CN102371005B - Zinc-doped porous nano-titanium oxide coating and its preparation method - Google Patents
Zinc-doped porous nano-titanium oxide coating and its preparation method Download PDFInfo
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- CN102371005B CN102371005B CN201010253123.8A CN201010253123A CN102371005B CN 102371005 B CN102371005 B CN 102371005B CN 201010253123 A CN201010253123 A CN 201010253123A CN 102371005 B CN102371005 B CN 102371005B
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Abstract
Belonging to the technical field of biomedical ceramic coatings and nano-materials, the invention relates to a zinc-doped porous nano-titanium oxide coating and its preparation method. The preparation method consists of the steps of: providing a zinc-containing electrolytic solution, and supplementing at least one electrolyte for assisting arc striking, and in the electrolytic solution, taking titanium or titanium alloy as the positive electrode and stainless steel as the negative electrode, conducting microarc oxidation treatment to the titanium or titanium alloy with a direct current pulse power supply, thus obtaining a coating with a porous nano-crystal structure, a pore size of less than 20micrometers and a surface crystal grain scale of less than 100nm. Specifically, the coating phase is anatase titanium oxide or a composite of anatase titanium oxide and rutile titanium oxide, and has zinc content of 0.01-50 wt%. The nano-titanium oxide coating of the invention has better biocompatibility than existing titanium oxide coatings. And osteoblasts on the surface of the coating have faster propagation rate and stronger vigor. Thus, the zinc-doped porous nano-titanium oxide coating in the invention can be used as a replacing material for positions such as thighbones, hip joints, dental implants and others that bear heavy loads.
Description
Technical field
The present invention relates to a kind of zinc-doped porous nano-titanium oxide coating and preparation method thereof, what relate to or rather is a kind of titanium base zinc-doped porous nano-titanium oxide coating as artificial bone, hip joint or tooth implant and preparation method thereof, belongs to medical bio ceramic coating and technical field of nano material.
Background technology
Titanium and titanium alloys is widely used as bone tissue restoration and replacement material with its lower Young's modulus, excellent biocompatibility, erosion resistance and mechanical property.It is reported, the biocompatibility of titanium and titanium alloys excellence and erosion resistance are mainly owing to one deck thin film of titanium oxide that its surface exists naturally.Therefore, titanium oxide ceramics and coated material become the study hotspot in technical field of biological material.Especially in recent years, nano-titanium oxide forms [Chinese patent ZL200510029743.2 at induction osteoid apatite, ZL 200510023170.2, Uchida M, Kim HM, Kokubo T, Fujibayashi S, Nakamura T.Structural dependence of apatite formation on titania gels in simulatedbody fluid.J.Biomed Mater Res.64A (2003) 164-170] and promote that sclerocyte adheres to and propagation [Webster TJ, Siegel RW, Bizios R.Enhanced functions of osteoblasts on nanophaseceramics.Biomaterials 21 (2000) 1803-1810.] etc. the outstanding behaviours of aspect, more cause people to pay close attention to more and more widely.But, titanium oxide is promoting that the performance in the absorption of sclerocyte reproduction restraint, specific proteins and genetic expression etc. still has much room for improvement, and titanium oxide does not have germ resistance, in prevention and therapy implant postoperative infection, seem helpless, limit its application clinically.
Zinc is a kind of important trace element of needed by human body.Research finds, most of zinc in human body all concentrate in bone, and zinc synthesizes in vivo in the process of phosphatic rock and plays positive role [Wei X, Ugurlu O, Ankit A, Acar HY, Akinc M.Dissolution behavior of Si, Zn-codoped tricalcium phosphates.MaterialsScience and Engineering C.29 (2009) 126-135], zinc to play an important role [Yamaguchi M to the growth of bone, maintenance and reparation, Oishi H, Suketa Y.Stimulatory effect of zinc on bone formationin tissue culture.Biochem Pharmacol 36 (1987) 4007-4012.], significantly can promote that sclerocyte is bred and alkaline phosphatase expression of enzymes containing the calcium phosphate of zinc and hydroxylapatite ceramic, promote that the osteogen of medullary cell is broken up and strengthens bone conduction [Ikeuchi M, Ito A, Dohi Y, Ohgushi H, Shimaoka H, Yonemasu K, TateishiT.Osteogenic differentiation of cultured rat and human bone marrow cells on thesurface of zinc-releasing calcium phosphate ceramics.J Biomed Mater Res A 67 (2003) 1115-1122.], zinc can also promote osteoblast activity and suppress the absorption of osteoclast, increase bone protein, calcium and DNA content [the Ito A in osseous tissue, Kawamura H, Otsuka M, Ikeuchi M, et al.Zinc-releasing calciumphosphate for stimulating bone formation.Materials Science and Engineering C 22 (2002) 21-25].On the other hand, zinc or a kind of efficient, clean inorganic antiseptic, remarkable restraining and sterilizing bacteria effect [Yamamoto O is had to the various bacteria such as intestinal bacteria and streptococcus aureus, Nakakoshi K, Sasamoto T, NakagawaH.MiuraK.Adsorption and growth inhibition of bacteria on carbon materialscontaining zinc oxide.Carbon 39 (2001) 1643-1651; Wang X, Du Y, Liu H.Preparation, characterization and antimicrobial activity of chitosan-Zn complex.CarbohydratePolymers 56 (2004) 21-26].The doping of zinc in calcium phosphate and hydroxylapatite ceramic is studied a lot, but the research that zinc doping titanium oxide improves its biology performance but has no report.Therefore, by zinc doping in nano-titanium oxide coating layer, be expected to improve its bone formation performance and germ resistance, obtain and can be applicable to clinical titanium oxide bone tissue restoration and replacement material.
In addition, there are some researches show, nano material shows clear superiority compared to traditional material in the adhesion of promotion sclerocyte, propagation and differentiation, nano material passes through the improvement of effects on surface energy and surface tissue, significantly can promote that albumen is in the absorption [Balasundaram G, Webster TJ.A perspective on nanophase materials fororthopedic implant applications.J Mater Chem 16 (2006) 3737-3745] of material surface.On the other hand, porous material, the material especially with micron order aperture also significantly can promote adhesion and the propagation of cell, and porous material is conducive to the interior growth of new bone in vivo, strengthen the combination between area of new bone and implant, accelerate Rehabilitation [Akin FA, Zreiqat H, Jordan S, Wijesundara MBJ, Hanley L.Preparation and analysis ofmacroporous TiO
2coatings on Ti surface for bone-tissue implants.J Biomed MaterRes 57 (2001) 588-596.].
Differential arc oxidization technique, also known as plasma electrolytic oxidation, is a kind of new technology directly generating ceramic coating in valve metal surface in situ oxidations such as titanium, magnesium, zirconium, aluminium.Its coating is porous and nanostructure, high with substrate combinating strength, and not by the restriction of workpiece geometric shape, can also by realizing the adjustment of membranous layer ingredient and function to the adjustment of electrolytic solution.The present invention intends, innovatively by the regulating and control to micro-arc oxidation electrolyte, obtaining the porous nano titanium oxide coating that zinc doping content is controlled, thus improves skeletonization and the anti-microbial property of coating.
Summary of the invention
The present invention is the biology performance based on the good biocompatibility of titanium oxide and zinc element excellence, and differential arc oxidization technique does not limit by workpiece geometric shape, and coating is combined firmly with matrix, and has porous and nanostructure proposes.Also namely adopt differential arc oxidization technique to select suitable processing condition, in certain electrolytic solution, at titanium or the preparation of titanium alloy-based surface, there is porous and nanostructure, and the zinc doping titanium oxide coating material of coating and matrix mortise.
Specific embodiment of the present invention is as follows:
A, provide a kind of electrolytic solution including zinc element, and be aided with the ionogen that at least one assists the starting the arc;
B, in above-mentioned specific electrolytic solution, with titanium or titanium alloy for anode, stainless steel is negative electrode, adopts direct current pulse power source to carry out differential arc oxidation process to titanium or titanium alloy;
C, current density 0.1 ~ 5A/cm
2, voltage 200 ~ 700V, frequency 500 ~ 2000Hz, dutycycle 10 ~ 80%;
D, differential arc oxidation time are 1 ~ 60min;
E, preparation process electrolyte temperature are no more than 60 DEG C.
In described electrolytic solution, the optimum content scope of zinc element is 0.01 ~ 0.5mol/L, and the ionogen optimum content scope of the auxiliary starting the arc is 0.01 ~ 2mol/L.At least one in the preferred zinc acetate of the ionogen of zinc element, zinc nitrate, zinc sulfate, zinc chloride or other soluble zinc salt is provided; Assist at least one in the preferred lime acetate of ionogen of the starting the arc, Sodium Glycerophosphate, secondary calcium phosphate, sodium hydroxide, potassium hydroxide, phosphoric acid, nitric acid or acetic acid.
Zinc doping titania coating prepared by aforesaid method, in porous with nanocrystalline structures form, aperture is less than 20 μm, and surface microstructure yardstick is less than 100nm; Coating substance is primarily of anatase titanium oxide and rutile titanium oxide or pure anatase octahedrite composition; Coating is combined with matrix closely; By adjustment electrolytic solution composition, concentration and processing condition, the content of zinc element in coating can be made controlled within the scope of 0.01 ~ 50wt%, and preferable range is 0.01 ~ 35wt%.
When coating being immersed in buffered soln, zine ion can continuous release from coating in a long time.Sclerocyte can adhere fast and propagation at this coatingsurface, demonstrates good biocompatibility, do not have cytotoxicity.Compared with non-adulterated TiOx coating, this coating can significantly improve sclerocyte at the multiplication rate of coatingsurface and vigor.Zinc doping nano-titanium oxide coating layer has obvious antibacterial effect to the intestinal bacteria of Gram-negative bacteria and the streptococcus aureus of gram-positive microorganism.Adopt the zinc-doped porous nano-titanium oxide coating that preparation technology of the present invention obtains at titanium or titanium alloy surface, directly can be used as carrying osseous tissue and replace and repair materials.
The present invention has following outstanding advantages:
1, the zinc-doped porous nano-titanium oxide coating prepared of the present invention, have close Young's modulus with sclerotin, anchoring strength of coating is high, stable chemical nature, has porous and nanostructure, is conducive to growth and the combination of new bone.
2, the present invention is at titanium or titanium alloy surface single stage method in-situ preparation zinc-doped porous nano-titanium oxide coating, and can, by adjustment electrolytic solution composition, concentration and processing condition, make zinc element content in coating controlled within the scope of 0.01 ~ 50wt%.
3, the zinc-doped porous nano-titanium oxide coating that prepared by the present invention has better biocompatibility than existing titania coating, sclerocyte is faster in this coatingsurface multiplication rate, vigor is stronger, can be used as the replacement material that femur, hip joint and tooth implant etc. bear large load position.
4, the zinc-doped porous nano-titanium oxide coating that prepared by the present invention has obvious antibacterial effect to the intestinal bacteria of Gram-negative bacteria and the streptococcus aureus of gram-positive microorganism, is expected to effective prevention and therapy implant postoperative infection.
5, preparation technology of the present invention is simple, quick, easy and simple to handle, controlled, is easy to apply.
Accompanying drawing explanation
The surface scan electromicroscopic photograph of Fig. 1 zinc-doped porous nano-titanium oxide coating provided by the invention.(a) 500 times; (b) 50000 times.Visible coating is porous and nanostructure.
The X ray diffracting spectrum of Fig. 2 zinc-doped porous nano-titanium oxide coating provided by the invention.Visible coating is made up of anatase tio2 and rutile TiO2.In figure, the characteristic peak of titanium is from Titanium base.
The surperficial EDS collection of illustrative plates of Fig. 3 zinc-doped porous nano-titanium oxide coating provided by the invention.Visible zinc element is successfully doped in coating.
The cross-sectional scans Electronic Speculum pattern of Fig. 4 zinc-doped porous nano-titanium oxide coating provided by the invention.Visible coating is combined closely with matrix.
The cell quantity of Fig. 5 sclerocyte after pure titanium, porous nano titanium oxide coating and zinc-doped porous nano-titanium oxide coating provided by the invention surface cultivates 1,4,12 and 24 hour.Visible zinc-doped porous nano-titanium oxide coating is more conducive to growth and the propagation of sclerocyte than another bi-material, shows better cell compatibility.
Specific embodiment
Feature of the present invention and effect is illustrated further below by embodiment.Limit the present invention absolutely not.
Embodiment 1:
A () uses deionized water that the Sodium Glycerophosphate of the zinc acetate of 0.02mol/L, the lime acetate of 0.1mol/L and 0.05mol/L is hybridly prepared into electrolytic solution.B () take titanium as anode, stainless steel is negative electrode, adopts direct current pulse power source at constant current density 0.5A/cm
2, voltage 400 ~ 460V, frequency 800Hz, dutycycle 10% condition under process 4min, keep electrolyte temperature lower than 60 DEG C.C () sample rinses and seasoning after taking out in deionized water.After testing, coat-thickness is about 5-10 μm, is elementary compositionly mainly Ti, O, Zn, Ca and P, and X-ray diffraction analysis shows that coating phase composite is mainly pure anatase octahedrite TiO
2, EDS result shows that in coating, zinc element content is about 3.4wt%, and sem analysis display coating aperture is less than 10 μm, crystal particle scale 10-100nm.
Embodiment 2:
A () uses deionized water that the Sodium Glycerophosphate of the zinc acetate of 0.04mol/L, the lime acetate of 0.1mol/L and 0.05mol/L is hybridly prepared into electrolytic solution.B () take titanium as anode, stainless steel is negative electrode, adopts direct current pulse power source at constant current density 0.5A/cm
2, voltage 400 ~ 480V, frequency 800Hz, dutycycle 10% condition under process 4min, keep electrolyte temperature lower than 60 DEG C.C () sample rinses and seasoning after taking out in deionized water.After testing, coat-thickness is about 6-12 μm, is elementary compositionly mainly Ti, O, Zn, Ca and P, and X-ray diffraction analysis shows that coating phase composite is mainly anatase octahedrite TiO
2with rutile TiO
2, EDS result shows that in coating, zinc element content is about 7.3wt%, and sem analysis display coating aperture is less than 10 μm, crystal particle scale 20-100nm.
Embodiment 3:
A () uses deionized water that the sodium hydroxide of the lime acetate of the zinc nitrate of 0.08mol/L, 0.2mol/L, the Sodium Glycerophosphate of 0.02mol/L and 0.1mol/L is hybridly prepared into electrolytic solution.B () take titanium as anode, stainless steel is negative electrode, adopts direct current pulse power source at constant current density 1A/cm
2, voltage 500 ~ 600V, frequency 1000Hz, dutycycle 30% condition under process 3min, keep electrolyte temperature lower than 60 DEG C.C () sample rinses and seasoning after taking out in deionized water.After testing, coat-thickness is about 25-35 μm, is elementary compositionly mainly Ti, O, Zn, Ca and P, and X-ray diffraction analysis shows that coating phase composite is mainly anatase octahedrite TiO
2with rutile TiO
2, EDS result shows that in coating, zinc element content is about 15.7wt%, and sem analysis display coating aperture is less than 20 μm, crystal particle scale 40-100nm.
Embodiment 4:
A () uses deionized water that the zinc acetate of 0.02mol/L and the lime acetate of 0.1mol/L are hybridly prepared into electrolytic solution.B () take titanium as anode, stainless steel is negative electrode, adopts direct current pulse power source at constant current density 1A/cm
2, voltage 250 ~ 320V, frequency 800Hz, dutycycle 20% condition under process 5min, keep electrolyte temperature lower than 60 DEG C.C () sample rinses and seasoning after taking out in deionized water.After testing, coat-thickness is about 3-10 μm, is elementary compositionly mainly Ti, O, Zn and Ca, and X-ray diffraction analysis shows that coating phase composite is pure anatase octahedrite TiO
2, EDS result shows that in coating, zinc element content is about 0.9wt%, and sem analysis display coating aperture is less than 1 μm, crystal particle scale 10-80nm.
Embodiment 5:
A () uses deionized water that the zinc sulfate of 0.1mol/L and the phosphoric acid of 0.15mol/L are hybridly prepared into electrolytic solution.B () take Ti6Al4V as anode, stainless steel is negative electrode, adopts direct current pulse power source at constant current density 1.5A/cm
2, voltage 450 ~ 530V, frequency 1500Hz, dutycycle 50% condition under process 15min, keep electrolyte temperature lower than 60 DEG C.C () sample rinses and seasoning after taking out in deionized water.After testing, coat-thickness is about 15-30 μm, is elementary compositionly mainly Ti, O, Zn, S and P, and X-ray diffraction analysis shows that coating phase composite is rutile TiO
2with anatase octahedrite TiO
2, EDS result shows that in coating, zinc element content is about 26.7wt%, and sem analysis display coating aperture is less than 15 μm, crystal particle scale 10-80nm.
Embodiment 6:
A () uses deionized water that the Sodium Glycerophosphate of the zinc chloride of 0.04mol/L, the sodium hydroxide of 0.1mol/L and 0.05mol/L is hybridly prepared into electrolytic solution.B () take Ni-Ti alloy as anode, stainless steel is negative electrode, adopts direct current pulse power source at constant current density 1.5A/cm
2, voltage 480 ~ 550V, frequency 600Hz, dutycycle 30% condition under process 30min, keep electrolyte temperature lower than 60 DEG C.C () sample rinses and seasoning after taking out in deionized water.After testing, coat-thickness is about 35-50 μm, is elementary compositionly mainly Ti, O, Zn, Na, P and Ni, and X-ray diffraction analysis shows that coating phase composite is mainly anatase octahedrite TiO
2with rutile TiO
2, EDS result shows that in coating, zinc element content is about 33.6wt%, and sem analysis display coating aperture is less than 20 μm, crystal particle scale 20-100nm.
Claims (1)
1. a preparation method for zinc-doped porous nano-titanium oxide coating, is characterized in that, comprises the steps:
(1) provide a kind of electrolytic solution including zinc element, and be aided with the ionogen that at least one assists the starting the arc;
(2) in above-mentioned specific electrolytic solution, with titanium or titanium alloy for anode, stainless steel is negative electrode, adopts direct current pulse power source to carry out differential arc oxidation process to titanium or titanium alloy,
Control current density 0.1 ~ 5A/cm
2, voltage 200 ~ 700V, frequency 500 ~ 2000Hz, dutycycle 10 ~ 80%; Controlling arc oxidization time is 1 ~ 60min; Control electrolyte temperature and be no more than 60 DEG C,
In electrolytic solution, the content range of zinc element is 0.01 ~ 0.5mol/L, and the electrolytical content range of the auxiliary starting the arc is 0.01 ~ 2mol/L,
The ionogen of zinc element is provided to be at least one in zinc acetate, zinc nitrate, zinc sulfate or zinc chloride soluble zinc salt; The ionogen of the auxiliary starting the arc is at least one in lime acetate, Sodium Glycerophosphate, secondary calcium phosphate, sodium hydroxide, potassium hydroxide, phosphoric acid, nitric acid or acetic acid.
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| CN102732882B (en) * | 2012-07-13 | 2014-08-13 | 东南大学 | Artificial joint with micro-nano graded topological surface structure and preparation method of artificial joint |
| CN102995092A (en) * | 2012-11-23 | 2013-03-27 | 北京星航机电设备厂 | Blue titan-alloy microarc oxidation coloring solution and preparation method thereof |
| CN103526261A (en) * | 2013-10-17 | 2014-01-22 | 赵全明 | Preparation method of zinc-containing micro-arc oxidation electrolyte and zinc-containing biological ceramic membrane |
| CN103911644B (en) * | 2014-04-09 | 2016-10-05 | 江西科技师范大学 | Titanium alloy micro-arc oxidation electrolyte and differential arc oxidation method |
| CN105420786A (en) * | 2015-11-19 | 2016-03-23 | 西安交通大学 | Preparation method for nano-sodium silicotitanate/titanium dioxide bio-coatings on titanium surfaces |
| 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 |
| CN110965108A (en) * | 2019-12-27 | 2020-04-07 | 沈兰兰 | Zn-TiO2Method for producing a coating |
| EP4112090A4 (en) * | 2020-02-25 | 2023-07-05 | Beijing AK Medical Co., Ltd. | Antibacterial three-dimensional porous bone implant material and preparation method therefor |
| CN111467572B (en) * | 2020-04-09 | 2022-07-29 | 上海交通大学医学院附属第九人民医院 | Implant material and preparation method and application thereof |
| CN111839768B (en) * | 2020-07-28 | 2021-09-03 | 中日友好医院(中日友好临床医学研究所) | Zinc-modified implant and preparation method thereof |
| CN112813478A (en) * | 2020-12-30 | 2021-05-18 | 西比里电机技术(苏州)有限公司 | Method for performing thermoelectric chemical oxidation on surface of niobium-titanium alloy and electrolyte |
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