CN102732882B - Artificial joint with micro-nano graded topological surface structure and preparation method of artificial joint - Google Patents
Artificial joint with micro-nano graded topological surface structure and preparation method of artificial joint Download PDFInfo
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- CN102732882B CN102732882B CN201210245093.5A CN201210245093A CN102732882B CN 102732882 B CN102732882 B CN 102732882B CN 201210245093 A CN201210245093 A CN 201210245093A CN 102732882 B CN102732882 B CN 102732882B
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61F—FILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
- A61F2/00—Filters implantable into blood vessels; Prostheses, i.e. artificial substitutes or replacements for parts of the body; Appliances for connecting them with the body; Devices providing patency to, or preventing collapsing of, tubular structures of the body, e.g. stents
- A61F2/02—Prostheses implantable into the body
- A61F2/30—Joints
- A61F2/30767—Special external or bone-contacting surface, e.g. coating for improving bone ingrowth
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61F—FILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
- A61F2/00—Filters implantable into blood vessels; Prostheses, i.e. artificial substitutes or replacements for parts of the body; Appliances for connecting them with the body; Devices providing patency to, or preventing collapsing of, tubular structures of the body, e.g. stents
- A61F2/02—Prostheses implantable into the body
- A61F2/30—Joints
- A61F2002/30001—Additional features of subject-matter classified in A61F2/28, A61F2/30 and subgroups thereof
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- Orthopedic Medicine & Surgery (AREA)
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- Oral & Maxillofacial Surgery (AREA)
- Transplantation (AREA)
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- Biomedical Technology (AREA)
- Heart & Thoracic Surgery (AREA)
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Abstract
The invention provides an artificial joint with a micro-nano graded topological surface structure and a preparation method of the artificial joint. The artificial joint is formed by compounding a titanium alloy substrate, a micro-porous titanium dioxide surface layer prepared by a micro-arc oxidization method, and a zinc oxide nano rod or a nano taper deposited and grown on the hole wall of the surface, namely the micro-porous titanium dioxide biological activity surface layer is obtained on the surface of an artificial joint titanium substrate through the micro-arc oxidization method; and furthermore, electric depositing parameters are adjusted and a zinc oxide nano rod/taper is deposited and prepared on the titanium dioxide biological activity surface layer, so as to form the artificial joint with the micro-nano graded topological surface structure. The artificial joint can utilize abundant titanium dioxide micron hole structures on the surface and a zinc oxide nano topological structure deposited and grown in the hole wall to enhance the biological effects of adhesion, growth, multiplication and the like of surface osteoblast, and realize the slow release of the element zinc; and therefore, the antibacterial capability, the biological activity, the biocompatibility and the cell regulating and controlling capability of the surface at an implantation initial stage are greatly improved.
Description
Technical field
The present invention relates to a kind of joint prosthesis with micro-nano hierarchical topology surface tissue and preparation method thereof, on the poriferous titanium dioxide upper layer that this joint prosthesis is prepared by titanium alloy substrate, differential arc oxidation method and surperficial hole wall thereof, zinc oxide nano rod or the nanocone of deposition growing are composited, and belong to substitute material for human hard tissues field.
Background technology
Joint prosthesis can recover the function of joint failure, disappearance, and this just makes the damage patient of joint sclerous tissues that cannot repair by traditional method can obtain basic treatment, improves the quality of living.Normally used artificial hard tissue substituting material is metallic substance, because it is bio-inert material, can not form firmly physiology and be combined between osseous tissue, after implantation, usually can become flexible, and causes replacing unsuccessfully.In addition, the inefficacy of implanting sclerous tissues can cause the complication such as bone resorption, has a strong impact on the late result of artificial substituting tissue.Adopt process for modifying surface to prepare functional living being coating (film) at artificial hard tissue substituting metal base surface, can reduce the stripping of harmful metal ion under human body environment, improve its biocompatibility and biological activity, and strengthen implant function.
The titanium dioxide ceramic layer lifeless matter toxicity of titanium alloy surface, wear resistance and corrosion resistance is good, has other traditional materials be beyond one's reach good biocompatibility and biological activity.If its surface forms the micro nano structures such as controlled porous, island, groove, can further increase the roughness of ceramic layer, can promote the combination of adhering to of cell tissue and material surface, preferentially stick scleroblast, cell growth has inducing action, can effectively improve the interface bond strength of osseous tissue and implant, promote knitting.The micro-nano surface topological framework energy remarkably influenced cell of different pore size, different-shape is in growthhabit and the function of implant surface, and meanwhile, the porous topological framework of superficial film also can be drug loading and slowly-releasing provides place.
Nanometer rod taper zincite crystal is also desirable biomaterial, at aspects such as biosensor, photodynamic therapy, has medical use prospect widely.Meanwhile, in physiological environment, nano zine oxide has low rate resolvability feature, and zinc element is the important component part of various enzymes and albumen, has the function of biology setter.
By differential arc oxidation method, coordinate cathode electrodeposition technology in pure titanium or titanium alloy surface preparation, to have the compound coating of bioactive porous titanium dioxide ceramic film/zinc-oxide nano topological framework, the formed joint prosthesis with micro-nano hierarchical topology surface tissue demonstrates huge biomedical applications potentiality.Yet, correlative study so far there are no report.Given this, draw the present invention.
Summary of the invention
Technical problem: the object of this invention is to provide a kind of joint prosthesis with micro-nano hierarchical topology surface tissue and preparation method thereof, intend first at joint prosthesis titanium matrix surface, passing through to regulate differential arc oxidation gain of parameter aperture regulatable poriferous titanium dioxide bioactivity surface layer, further by regulating galvanic deposit parameter, on titanium dioxide bioactivity surface layer, deposition is prepared zinc oxide nano rod/cone, forms the joint prosthesis with micro-nano hierarchical topology surface tissue.This joint prosthesis can utilize the zinc-oxide nano topological framework of deposition growing on the abundant titanium dioxide micrometer pore structure in surface and hole wall thereof, strengthen the biological effects such as surperficial osteoblastic adhesion, growth, propagation, realize the slowly-releasing of element zinc, greatly improved bacteriostasis, biological activity, biocompatibility, the cell regulate and control ability on implantation initial stage surface.
Technical scheme: this joint prosthesis with micro-nano hierarchical topology surface tissue is that good poriferous titanium dioxide upper layer and the zinc oxide nano rod/cone of biocompatibility of being prepared in titanium alloy-based surface by differential arc oxidization technique and electro-deposition techniques is composited.Titanium dioxide surface layer prepared by differential arc oxidization technique has the structures such as porous, groove, improves implant surface roughness, and for cell proliferation growth and medicament slow release provide useful place, good wear resistance and corrosion resistance is conducive to extend joint prosthesis work-ing life; The micro-nano hierarchical topology structure that nanometer rod/taper zinc oxide and titanium dioxide micrometer hole form, can realize the slowly-releasing of element zinc, and the bacterium suppressing in joint prosthesis implantation process infects, and regulates biology performance.
The joint prosthesis that the present invention has micro-nano hierarchical topology surface tissue is to be matrix by titanium alloy, and on poriferous titanium dioxide upper layer prepared by employing differential arc oxidation method and surperficial hole wall thereof, zinc oxide nano rod or the nanocone of deposition growing are composited; Wherein, poriferous titanium dioxide upper layer generates at surface of metal titanium in-situ oxidation by differential arc oxidation method, and in titanium dioxide surface layer, disperse is distributed with aperture and is
micron hole; Zinc oxide nano rod or nanocone are by electro-deposition method deposition growing on the hole wall of poriferous titanium dioxide layer surface, and zinc oxide nano rod or nanocone diameter exist
between, length exists
between.
Described titanium alloy is medical Ti 6Al4V alloy, or the medical low-elastic modulus beta titanium alloy that contains one or more elements in Nb, Sn, Mo or Zr.
The preparation method with the joint prosthesis of micro-nano hierarchical topology surface tissue of the present invention specifically realizes by following step:
1) first select titanium alloy to process the model of joint prosthesis;
2) differential arc oxidation electrolyte quota: adopt carbonate system aqueous electrolyte liquid, include the Na of 2 ~ 50g/L
2cO
3, 0.5 ~ 5g/L KOH;
3) the model surface sanding and polishing of joint prosthesis, the model of joint prosthesis of take in above-mentioned carbonate system special electrolytic solutions is anode, stainless steel is negative electrode, adopt that bipolar pulse is microarc oxidation equipment provided carries out differential arc oxidation processing to the model of joint prosthesis, at titanium matrix surface, build poriferous titanium dioxide bioactivity surface layer;
4) preparation galvanic deposit electrolytic solution: configuration packet is containing the Zn of 0.5~10mM
2+and and Zn
2+the galvanic deposit aqueous electrolyte liquid of the hexamethylenetetramine of equimolar amount (HMT), is placed in thermostat water bath, regulates temperature to be fixed between 65~95 ℃;
5) the joint prosthesis model of above-mentioned differential arc oxidation being processed is with after alcohol drip washing, vacuum-drying, be re-used as negative electrode, Graphite Electrodes is anode, adopt two electrode cathode galvanic deposit systems, in above-mentioned galvanic deposit electrolytic solution, carry out the deposition growing of zinc oxide nano rod or nanocone, employing deposition voltage is 1.0~100V, depositing time 10 ~ 100min;
6) by the model of above-mentioned taking-up joint prosthesis with after alcohol drip washing, vacuum-drying, Preservation in sterile condition after sterilization, standby, get final product to such an extent that the present invention has the joint prosthesis of micro-nano hierarchical topology surface tissue.
Adopt when bipolar pulse is microarc oxidation equipment provided carries out differential arc oxidation processing to the model of joint prosthesis, adopt forward voltage 200 ~ 1000V, negative voltage 0 ~ 300V, pulse-repetition regulation range: direct impulse 50Hz ~ 3000Hz, negative-going pulse frequency 1Hz ~ 3000Hz, dutycycle: forward 4% ~ 80%, negative sense 0% ~ 50%, the differential arc oxidation reaction times is 0.5 ~ 120min.
Beneficial effect:
(1) the present invention passes through to regulate differential arc oxidation gain of parameter aperture regulatable poriferous titanium dioxide bioactivity surface layer at joint prosthesis titanium matrix surface, further by regulating galvanic deposit parameter, on titanium dioxide bioactivity surface layer, deposition is prepared zinc oxide nano rod/cone, formation has the joint prosthesis of micro-nano hierarchical topology surface tissue, is a kind of desirable joint prosthesis equivalent material with biological activity, cell regulate and control ability, antibacterial anticancer and biocompatibility.
(2) the bioactivity, porous ceramic coating of titanium dioxide and the metallic matrix bonding strength that prepared by differential arc oxidization technique are high, and have aperture and arrive at 500nm
between change and can regulate and control pore structure, can promote the deposition growing of apatite layer; Micro-/ nano pore structure is conducive to the load of trace element and medicine, increases the contact area of implant surrounding bone tissue and cell, is again the ideal place of cell adhesion, propagation and growth simultaneously.
(3) at titanium dioxide porous ceramic rete substrates taper, the different shape nano zine oxide such as bar-shaped, can improve the metabolic function of embedded material peripheral cell, promote the growth of osteocyte and bone resorption is had to restraining effect; Zincite crystal is not only good antiseptic-germicide, improves material anti-microbial property, but also can be used as pharmaceutical carrier, accelerates the postoperative recovering process of joint prosthesis.
This artificial joint material can form firmly physiology with osseous tissue and be combined, and promotes the adhesion, propagation, growth, growth of osteocyte and osseous tissue etc., can also carried medicine sustained-release, antibacterial anticancer, and be the hard tissue substituting material that has good biological activity and biocompatibility concurrently.
Specific examples mode
Differential arc oxidation of the present invention and electro-deposition preparation method carry out as follows:
1) first titanium alloy is processed into joint prosthesis model, then surface is passed through to mechanical polishing, ultrasonic cleaning, chemical rightenning, deionized water drip washing, drying and other steps successively, be placed in drying basin standby;
2) special electrolytic solutions of configuration carbonate system;
3) in above-mentioned carbonate system special electrolytic solutions, take titanium alloy artificial joint model as anode, stainless steel is negative electrode, adopt bipolar pulse differential arc oxidization technique to process sample surfaces, at matrix surface, build poriferous titanium dioxide bioactivity surface layer, change differential arc oxidation processing parameter with adjustment aperture size and pore structure, use successively alcohol and deionized water drip washing, dry, standby;
4) configuration packet is containing the Zn of 0.5~10mM
2+, with Zn
2+the HMT deposit fluid of equimolar amount, pre-bubbling 1~15h, is placed in thermostat water bath, regulates temperature to be fixed between 65~95 ℃;
5) by 3) in sample be negative electrode, Graphite Electrodes is anode, adopts two electrode cathode galvanic deposit systems to prepare rod/taper zinc oxide;
6) above-mentioned materials is taken out, deionized water drip washing, Preservation in sterile condition after sterilization, standby, get final product to such an extent that there is the joint prosthesis of micro-nano hierarchical topology surface tissue.
The carbonate system special electrolytic solutions of addressing, includes the Na of 2 ~ 50g/L
2cO
3, 0.5 ~ 5g/L KOH.
The differential arc oxidation processing mode operating voltage regulation range of addressing: forward voltage 200 ~ 1000V, negative voltage 0 ~ 300V, pulse-repetition regulation range: direct impulse 50 ~ 3000Hz, negative-going pulse frequency 1 ~ 3000Hz, dutycycle: forward 4% ~ 80%, negative sense 0% ~ 50%, the differential arc oxidation reaction times is 0.5 ~ 120min.
The electrodeposition process mode processing parameter regulation range of addressing: Zn in boosting voltage 1.0~100V, deposit fluid
2+concentration 0.5 ~ 10mM, the concentration of HMT and Zn
2+equate depositing time 10 ~ 100min.
Embodiment 1
(1) first select medical Ti 6Al4V to process joint prosthesis;
(2) joint prosthesis pre-treatment: by joint prosthesis use abrasive paper for metallograph that label is followed successively by 600#, 800#, 1000#, 1200# by coarse sand to fine sand sanding and polishing step by step, then use acetone, alcohol, distilled water ultrasonic cleaning, dried for standby.
(3) configuration of electrolytic solution: adopt sodium carbonate solution system, it is the sodium carbonate solution of 20g/L and the potassium hydroxide solution of 1g/L that configuration 10L contains concentration, and 40 ℃ of constant temperature stirring and dissolving are stand-by;
(4) differential arc oxidation of joint prosthesis: joint prosthesis is placed in to the microarc oxidation equipment provided electrolyzer of bipolar pulse and adds the electrolytic solution configuring, take joint prosthesis as anode, stainless steel electrolytic groove is negative electrode, and adjusting process parameter is carried out differential arc oxidation to joint prosthesis.Processing parameter is: constant voltage mode, operating voltage regulation range forward voltage 300 ~ 600V, negative voltage 0 ~ 50V, pulse-repetition regulation range direct impulse 100 ~ 600Hz, dutycycle forward 12%, negative sense 12%, reaction times 10 ~ 15min;
(5) load of ZnO nanorod: by above-mentioned taking-up for joint prosthesis after alcohol, distilled water drip washing, be placed in the deposit fluid of electrodeposition apparatus electrolyzer, take joint prosthesis as negative electrode, and Graphite Electrodes is anode, and adjusting process parameter is at joint prosthesis surface deposition growth ZnO nano-structure.Processing parameter is: constant voltage mode, deposition voltage 10 ~ 25V, Zn
2+concentration is 0.5 ~ 10mM, the concentration of additive HMT and Zn
2+concentration equimolar amount, depositing time 10 ~ 100min;
(6) by above-mentioned taking-up for joint prosthesis after alcohol, distilled water drip washing, vacuum-drying, Preservation in sterile condition after sterilization, standby, get final product to such an extent that the present invention has the joint prosthesis of micro-nano hierarchical topology surface tissue, in the time of the biological effects such as the adhesion of enhancing cell, growth, propagation, also can realize the slowly-releasing of element zinc, improve bacteriostasis, biological activity, biocompatibility and the cell regulate and control ability on implantation initial stage surface.
Embodiment 2
(1) first select Ti6Al4V alloy to process joint prosthesis;
(2) joint prosthesis pre-treatment: by joint prosthesis use abrasive paper for metallograph that label is followed successively by 600#, 800#, 1000#, 1200# by coarse sand to fine sand sanding and polishing step by step, then use acetone, alcohol, distilled water ultrasonic cleaning, dried for standby.
(3) configuration of electrolytic solution: adopt sodium carbonate solution system, it is the sodium carbonate solution of 20g/L and the potassium hydroxide solution of 1g/L that configuration 10L contains concentration, and 40 ℃ of constant temperature stirring and dissolving are stand-by;
(4) differential arc oxidation of joint prosthesis: joint prosthesis is placed in to the microarc oxidation equipment provided electrolyzer of bipolar pulse and adds the electrolytic solution configuring, take joint prosthesis as anode, stainless steel electrolytic groove is negative electrode, and adjusting process parameter is carried out differential arc oxidation to joint prosthesis.Processing parameter is: constant voltage mode, operating voltage regulation range forward voltage 350V, negative voltage 0V, pulse-repetition regulation range direct impulse 300Hz, dutycycle forward 15%, negative sense 0%, reaction times 15min;
(5) load of ZnO nanorod: by above-mentioned taking-up for joint prosthesis after alcohol, distilled water drip washing, be placed in the deposit fluid of electrodeposition apparatus electrolyzer, take joint prosthesis as negative electrode, and Graphite Electrodes is anode, and adjusting process parameter is at joint prosthesis surface deposition growth ZnO nano-structure.Processing parameter is: constant voltage mode, deposition voltage 1.5V, Zn
2+concentration is 2.5mM, the concentration of additive HMT and Zn
2+concentration equimolar amount, depositing time 15min;
(6) by above-mentioned taking-up for joint prosthesis after alcohol, distilled water drip washing, vacuum-drying, Preservation in sterile condition after sterilization, standby, get final product to such an extent that the present invention has the joint prosthesis of micro-nano hierarchical topology surface tissue.
Embodiment 3
(1) first select medical Ti 6Al4V to process joint prosthesis;
(2) joint prosthesis pre-treatment: by joint prosthesis use abrasive paper for metallograph that label is followed successively by 600#, 800#, 1000#, 1200# by coarse sand to fine sand sanding and polishing step by step, then use acetone, alcohol, distilled water ultrasonic cleaning, dried for standby.
(3) configuration of electrolytic solution: adopt sodium carbonate solution system, it is the sodium carbonate solution of 20g/L and the potassium hydroxide solution of 1g/L that configuration 10L contains concentration, and 40 ℃ of constant temperature stirring and dissolving are stand-by;
(4) differential arc oxidation of joint prosthesis: joint prosthesis is placed in to the microarc oxidation equipment provided electrolyzer of bipolar pulse and adds the electrolytic solution configuring, take joint prosthesis as anode, stainless steel electrolytic groove is negative electrode, and adjusting process parameter is carried out differential arc oxidation to joint prosthesis.Processing parameter is: constant voltage mode, operating voltage regulation range forward voltage 400V, negative voltage 20V, pulse-repetition regulation range direct impulse 800Hz, dutycycle forward 15%, negative sense 15%, reaction times 15min;
(5) load of ZnO nanorod: by above-mentioned taking-up for joint prosthesis after alcohol, distilled water drip washing, be placed in the deposit fluid of electrodeposition apparatus electrolyzer, take joint prosthesis as negative electrode, and Graphite Electrodes is anode, and adjusting process parameter is at joint prosthesis surface deposition growth ZnO nano-structure.Processing parameter is: constant voltage mode, deposition voltage 2.5V, Zn
2+concentration is 8mM, the concentration of additive HMT and Zn
2+concentration equimolar amount, depositing time 60min;
(6) by above-mentioned taking-up for joint prosthesis after alcohol, distilled water drip washing, vacuum-drying, Preservation in sterile condition after sterilization, standby, get final product to such an extent that the present invention has the joint prosthesis of the micro-nano hierarchical topology surface tissue of aperture 10-500 μ m titanium dioxide channel form biological activity substrate and the bar-shaped zinc oxide of 1-10 μ m.
Embodiment 4
(1) first select Ti6Al4V alloy to process joint prosthesis;
(2) joint prosthesis pre-treatment: by joint prosthesis use abrasive paper for metallograph that label is followed successively by 600#, 800#, 1000#, 1200# by coarse sand to fine sand sanding and polishing step by step, then use acetone, alcohol, distilled water ultrasonic cleaning, dried for standby.
(3) configuration of electrolytic solution: adopt sodium carbonate solution system, it is the sodium carbonate solution of 20g/L and the potassium hydroxide solution of 1g/L that configuration 10L contains concentration, and 40 ℃ of constant temperature stirring and dissolving are stand-by;
(4) differential arc oxidation of joint prosthesis: joint prosthesis is placed in to the microarc oxidation equipment provided electrolyzer of bipolar pulse and adds the electrolytic solution configuring, take joint prosthesis as anode, stainless steel electrolytic groove is negative electrode, and adjusting process parameter is carried out differential arc oxidation to joint prosthesis.Processing parameter is: constant voltage mode, operating voltage regulation range forward voltage 300V, negative voltage 20V, pulse-repetition regulation range direct impulse 50Hz, dutycycle forward 15%, negative sense 15%, reaction times 15min;
(5) load of ZnO nanorod: by above-mentioned taking-up for joint prosthesis after alcohol, distilled water drip washing, be placed in the deposit fluid of electrodeposition apparatus electrolyzer, take joint prosthesis as negative electrode, and Graphite Electrodes is anode, and adjusting process parameter is at joint prosthesis surface deposition growth ZnO nano-structure.Processing parameter is: constant voltage mode, deposition voltage 2.0V, Zn
2+concentration is 5mM, the concentration of additive HMT and Zn
2+concentration equimolar amount, depositing time 30min;
(6) by above-mentioned taking-up for joint prosthesis after alcohol, distilled water drip washing, vacuum-drying, Preservation in sterile condition after sterilization, standby, get final product to such an extent that the present invention has the joint prosthesis planting body of micro-nano hierarchical topology surface tissue.
Obviously, the above embodiment of the present invention is only used to clearly demonstrate example of the present invention, and is not the restriction to embodiments of the present invention.For those of ordinary skill in the field; also can make other changes in different forms on the basis of the above description; here exhaustive without also giving all embodiments, and these belong to apparent variation that spirit of the present invention amplified out or change still in protection scope of the present invention.
Claims (4)
1. a joint prosthesis with micro-nano hierarchical topology surface tissue, it is characterized in that this joint prosthesis is is matrix by titanium alloy, on poriferous titanium dioxide upper layer prepared by employing differential arc oxidation method and surperficial hole wall thereof, zinc oxide nano rod or the nanocone of deposition growing are composited; Wherein, poriferous titanium dioxide upper layer generates at surface of metal titanium in-situ oxidation by differential arc oxidation method, and in titanium dioxide surface layer, disperse is distributed with the micron hole that aperture is 0.5 μ m-500 μ m; Zinc oxide nano rod or nanocone by electro-deposition method deposition growing on the hole wall of poriferous titanium dioxide layer surface, zinc oxide nano rod or nanocone diameter between 0.05~1.5 μ m, length is between 0.1~10 μ m.
2. the joint prosthesis with micro-nano hierarchical topology surface tissue as claimed in claim 1, it is characterized in that described titanium alloy is medical Ti 6Al4V alloy, or the medical low-elastic modulus beta titanium alloy that contains one or more elements in Nb, Sn, Mo or Zr.
3. a preparation method with the joint prosthesis of micro-nano hierarchical topology surface tissue as claimed in claim 1, is characterized in that the method specifically realizes by following step:
1) first select titanium alloy to process the model of joint prosthesis;
2) differential arc oxidation electrolyte quota: adopt carbonate system aqueous electrolyte liquid, include the Na of 2~50g/L
2cO
3, 0.5~5g/L KOH;
3) the model surface sanding and polishing of joint prosthesis, the model of joint prosthesis of take in above-mentioned carbonate system special electrolytic solutions is anode, stainless steel is negative electrode, adopt that bipolar pulse is microarc oxidation equipment provided carries out differential arc oxidation processing to the model of joint prosthesis, at titanium matrix surface, build poriferous titanium dioxide bioactivity surface layer;
4) preparation galvanic deposit electrolytic solution: configuration packet is containing the Zn of 0.5~10mM
2+and and Zn
2+the galvanic deposit aqueous electrolyte liquid of the hexamethylenetetramine of equimolar amount (HMT), is placed in thermostat water bath, regulates temperature to be fixed between 65~95 ℃;
5) the joint prosthesis model of above-mentioned differential arc oxidation being processed is with after alcohol drip washing, vacuum-drying, be re-used as negative electrode, Graphite Electrodes is anode, adopt two electrode cathode galvanic deposit systems, in above-mentioned galvanic deposit electrolytic solution, carry out the deposition growing of zinc oxide nano rod or nanocone, employing deposition voltage is 1.0~100V, depositing time 10~100min;
6) by the model of the joint prosthesis taking out with after alcohol drip washing, vacuum-drying, Preservation in sterile condition after sterilization, standby, get final product to such an extent that there is the joint prosthesis of micro-nano hierarchical topology surface tissue.
4. the preparation method with the joint prosthesis of micro-nano hierarchical topology surface tissue as claimed in claim 3, it is characterized in that adopting that bipolar pulse is microarc oxidation equipment provided that the model of joint prosthesis is carried out to differential arc oxidation while processing, adopt forward voltage 200~1000V, negative voltage 0~300V, pulse-repetition regulation range: direct impulse 50Hz~3000Hz, negative-going pulse frequency 1Hz~3000Hz, dutycycle: forward 4%~80%, negative sense 0%~50%, the differential arc oxidation reaction times is 0.5~120min.
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CN103668390B (en) * | 2014-01-02 | 2016-10-26 | 四川大学 | There is the titanium on micro-nano rough structure surface or titanium alloy material and preparation method |
CN105648497B (en) * | 2016-01-13 | 2018-06-26 | 西安交通大学 | A kind of titanium surface zinc titanate-titanium oxide composite antibacterial coating and preparation method thereof |
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CN110965108A (en) * | 2019-12-27 | 2020-04-07 | 沈兰兰 | Zn-TiO2Method for producing a coating |
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CN114293237B (en) * | 2022-01-04 | 2023-05-12 | 合肥工业大学 | Preparation method of one-dimensional topological photonic crystal based on porous alumina |
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