteocyte.Meanwhile, zinc also have compared with
Good fungistatic effect, Nano-class zinc oxide can effectively suppress streptococcus mutans activity, and can effectively suppress golden yellow Portugal
Grape coccus and the growth of Escherichia coli.
Chelating calcium is prepared with chelated zinc：Because differential arc oxidation is a kind of anodic oxidation of growth in situ, will be positively charged
Calcium/zinc ion is formed it into negatively charged chelating calcium/chelated zinc ions by chelating method, not only increased the stabilization of solution
Property, can more promote deposition of the calcium/zinc in film.Concrete operation method：Using acid Na2EDTA solution is by calcic/zinc chemical
Reagent dissolves, make+divalent calcium/zinc ion is free in the middle of solution.Then the pH value of the solution is adjusted to 2mol/L NaOH
12.Now, major part EDTA is changed into the Y of -4 valencys in solution4-In corresponding solution+divalent calcium/zinc ion progressively chelates to-divalent calcium
Ion [CaY]2-/ zinc chelating ion [ZnY]2-Transformation.Chelate [CaY] with five-membered ring structure2-/[ZnY]2-Chemically stable
Property it is stronger, stability constant is 10, in order to ensure to be complexed completely, at a temperature of 40~50 DEG C, with magnetic stirring apparatus by the solution connect
Continuous stirring 24 hours.
Compared with prior art, the present invention has following significant advantage：
1st, wear-resisting antibacterial bioactive ceramics film thickness of the invention is uniform, is well combined with matrix, not only with good
Wearability and corrosion resistance, and introducing due to ultimately generating HA and Zn makes it have bioactivity higher and antibacterial
Property.The coating can both be used separately as bioactivity coatings, can also be by post processing（Cold spraying, thermal spraying and electrophoresis etc.）,
It is prepared into more anti-corrosion, wear-resisting and high bioactivity function of surface coating.
2nd, microplasma is formed in pure titanium to be processed or titanium alloy surface using the inventive method, is joined by controlling technique
Number generates wear-resisting antibacterial bioactive ceramics film in titanium to be processed or titanium alloy surface.Performance test shows the hard of the ceramic membrane
The surface microhardness of fine and close bottom reaches 600~800HV, and the corrosion current density of ceramic layer is in biosimulation solution
1.0E-9~1.0E-8A/cm2；The induction hydroxyapatite of its porous surface bioactivity coatings formed the time for 10~15 days,
It is 15~25 days that cell is sprawled with repoductive time, and compared with spelter coating is not added with, fungistatic effect improves 50~70%.
3rd, the inventive method has compared with conventional similar antibacterial bioactive ceramics membrane process wear-resisting containing Zn, Ca, P
Advantages below：（1）Chelating calcium, the chelated zinc/nano granular of zinc oxide of negative valency are added in electrolyte, it is more stablized, technique
It is repeated preferable.（2）The content of Ca is higher in prepared coating, and HA contents are high during coating is finally obtained by hydro-thermal process；
Thus protein adsorption ability, cell propagation, absorption, differentiation capability are stronger.
4th, tooth implant for oral cavity field of the present invention based on the method manufacture, shortens traditional tooth implant and bone
With reference to time.Manufactured titanium or titanium alloy implant is tested by zoopery, and its synosteosis time is 15~20 days.
5th, the medicine applied in preparation process is common and more cheap, reduces production cost, is suitable to extensive work
Industry metaplasia is produced.
Brief description of the drawings：
Fig. 1 is scanning electron microscope (SEM) photograph of the positive direction square-wave pulse without zinc ceramic membrane of comparative example 1.
Fig. 2 is scanning electron microscope (SEM) photograph of the positive direction square-wave pulse of the embodiment of the present invention 1 containing zinc ceramic membrane.
Specific embodiment：
The present invention is described further with reference to embodiment.
Comparative example 1
1. material prepares：After the pure cleaved polishing of titanium, oil removing is cleaned with ultrasonic wave in acetone soln.
2. sandblasting：The silicon sand size of sandblasting is 0.2mm, and compressed air intensity is 0.2MPa, obtains matrix surface coarse
It is Ra3.0 μm to spend, and sandblasting instrument is RH-1010P high pressure dry blasting machines.
3. chemical passivation：In passivating solution, 40%（Volumetric concentration）HF is 2mL/L, 70%（Volumetric concentration）HNO310mL/L, body
Product ratio is 1：5, remaining is water.Temperature is room temperature, is processed 2 minutes, is cleaned with running water 1~2 minute immediately after taking-up, then use
Deionized water is cleaned 1~2 minute, and passivation film thickness is 1 μm.
4. prepared by positive square-wave pulse ceramic coating formed by micro-arc oxidation：Electrolyte：Concentration is 0.3mol/L calcium acetates, and concentration is
The sodium glycero-phosphate of 0.01mol/L, remaining is water.
In ceramic membrane preparation process, ultrasonic power 50W, 30 DEG C of electrolyte temperature, electric source modes are positive direction square-wave pulse,
The whole voltage of forward direction oxidation is 350V, and oxidization time is 25 minutes, current density 2A/dm2, frequency is 500Hz, and dutycycle is 50%,
The ceramic film thickness of acquisition is 14 μm, and porosity is 55%.
5. hydro-thermal process：The aqueous solution is the NaOH aqueous solution, and its pH value is 10.Hydro-thermal reaction is carried out in autoclave,
Heating-up temperature is 200 DEG C, and soaking time 10h, pressing force is 8MPa, ceramic membrane is taken out and is cooled down in atmosphere after drying.
By after drying, ceramic membrane being obtained on pure titanium surface.Fig. 1 is the scanning electron microscope (SEM) photograph of ceramic membrane prepared by this example.This
The correlated performance data of example is as follows：
Ceramic of compact bottom is more than 22MPa with basal body binding force, and hardness is 600HV, and the content of calcium constituent is in film layer
6.98%, the content of P elements is 4.59%.The corrosion current density of ceramic layer is 8,123E-9A/ in biosimulation solution
cm2；The induction hydroxyapatite of its porous surface bioactivity coatings formed the time for 15 days, and cell is sprawled and is with repoductive time
28 days, bacteriostasis rate was 31.58%.Passed through in wear-resisting antibacterial bioactive ceramics film prepared by pure titanium implant surface using this method
Zoopery proves that its synosteosis time is 28 days.
Embodiment 1
1. material prepares：After the pure cleaved polishing of titanium, oil removing is cleaned with ultrasonic wave in acetone soln.
2. sandblasting：The silicon sand size of sandblasting is 0.2mm, and compressed air intensity is 0.2MPa, obtains matrix surface coarse
It is Ra3.0 μm to spend, and sandblasting instrument is RH-1010P high pressure dry blasting machines.
3. chemical passivation：In passivating solution, 40%（Volumetric concentration）HF is 2mL/L, 70%（Volumetric concentration）HNO310mL/L, body
Product ratio is 1：5, remaining is water.Temperature is room temperature, is processed 2 minutes, is cleaned with running water 1~2 minute immediately after taking-up, then use
Deionized water is cleaned 1~2 minute, and passivation film thickness is 1 μm.
4. prepared by positive square-wave pulse ceramic coating formed by micro-arc oxidation：Electrolyte：Concentration is 0.3mol/L calcium acetates, and concentration is
The sodium glycero-phosphate of 0.01mol/L, concentration is the zinc acetate of 0.01mol/L, and concentration is 0.3mol/LNa2EDTA, remaining is water.
In ceramic membrane preparation process, ultrasonic power 50W, 30 DEG C of electrolyte temperature, electric source modes are positive direction square-wave pulse,
The whole voltage of forward direction oxidation is 350V, and oxidization time is 20 minutes, current density 2A/dm2, frequency is 500Hz, and dutycycle is 50%,
The ceramic film thickness of acquisition is 12 μm, and porosity is 50%.
5. hydro-thermal process：The aqueous solution is the NaOH aqueous solution, and its pH value is 10.Hydro-thermal reaction is carried out in autoclave,
Heating-up temperature is 200 DEG C, and soaking time 10h, pressing force is 8MPa, ceramic membrane is taken out and is cooled down in atmosphere after drying.
By after drying, wear-resisting antibacterial bioactive ceramics film being obtained on pure titanium surface.Fig. 2 is the prepared pottery of the present embodiment
The scanning electron microscope (SEM) photograph of porcelain film.The correlated performance data of the present embodiment is as follows：
Ceramic of compact bottom is more than 20MPa with basal body binding force, and hardness is 600HV, and the content of calcium constituent is in film layer
12.75%, the content of P elements is 5.62%, and the content of Zn-ef ficiency is 3.12%.The self-corrosion of ceramic layer in biosimulation solution
Current density is 7.38E-9A/cm2；The induction hydroxyapatite of its porous surface bioactivity coatings formed the time for 12 days,
It is 20 days that cell is sprawled with repoductive time, and bacteriostasis rate is 60.78%.
The wear-resisting antibacterial bioactive ceramics film that is prepared on pure titanium implant surface using this method animal experiments prove that
Its synosteosis time is 20 days.
Embodiment 2
1. material prepares：After the pure cleaved polishing of titanium, oil removing is cleaned with ultrasonic wave in acetone soln.
2. sandblasting：The silicon sand size of sandblasting is 0.8mm, and compressed air intensity is 0.5MPa, obtains matrix surface coarse
It is Ra5.0 μm to spend, and sandblasting instrument is RH-1010P high pressure dry blasting machines.
3. chemical passivation：In passivating solution, 40%（Volumetric concentration）HF is 2ml/L, 70%（Volumetric concentration）HNO38ml/L, body
Product ratio is 1：4, remaining is water.Temperature is room temperature, is processed 3 minutes, is cleaned with running water 1~2 minute immediately after taking-up, then use
Deionized water is cleaned 1~2 minute, and passivation film thickness is 1 μm.
4. prepared by positive square-wave pulse ceramic coating formed by micro-arc oxidation：Electrolyte：Concentration is the calcium dihydrogen phosphate of 0.2mol/L, dense
The sodium phosphate for 0.015mol/L is spent, concentration is the zinc nitrate of 0.03mol/L, and concentration is the EDTA of 0.25mol/L, and remaining is
Water.
In ceramic membrane preparation process, 40 DEG C of electrolyte temperature, electric source modes are positive direction square-wave pulse, and forward direction oxidation is electric eventually
It is 450V to press;Oxidization time is 10 minutes, current density 2A/dm2, frequency is 800Hz, and dutycycle is 50%, the ceramic membrane of acquisition
Thickness is 12 μm, and porosity is 40%.
5. hydro-thermal process：The aqueous solution is the NaOH aqueous solution, its pH value 11.Hydro-thermal reaction is carried out in autoclave, plus
Hot temperature is 180 DEG C, and soaking time is 8h, and pressing force is 10MPa, ceramic membrane is taken out and is cooled down in atmosphere after drying.
By after drying, wear-resisting antibacterial bioactive ceramics film being obtained on pure titanium surface.The correlated performance number of the present embodiment
According to as follows：
Ceramic of compact bottom is more than 22MPa with basal body binding force, and hardness is 700HV, and the content of calcium constituent is in film layer
11.69%, the content of P elements is 6.75%, and the content of Zn-ef ficiency is 4.85%.The self-corrosion of ceramic layer in biosimulation solution
Current density is 7.46E-9A/cm2；The induction hydroxyapatite of its porous surface bioactivity coatings formed the time for 10 days,
It is 15 days that cell is sprawled with repoductive time, and bacteriostasis rate is 71.93%.
The wear-resisting antibacterial bioactive ceramics film that is prepared on pure titanium implant surface using this method animal experiments prove that
Its synosteosis time is 15 days.
Embodiment 3
1. material prepares：Titanium alloy（Ti6Al4V）After cleaved polishing, oil removing is cleaned with ultrasonic wave in acetone soln.
2. sandblasting：The silicon sand size of sandblasting is 1.0mm, and compressed air intensity is 0.6MPa, obtains matrix surface coarse
It is Ra4.0 μm to spend, and sandblasting instrument is RH-1010P high pressure dry blasting machines.
3. chemical passivation：In passivating solution, 70%（Volumetric concentration）HNO34ml/L, HNO38ml/L, volume ratio is 1：4, its
Yu Weishui.Temperature is room temperature, is processed 5 minutes, is cleaned with running water 1~2 minute immediately after taking-up, then clean 1 with deionized water
~2 minutes, passivation film thickness was 1 μm.
4. prepared by positive square-wave pulse ceramic coating formed by micro-arc oxidation：Electrolyte：Concentration is the calcium glycerophosphate of 0.25mol/L,
Concentration is the polyphosphate sodium of 0.012mol/L, and concentration is the zinc chloride of 0.02mol/L, and concentration is 0.25mol/L EDTA2Na, its
Yu Weishui.
In oxide-film preparation process, 20~50 DEG C of electrolyte temperature, electric source modes are positive direction square-wave pulse, forward direction oxidation
Whole voltage is 400V, and oxidization time is 15 minutes, current density 3A/dm2, frequency is 1000Hz, and dutycycle is 60%, acquisition
Oxide thickness is 20 μm, and porosity is 60%.
5. hydro-thermal process：The aqueous solution is the NaOH aqueous solution, its pH value 12.Hydro-thermal reaction is carried out in autoclave, plus
Hot temperature is 180 DEG C, and soaking time is 8h, and pressing force is 10MPa, ceramic membrane is taken out and is cooled down in atmosphere after drying.
By after drying, wear-resisting antibacterial bioactive ceramics film being obtained in titanium alloy surface.The correlated performance of the present embodiment
Data are as follows：
Ceramic of compact bottom is more than 25MPa with basal body binding force, and hardness is 750HV, and the content of calcium constituent is in film layer
12.31%, the content of P elements is 6.02%, and the content of Zn-ef ficiency is 4.31%.The self-corrosion of ceramic layer in biosimulation solution
Current density is 1.25E-8A/cm2；The induction hydroxyapatite of its porous surface bioactivity coatings formed the time for 12 days,
It is 20 days that cell is sprawled with repoductive time, and bacteriostasis rate is 64.68%.
Demonstrate,proved through zoopery in wear-resisting antibacterial bioactive ceramics film prepared by titanium alloy implant surface using this method
Bright its synosteosis time is 18 days.
Embodiment 4
1. material prepares：Titanium alloy（Ti6Al4V）After cleaved polishing, oil removing is cleaned with ultrasonic wave in acetone soln.
2. sandblasting：The silicon sand size of sandblasting is 1.0mm, and compressed air intensity is 0.4MPa, obtains matrix surface coarse
It is Ra6.0 μm to spend, and sandblasting instrument is RH-1010P high pressure dry blasting machines.
3. chemical passivation：In passivating solution, 40%（Volumetric concentration）HF2mL/L, 70%（Volumetric concentration）HNO36mL/L, volume
Ratio is 1：3, remaining is water.Temperature：Room temperature, is processed 5 minutes, is cleaned with running water 1~2 minute immediately after taking-up, then spend
Ionized water is cleaned 1~2 minute, and passivation film thickness is 1 μm.
4. prepared by positive square-wave pulse ceramic coating formed by micro-arc oxidation：Electrolyte：Concentration is the calcium citrate of 0.15mol/L, dense
The sodium metaphosphate for 0.015mol/L is spent, concentration is the zinc nitrate of 0.02mol/L, and concentration is the EDTA of 0.2mol/L2Na, remaining
It is water.
In ceramic membrane preparation process, 40 DEG C of electrolyte temperature, electric source modes are positive direction square-wave pulse, and forward direction oxidation is electric eventually
It is 380V to press；Oxidization time is 35 minutes, current density 1A/dm2, frequency is 1000Hz, and dutycycle is 70%, the ceramics of acquisition
Film thickness is 25 μm, and porosity is 65%.
5. hydro-thermal process：The aqueous solution is the NaOH aqueous solution, its pH value 12.Hydro-thermal reaction is carried out in autoclave, plus
Hot temperature is 180 DEG C, and soaking time is 8h, and pressing force is 10MPa, ceramic membrane is taken out and is cooled down in atmosphere after drying.
By after drying, wear-resisting antibacterial bioactive ceramics film being obtained in titanium alloy surface.The correlated performance of the present embodiment
Data are as follows：
Ceramic of compact bottom is more than 30MPa with basal body binding force, and hardness is 900HV, and the content of calcium constituent is in film layer
10.31%, the content of P elements is 5.98%, and the content of Zn-ef ficiency is 4.12%.The self-corrosion of ceramic layer in biosimulation solution
Current density is 9.45E-9A/cm2；The induction hydroxyapatite of its porous surface bioactivity coatings formed the time for 15 days,
It is 15 days that cell is sprawled with repoductive time, and bacteriostasis rate is 63.49%.
Demonstrate,proved through zoopery in wear-resisting antibacterial bioactive ceramics film prepared by titanium alloy implant surface using this method
Bright its synosteosis time is 20 days.
Embodiment 5
1. material prepares：Titanium alloy（Ti-13Nb-13Zr）After cleaved polishing, cleaned with ultrasonic wave in acetone soln
Oil removing.
2. sandblasting：The silicon sand size of sandblasting is 0.8mm, and compressed air intensity is 0.25MPa, obtains matrix surface coarse
It is Ra5.0 μm to spend, and sandblasting instrument is RH-1010P high pressure dry blasting machines.
3. chemical passivation：In passivating solution, 40%（Volumetric concentration）HF5mL/L, 70%（Volumetric concentration）Nitric acid 20mL/L, its
Yu Weishui.Temperature：Room temperature, is processed 5 minutes, is cleaned with running water 1~2 minute immediately after taking-up, then clean 1 with deionized water~
2 minutes, passivation film thickness was 1 μm.
4. prepared by positive square-wave pulse ceramic coating formed by micro-arc oxidation：Electrolyte：Concentration is the calcium lactate of 0.2mol/L, and concentration is
The sodium dihydrogen phosphate of 0.01molg/L, concentration is the zinc nitrate of 0.015mol/L, and concentration is the EDTA of 0.2mol/L, and remaining is
Water.
In ceramic membrane preparation process, 30 DEG C of electrolyte temperature, electric source modes are positive direction square-wave pulse, and forward direction oxidation is electric eventually
It is 400V to press, and oxidization time is 30 minutes, current density 1.5A/dm2, frequency is 800Hz, and dutycycle is 80%, the ceramics of acquisition
Film thickness is 20 μm, and porosity is 75%.
5. hydro-thermal process：The aqueous solution is the NaOH aqueous solution, its pH value 12.Hydro-thermal reaction is carried out in autoclave, plus
Hot temperature is 180 DEG C, and soaking time is 8h, and pressing force is 10MPa, ceramic membrane is taken out and is cooled down in atmosphere after drying.
By after drying, wear-resisting antibacterial bioactive ceramics film being obtained in titanium alloy surface.The correlated performance of the present embodiment
Data are as follows：
Ceramic of compact bottom is more than 30MPa with basal body binding force, and hardness is 1000HV, and the content of calcium constituent is in film layer
14.36%, the content of P elements is 5.09%, and the content of Zn-ef ficiency is 3.98%.The self-corrosion of ceramic layer in biosimulation solution
Current density is 8.32E-9A/cm2；The induction hydroxyapatite of its porous surface bioactivity coatings formed the time for 12 days,
It is 15 days that cell is sprawled with repoductive time, and bacteriostasis rate is 61.33%.
Demonstrate,proved through zoopery in wear-resisting antibacterial bioactive ceramics film prepared by titanium alloy implant surface using this method
Bright its synosteosis time is 18 days.
Claims (10)
1. the preparation method of a kind of titanium or the wear-resisting antibacterial bioactive ceramics film of titanium alloy surface, it is characterised in that：The method bag
Include following steps：
(1) chemical passivation treatment：After titanium or titanium alloy surface are through blasting treatment, it is passivated in passivating solution；
(2) preparation of the porous hard ceramic membrane containing Zn, Ca and P：By the titanium or titanium alloy after Passivation Treatment in combination of ultrasound just
To differential arc oxidation is carried out under the conditions of square-wave pulse, the porous hard ceramic membrane containing Zn, Ca and P is prepared in titanium or titanium alloy surface；
Its composition of the electrolyte of the differential arc oxidation use is as follows：
The chelating calcium is obtained by being chelated calcium salt and chelating agent using complexometry；The calcium salt is calcium acetate, chlorination
One or more of calcium, calcium dihydrogen phosphate, calcium glycerophosphate, calcium citrate, calcium lactate and calcium oxide；The phosphate is glycerine
One or more in sodium phosphate, sodium dihydrogen phosphate, sodium metaphosphate and polyphosphate sodium；Described chelated zinc is will using complexometry
Obtained by zinc salt is chelated with chelating agent；The zinc salt is the one kind or several in zinc acetate, zinc chloride, zinc nitrate and zinc sulfate
Kind；The chelating calcium is negatively charged with chelated zinc；Described chelating agent is Na2EDTA or EDTA；Described nano zine oxide
Grain average-size is 20~60nm；
(3) hydro-thermal process：Titanium or titanium alloy that surface prepares porous hard ceramic membrane are put into and contain the closed of alkaline aqueous solution
Heated in autoclave, cooled down in atmosphere after taking out drying, obtained in titanium or titanium alloy surface and contain HA and Zn
Wear-resisting antibacterial bioactive ceramics film.
2. the preparation method of titanium according to claim 1 or the wear-resisting antibacterial bioactive ceramics film of titanium alloy surface, it is special
Levy and be：Containing in the porous hard ceramic membrane preparation process of Zn, Ca and P, ultrasonic power is 20~90W, electrolyte temperature 20~50
DEG C, electric source modes are positive square-wave pulse, oxide termination 250~450V of voltage, oxidization time 5~30 minutes, current density 1~
5A/dm2, 100~1000Hz of frequency, dutycycle 30%~90%.
3. the preparation method of titanium according to claim 1 or the wear-resisting antibacterial bioactive ceramics film of titanium alloy surface, it is special
Levy and be：In step (3) hydrothermal treatment process, alkaline aqueous solution used is the NaOH aqueous solution, and its pH value is 10-12.
4. the preparation method of the wear-resisting antibacterial bioactive ceramics film of titanium or titanium alloy surface according to claim 1 or 3, its
It is characterised by：In step (3) hydrothermal treatment process, heating-up temperature is 150~250 DEG C, 8~12h of soaking time, and pressing force is
5~15MPa.
5. the preparation method of titanium according to claim 1 or the wear-resisting antibacterial bioactive ceramics film of titanium alloy surface, it is special
Levy and be：Titanium or the cutting of titanium alloy substrate material are polished before step (1) after, ultrasonic wave cleaning in acetone removes surface oil
Dirt, ultrasonic time is 10~20min.
6. the preparation method of titanium according to claim 1 or the wear-resisting antibacterial bioactive ceramics film of titanium alloy surface, it is special
Levy and be：During the blasting treatment：Material spray is silica sand, 0.2~1mm of silicon sand size, compressed air intensity 0.2~
0.5MPa；Substrate Surface Roughness Ra3.0~6.5 μm after blasting treatment.
7. the preparation method of titanium according to claim 1 or the wear-resisting antibacterial bioactive ceramics film of titanium alloy surface, it is special
Levy and be：Passivating solution is mixed by hydrofluoric acid and nitric acid described in step (1), and the volume ratio of hydrofluoric acid and nitric acid is 1:3
~1:5；Hydrofluoric acid is the hydrofluoric acid that volumetric concentration is 40%, and nitric acid is the nitric acid that volumetric concentration is 70%；Passivation time 1~
5min, the thickness of resulting passivating film is 1~5 μm.
8. the preparation method of titanium according to claim 1 or the wear-resisting antibacterial bioactive ceramics film of titanium alloy surface, it is special
Levy and be：The wear-resisting antibacterial bioactive ceramics film thickness is 10~30 μm, the hole of wear-resisting antibacterial bioactive ceramics film
Rate is 30~60%.
9. the application of titanium according to claim 1 or the wear-resisting antibacterial bioactive ceramics film of titanium alloy surface, its feature exists
In：The titanium or the wear-resisting antibacterial bioactive ceramics film of titanium alloy surface are used for the tooth implant in Medical oral cavity field.
10. the application of titanium according to claim 9 or the wear-resisting antibacterial bioactive ceramics film of titanium alloy surface, its feature exists
In：The wear-resisting antibacterial bioactive ceramics film is put on the tooth implant of machined shaping.
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| CN106676604B (en) * | 2015-11-05 | 2018-07-20 | 中国科学院金属研究所 | Preparation method and applications with the porous titanium of lattice structure or the antibacterial bioactive ceramics film of titanium alloy surface |
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| CN109097760B (en) * | 2018-10-19 | 2020-09-08 | 济南大学 | Preparation method of medical titanium material |
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| CN111218706A (en) * | 2020-02-25 | 2020-06-02 | 北京爱康宜诚医疗器材有限公司 | Preparation method of antibacterial three-dimensional porous bone implant material |
| CN111359009B (en) * | 2020-03-25 | 2022-06-24 | 天衍医疗器材有限公司 | Porous tantalum implant with biological activity function and processing technology |
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| WO2022059672A1 (en) * | 2020-09-16 | 2022-03-24 | 日本製鉄株式会社 | Titanium material and method for manufacturing titanium material |
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| CN113235146B (en) * | 2021-05-21 | 2023-01-24 | 江西科技师范大学 | Micro-arc oxidation electrolyte and application method thereof |
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