CN104562145B - A kind of method that combined oxidation prepares bioceramic film - Google Patents

A kind of method that combined oxidation prepares bioceramic film Download PDF

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CN104562145B
CN104562145B CN201410803384.0A CN201410803384A CN104562145B CN 104562145 B CN104562145 B CN 104562145B CN 201410803384 A CN201410803384 A CN 201410803384A CN 104562145 B CN104562145 B CN 104562145B
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oxidation
electrolyte
titanium alloy
carries
titanium
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CN104562145A (en
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严继康
唐婉霞
倪尔鑫
段志操
甘国友
杜景红
张家敏
刘意春
鲍瑞
易健宏
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Kunming University of Science and Technology
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    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25DPROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02Anodisation
    • C25D11/26Anodisation of refractory metals or alloys based thereon

Abstract

The present invention discloses a kind of method that combined oxidation prepares bioceramic film, belongs to biological and medicinal implant material process for treating surface.Titanium alloy style is first carried out pretreatment and is placed in electrolyte as anode by the method for the invention, and stainless steel electrolytic groove is cathode, carries out anodic oxidation;Then it is again placed in being used as anode in above-mentioned electrolyte through anodized titanium alloy style, stainless steel electrolytic groove is cathode, then carries out drying after being cleaned with deionized water after differential arc oxidation and obtain combined oxidation preparing bioceramic film;This bioceramic film forms metallurgical binding, compact structure, toughness height with titanium alloy substrate surface;Hydroxyapatite phase and more Rutile Type are contained in outside, have certain biocompatibility, have good mechanical property, and corrosion resistance, chemical stability is good, meets the requirement of body implanting material, are one of bone implantation and the main material repaired.

Description

A kind of method that combined oxidation prepares bioceramic film
Technical field
The present invention relates to a kind of method that combined oxidation prepares bioceramic film, belong at biological and medicinal implant material surface Reason technology.
Background technology
With aging of population aggravation and the unexpected increase for causing injury, people are to bio-medical material and its product Demand is increasing.Current clinically widely used medical equipment is manufactured by stainless steel and titanium alloy more.Titanium alloy is because having Good biocompatibility and high specific strength and be used widely in biomedical sector, but industrial titanium be metal life Thing inert material, it is longer with the healing time of wound;The abrasion resistance properties of titanium and its alloy are poor, be implanted into human body after due to for a long time with The abrasive dust that other sclerous tissueses of human body rub and produce can dissociate around implant, cause inflammation even graft failure.Then it is Medical titanium alloy is surface-treated, it is improved and is implanted into performance and biocompatibility, strengthen its biology with tissue The precipitation of compatibility and poisonous and harmful substance, reduces the formation of platelet adhesion reaction and thrombus, using composite oxidation technology, contains calcium In the electrolyte of P elements, anodized first is carried out to titanium alloy, in one layer of smooth fine and close anodic oxidation of Surface Creation Film, then carries out differential arc oxidation processing again so that surface regenerates one layer on the basis of smooth fine and close anode oxide film and contains Hydroxyapatite and rough porous form the porous ceramics film layer of three-dimensional communication state.
The thickness of surface ceramic film layer is adjusted by adjusting the electrical parameter of anodic oxidation and differential arc oxidation, by adjusting electricity Solution liquid is formed to control chemical composition, thing phase composition and the pore structure of porous bio-ceramic, so as to form titanium alloy bioceramic The gradient-structure of film layer, and form the hydroxyapatite with good biocompatibility on surface.Since anode oxide film is fine and close, It is high with substrate combinating strength, the precipitation of poisonous and harmful substance in matrix can be effectively reduced, micro-arc oxidation films are coarse and formed three-dimensional Connected state, containing hydroxyapatite, has the characteristics that tissue quickly grows into and heals with human body, so as to fulfill good biology Compatibility.
Method by being modified to titanium alloy combined oxidation surface, its internal compacted zone can not only effectively improve its use Performance, reduces the precipitation of internal poisonous and harmful substances, can also there is three-dimensional connected porous weaker zone containing hydroxyapatite outside it Effect makes area of new bone be deposited directly to titanium alloy surface and promotes bone uptake, and combined oxidation can not only improve titanium alloy implantation body surface The stability and wearability in face, can also improve its surface bioactive, so as to be allowed to preferably serve medical domain.
The content of the invention
It is an object of the invention to provide a kind of method that combined oxidation prepares bioceramic film, the method passes through anode Oxidation prepares one layer and the compact interior solid layer of titanium alloy substrate, then by differential arc oxidation on the basis of anode oxide film Upper one layer of preparation has anti-corrosion, wear-resisting and good biological performance ceramic coating formed by micro-arc oxidation, specifically includes following steps:
(1)Pretreatment:Surface grinding process is carried out to titanium alloy style to specimen surface no marking, is then removed again Oil, alkali cleaning and deionization washing, natural drying;
(2)Titanium alloy style after will be pretreated is placed in electrolyte as anode, and stainless steel electrolytic groove is cathode, into The component and content of row anodic oxidation, wherein electrolyte be:Calcic electrolyte 0.10mol/L ~ 0.20mol/L, phosphorous electrolyte 0.10mol/L ~ 0.20mol/L, complexing agent 0.02mol/L ~ 0.06mol/L;
(3)By step(2)It is again placed in through anodized titanium alloy style and step(2)Make in identical electrolyte For anode, stainless steel electrolytic groove is cathode, then carries out differential arc oxidation;
(4)Drying is obtained with loose outside interior solid after sample after combined oxidation is handled is cleaned with deionized water Bioceramic film layer titanium.
Step of the present invention(2)Described in calcic electrolyte for calcium acetate, calcium carbonate, calcium dihydrogen phosphate, calcium hydroxide, glycerine One or more of materials in calcium phosphate are mixed to get in any proportion.
Step of the present invention(2)Described in phosphorous electrolyte for potassium dihydrogen phosphate, sodium phosphate, calgon, tripolyphosphate One or more of materials in sodium, sodium polyphosphate are mixed to get in any proportion.
Step of the present invention(2)Described in complexing agent select EDTA-2Na or citric acid.
Step of the present invention(2)Described in the power supply of anodic oxidation be the pulse power, power parameter is:Forward voltage 30 ~ 100V, positive duty cycle are 10% ~ 50%, and frequency is 100Hz ~ 600Hz, and positive negative pulse stuffing number is 0 ~ 5, and oxidization time is 5 ~ 30min.
Step of the present invention(3)Described in the power supply of differential arc oxidation be the pulse power, power parameter is:Forward voltage 400 ~ 500V, positive duty cycle are 10% ~ 50%, and frequency be 100Hz ~ 600Hz, and positive negative pulse stuffing number is 0 ~ 5, oxidization time is 20 ~ 80min。
The bioceramic film that the present invention is prepared is detected through XRD and SEM, can obtain combined oxidation film layer by interior solid layer And exterior weaker zone is formed, for hardness number between 307 ~ 330Hv, thickness contains anatase, rutile between 40 ~ 130 μm And hydroxyapatite phase.
The invention has the advantages that:
(1)Outside the interior solid of the bioceramic film that the present invention is prepared loose bioceramic film layer with it is titanium alloy-based Body surface face forms metallurgical binding, and bond strength is high and biocompatibility is good, meets the requirement of body implanting material;
(2)The method of the invention first carries out anodic oxidation to titanium alloy, then carries out differential arc oxidation processing again, can be in titanium Alloy surface forms the fine and close interior layer of metallurgy with matrix, can effectively improve the corrosion resistance of film layer and prevent internal poisonous and harmful substances Precipitation, one layer of loose porous pottery containing hydroxyapatite is then formed on the basis of anode oxide film by differential arc oxidation again Enamel coating, has preferable effect to improving titanium alloy biocompatibility;
(3)Without the material being harmful to human body and environment in electrolyte used in this combined oxidation, for green electrolyte;
(4)The combined oxidation electrolyte raw material of the present invention is easy to get, and technique is easily controllable, decomposes component without easy, component is steady It is fixed, suitable for industrialized production;
(5)Loose porous ceramic film is titanium alloy in-situ preparation outside the interior solid of gained of the invention, interior solid, Outside is loose porous, has ceramic appearance, and good with basal body binding force, oxidation film layer thickness is 10 ~ 80 μm, has well anti-corrosion And biological property;
(6)Loose bioceramic film surface is through XRD detections and SEM outside interior solid prepared by the method for the invention Testing result shows, the film layer hole three-dimensional communication and containing with hydroxyapatite component as body bone inorganic substance constituent class, With preferable biocompatibility, be conducive to implant and merged with the good of body.
Brief description of the drawings
Fig. 1 is combined oxidation flow chart;
Fig. 2 is the forming process schematic diagram of the fine and close exterior loose bioceramic film layer of titanium alloy substrate interior surface.
In Fig. 2:Figure(a)For titanium alloy substrate, figure(b)Formed, schemed for anode oxidation membrane(c)For anode oxidation membrane and Differential arc oxidation film layer is formed,(d)Micro-arc oxidation films layer surface forms hole.
Embodiment
The present invention is described in further detail with reference to the accompanying drawings and detailed description, but protection scope of the present invention It is not limited to the content.
Embodiment 1
(1)Pretreatment:Titanium alloy ti6al4v is cut into cylindrical titanium, sample top punch, to titanium alloy into Then row surface grinding process carries out oil removing, alkali cleaning and deionization washing, natural drying again to specimen surface no marking;
(2)Anodic oxidation:By step(1)Cylindrical titanium after preprocessed is hung in electrolyte as anode, Stainless steel electrolytic groove is cathode, carries out anodic oxidation, power supply used is the pulse power, and power parameter is set as:Forward voltage 30V, positive duty cycle are 10%, and frequency 200Hz, positive negative pulse stuffing number is 1, oxidization time 5min.Electrolyte quota is:Second Sour calcium 0.05mol/L, EDTA-2Na0.10mol/L, potassium dihydrogen phosphate 0.01mol/L;
(3)Differential arc oxidation:By step(2)Through anodized, the cylindrical titanium with dense oxidation film is hung again Anode is used as in identical electrolyte, stainless steel electrolytic groove is cathode, then carries out differential arc oxidation, and power supply used is the pulse power, Power parameter is set as:Forward voltage 400V, positive duty cycle are 10%, and frequency 200Hz, positive negative pulse stuffing number is 1, during oxidation Between be 20min.Electrolyte quota is:Calcium acetate 0.05mol/L, EDTA-2Na0.10mol/L, potassium dihydrogen phosphate 0.01mol/L;
(4)Drying is obtained with loose outside interior solid after sample after combined oxidation is handled is cleaned with deionized water Bioceramic film layer titanium.
The titanium material for the bioceramic film layer that the present embodiment is prepared is detected through XRD and SEM, compound obtained by the embodiment Oxidation film layer is made of interior solid layer and exterior weaker zone, and up to 310Hv, thickness contains more sharp hardness up to 45 μm Titanium ore and hydroxyapatite phase.
Embodiment 2
(1)Pretreatment:Titanium alloy ti6al4v is cut into cylindrical titanium, sample top punch, to titanium alloy into Row surface grinding process, without obvious cut, then carries out oil removing, alkali cleaning and deionization washing, dries naturally again to specimen surface It is dry;
(2)Anodic oxidation:By step(1)Cylindrical titanium after preprocessed is hung in electrolyte as anode, Stainless steel electrolytic groove is cathode, carries out anodic oxidation, power supply used is the pulse power, and power parameter is set as:Forward voltage 40V, positive duty cycle are 20%, and frequency 300Hz, positive negative pulse stuffing number is 1, oxidization time 10min.Electrolyte quota is:Second Sour calcium 0.1mol/L, EDTA-2Na0.15mol/L, potassium dihydrogen phosphate 0.2mol/L;
(3)Differential arc oxidation:By step(2)Through anodized, the cylindrical titanium with dense oxidation film is hung again Anode is used as in identical electrolyte, stainless steel electrolytic groove is cathode, then carries out differential arc oxidation, and power supply used is the pulse power, Power parameter is set as:Forward voltage 450V, positive duty cycle are 20%, and frequency 300Hz, positive negative pulse stuffing number is 1, during oxidation Between be 40min.Electrolyte quota is:Calcium acetate 0.1mol/L, EDTA-2Na0.15mol/L, potassium dihydrogen phosphate 0.2mol/L;
(4)Drying is obtained with loose outside interior solid after sample after combined oxidation is handled is cleaned with deionized water Bioceramic film layer titanium.
The titanium material for the bioceramic film layer that the present embodiment is prepared is detected through XRD and SEM, compound obtained by the embodiment Oxidation film layer is made of interior solid layer and exterior weaker zone, and up to 317Hv, thickness contains more sharp hardness up to 56 μm Titanium ore and hydroxyapatite phase.
Embodiment 3
(1)Pretreatment:Titanium alloy ti6al4v is cut into cylindrical titanium, sample top punch, to titanium alloy into Row surface grinding process, without obvious cut, then carries out oil removing, alkali cleaning and deionization washing, dries naturally again to specimen surface It is dry;
(2)Anodic oxidation:By step(1)Cylindrical titanium after preprocessed is hung in electrolyte as anode, Stainless steel electrolytic groove is cathode, carries out anodic oxidation, power supply used is the pulse power, and power parameter is set as:Forward voltage 60V, positive duty cycle are 20%, and frequency 400Hz, positive negative pulse stuffing number is 1, oxidization time 20min.Electrolyte quota is:Second Sour calcium 0.1mol/L, EDTA-2Na0.15mol/L, potassium dihydrogen phosphate 0.2mol/L;
(3)Differential arc oxidation:By step(2)Through anodized, the cylindrical titanium with dense oxidation film is hung again Anode is used as in identical electrolyte, stainless steel electrolytic groove is cathode, then carries out differential arc oxidation, and power supply used is the pulse power, Power parameter is set as:Forward voltage 450V, positive duty cycle are 20%, and frequency 400Hz, positive negative pulse stuffing number is 1, during oxidation Between be 60min.Electrolyte quota is:Calcium acetate 0.1mol/L, EDTA-2Na0.15mol/L, potassium dihydrogen phosphate 0.2mol/L;
(4)Drying is obtained with loose outside interior solid after sample after combined oxidation is handled is cleaned with deionized water Bioceramic film layer titanium.
The titanium material for the bioceramic film layer that the present embodiment is prepared is detected through XRD and SEM, compound obtained by the embodiment Oxidation film layer is made of interior solid layer and exterior weaker zone, and up to 319Hv, thickness contains more sharp hardness up to 90 μm Titanium ore and hydroxyapatite phase.
Embodiment 4
(1)Pretreatment:Titanium alloy ti6al4v is cut into cylindrical titanium, sample top punch, to titanium alloy into Row surface grinding process, without obvious cut, then carries out oil removing, alkali cleaning and deionization washing, dries naturally again to specimen surface It is dry;
(2)Anodic oxidation:By step(1)Cylindrical titanium after preprocessed is hung in electrolyte as anode, Stainless steel electrolytic groove is cathode, carries out anodic oxidation, power supply used is the pulse power, and power parameter is set as:Forward voltage 80V, positive duty cycle are 40%, and frequency 600Hz, positive negative pulse stuffing number is 1, oxidization time 30min.Electrolyte quota is:Second Sour calcium 0.1mol/L, EDTA-2Na0.15mol/L, potassium dihydrogen phosphate 0.2mol/L;
(3)Differential arc oxidation:By step(2)Through anodized, the cylindrical titanium with dense oxidation film is hung again Anode is used as in identical electrolyte, stainless steel electrolytic groove is cathode, then carries out differential arc oxidation, and power supply used is the pulse power, Power parameter is set as:Forward voltage 500V, positive duty cycle are 40%, and frequency 600Hz, positive negative pulse stuffing number is 1, during oxidation Between be 80min.Electrolyte quota is:Calcium acetate 0.1mol/L, EDTA-2Na0.15mol/L, potassium dihydrogen phosphate 0.2mol/L;
(4)Drying is obtained with loose outside interior solid after sample after combined oxidation is handled is cleaned with deionized water Bioceramic film layer titanium.
The titanium material for the bioceramic film layer that the present embodiment is prepared is detected through XRD and SEM, compound obtained by the embodiment Oxidation film layer is made of interior solid layer and exterior weaker zone, and for hardness up to 327Hv, thickness contains more gold up to 110 μm Red stone and hydroxyapatite phase.
Embodiment 5
(1)Pretreatment:Titanium alloy ti6al4v is cut into cylindrical titanium, sample top punch, to titanium alloy into Row surface grinding process, without obvious cut, then carries out oil removing, alkali cleaning and deionization washing, dries naturally again to specimen surface It is dry;
(2)Anodic oxidation:By step(1)Cylindrical titanium after preprocessed is hung in electrolyte as anode, Stainless steel electrolytic groove is cathode, carries out anodic oxidation, power supply used is the pulse power, and power parameter is set as:Forward voltage 100V, positive duty cycle are 40%, and frequency 600Hz, positive negative pulse stuffing number is 1, oxidization time 30min.Electrolyte quota is: Calcium acetate 0.1mol/L, EDTA-2Na0.15mol/L, potassium dihydrogen phosphate 0.2mol/L;
(3)Differential arc oxidation:By step(2)Through anodized, the cylindrical titanium with dense oxidation film is hung again Anode is used as in identical electrolyte, stainless steel electrolytic groove is cathode, then carries out differential arc oxidation, and power supply used is the pulse power, Power parameter is set as:Forward voltage 500V, positive duty cycle are 40%, and frequency 600Hz, positive negative pulse stuffing number is 1, during oxidation Between be 80min.Electrolyte quota is:Calcium acetate 0.1mol/L, EDTA-2Na0.15mol/L, potassium dihydrogen phosphate 0.2mol/L;
(4)Drying is obtained with loose outside interior solid after sample after combined oxidation is handled is cleaned with deionized water Bioceramic film layer titanium.
The titanium material for the bioceramic film layer that the present embodiment is prepared is detected through XRD and SEM, compound obtained by the embodiment Oxidation film layer is made of interior solid layer and exterior weaker zone, and for hardness up to 326Hv, thickness contains more gold up to 128 μm Red stone and hydroxyapatite phase.

Claims (4)

1. a kind of method that combined oxidation prepares bioceramic film, it is characterised in that specifically include following steps:
(1)Pretreatment:Surface grinding process is carried out to titanium alloy sample to specimen surface no marking, then carries out oil removing, alkali again Wash and deionization is washed, natural drying;
(2)Titanium alloy sample after will be pretreated is placed in electrolyte as anode, and stainless steel electrolytic groove is cathode, is carried out The component and content of anodic oxidation, wherein electrolyte be:Calcic electrolyte 0.10mol/L ~ 0.20mol/L, phosphorous electrolyte 0.10mol/L ~ 0.20mol/L, complexing agent 0.02mol/L ~ 0.06mol/L;
(3)By step(2)It is again placed in through anodized titanium alloy style and step(2)As sun in identical electrolyte Pole, stainless steel electrolytic groove is cathode, then carries out differential arc oxidation;
(4)Drying obtains having life loose outside interior solid after sample after combined oxidation is handled is cleaned with deionized water The titanium of thing ceramic film;
Step(2)Described in the power supply of anodic oxidation be the pulse power, power parameter is:30 ~ 100V of forward voltage, positive duty Than for 10% ~ 50%, frequency is 100Hz ~ 600Hz, positive negative pulse stuffing number is 0 ~ 5, and wherein positive negative pulse stuffing number is not 0, oxidization time 5 ~30min;
Step(3)Described in the power supply of differential arc oxidation be the pulse power, power parameter is:400 ~ 500V of forward voltage, forward direction account for For sky than being 10% ~ 50%, frequency is 100Hz ~ 600Hz, and positive negative pulse stuffing number is 0 ~ 5, and wherein positive negative pulse stuffing number is not 0, oxidization time For 20 ~ 80min.
2. the method that combined oxidation according to claim 1 prepares bioceramic film, it is characterised in that:Step(2)Middle institute Calcic electrolyte is stated as one or more of materials in calcium acetate, calcium carbonate, calcium dihydrogen phosphate, calcium hydroxide, calcium glycerophosphate It is mixed to get in any proportion.
3. the method that combined oxidation according to claim 1 prepares bioceramic film, it is characterised in that:Step(2)Middle institute Phosphorous electrolyte is stated as potassium dihydrogen phosphate, sodium phosphate, calgon, sodium tripolyphosphate, one kind in sodium polyphosphate or several Kind material is mixed to get in any proportion.
4. the method that combined oxidation according to claim 1 prepares bioceramic film, it is characterised in that:Step(2)Middle institute It is EDTA-2Na or citric acid to state complexing agent.
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CN104911671B (en) * 2015-05-13 2017-10-27 昆明理工大学 A kind of preparation method of titanium alloy surface combined oxidation bioceramic film
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
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
US20180195196A1 (en) * 2017-01-06 2018-07-12 Mks Instruments, Inc. Protective oxide coating with reduced metal concentrations
CN108716016B (en) * 2018-06-16 2019-08-06 宁波润楠机电实业有限公司 A kind of surface treatment method of automobile parts
CN111733436A (en) * 2020-06-19 2020-10-02 浙江大学 Silver-iodine surface modified titanium alloy implant and preparation method thereof
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

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CN100346845C (en) * 2004-01-16 2007-11-07 清华大学 Metal surface constructional gradient biological layer and its preparation and usage
CN101570874B (en) * 2008-06-30 2010-09-15 华南理工大学 In situ formation method of gradient film containing TiO*/HA/CaCO*
CN102758202B (en) * 2012-08-11 2014-05-07 西北有色金属研究院 Method for preparing biomedical titanium and titanium alloy surface antibacterial coatings
CN103451706B (en) * 2013-09-02 2016-01-27 吉林大学 A kind of titanium surface directly generates the preparation method of hydroxyl apatite bioceramic film
CN103695986B (en) * 2013-12-25 2016-04-13 昆明冶金研究院 A kind of preparation method of Superhydrophilic titanium alloy ceramic coating formed by micro-arc oxidation
CN103898591B (en) * 2014-03-27 2016-05-25 昆明冶金研究院 The method of the ceramic coating formed by micro-arc oxidation that a kind of direct preparation contains hydroxyapatite

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