CN101880890A - Electrochemical method for preparing HA/ZrO2 (hydroxylapatite/zirconia) gradient coating on surface of medical titanium - Google Patents
Electrochemical method for preparing HA/ZrO2 (hydroxylapatite/zirconia) gradient coating on surface of medical titanium Download PDFInfo
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Abstract
The invention discloses an electrochemical method for preparing a HA/ZrO2 (hydroxylapatite/zirconia) gradient coating on the surface of medical titanium. The method comprises the following steps of: carrying out electro-deposition in an electrolytic cell with a three-electrode system, wherein the medical titanium to be coated is a working electrode; carrying out electro-deposition to obtain a Zr (OH) 4 coating in a zirconium oxynitrate solution with certain concentration and pH value, wherein the deposition current is 20mA, and the deposition time is 600s; then, depositing a CaHPO42H2O coating in an electrolyte which has certain concentration and pH value and consists of calcium nitrate and ammonium dihydrogen phosphate, wherein the deposition current is 1.5mA, and the deposition time is 900s; and finally, carrying out vacuum sintering on the obtained coating materials, and raising the sintering temperature to 650 DEG C at a heating rate of 10 DEG C/min, then preserving the heat for two hours, and subsequently cooling the coating materials with a furnace so as to obtain the HA/ZrO2 composite coating. The electrochemical method of the invention has the advantages that: the ingredients of the coating are deposited on a substrate in the form of ions, so that the bonding strength of the HA/ZrO2 gradient coating and the Ti substrate is improved greatly; and the anti-corrosion and simulated body fluid experiment shows that even the HA on the surface is dissolved completely due to the biological effect, the remaining ZrO2 coating still has good anti-corrosion performance and certain biocompatibility.
Description
Technical field
The present invention relates to a kind of preparation method who passes through galvanostatic method prepared by electrodeposition HA/ZrO 2 (hydroxylapatite/zirconia) gradient coating on the biomaterial for medical purpose surface, be particularly useful for the preparation of the biomedical metal material bioactive coating on surface of tooth implant.
Background technology
Hydroxyapatite [Ca
10(PO
4)
6(OH)
2] be the main inorganic composition of vertebrates bone and tooth, have excellent biocompatibility, can with body osseous tissue generation surface reaction, form chemical bonding.Under humoral effect, the part degraded can take place in HA, discharges free calcium and phosphorus, is absorbed, utilizes by tissue, brings out neoblastic growth, thereby produces bone conduction effect, thereby cause material supplier author and medical worker's extensive concern.One of sclerous tissues's implant research and development emphasis concentrates on HA is coated in titanium alloy surface at present, the material that obtains had both had the intensity and the toughness of matrix metal, the biological activity and the biocompatibility that have HA again, thereby on allomeric function, approach natural bone, obtain lasting implant material reliably.Furlong in 1985 and Osborn will have the implant of HA coating for the first time and repair experiment clinically.
Shortcomings such as the not high and degree of crystallinity of the bonding strength between HA coating and Ti matrix is lower make coating under the erosion action of stressed effect and biological liquid, exist come off, potential problem such as dissolving, and shorten work-ing life of material.In the HA powder, add ceramics powder, as preparation HA/ZrO
2Deng the functionally gradient compound coating, keeping improving the bond quality of coating and matrix and the mechanical property of coating under the active prerequisite of coating biology.
ZrO
2Thermal expansivity between HA and titanium alloy, ZrO
2Have the biocompatibility that good wear resistance, antibiosis reason corrodibility is become reconciled, its intensity height, fracture toughness property index also are higher than other bioceramic material (referring to table 1), thereby preparation is with ZrO
2For the compound or gradient cladding of additive is a kind of method that overcomes the above problems, be implemented between matrix and the HA coating and introduce buffer layer, adjust thermal expansivity, improve the bonding strength of coating interface.ZrO
2The solid solution particle that forms in coating can strengthen the linkage force between titanium alloy substrate and the coating and reduce residual thermal stress, and it is toughness reinforcing to cause that phase transformation transforms, and microhardness of coating, Young's modulus, fracture toughness property and bonding strength are significantly increased.
Existing HA/ZrO
2Coating process comprises plasma spraying method, electrophoretic deposition, magnetron sputtering method etc.The plasma spraying coating material remains in some problems: (1) is caused the inhomogeneous of rough base top coat owing to linear spraying coating process and can't be carried out the top coat of complex shaped substrate; (2) produce very high residual interfacial stress between process of cooling floating coat and substrate, even coating is cracked, cause that coating is loosening or come off; (3) pyroprocess in the spraying makes HA decompose easily, produces Ca in coating
3(PO
4)
2With dephasigns such as amorphous HA, thereby influence the biological property of coating.In the electrophoretic deposition process, HA and ZrO
2All be to be present in the electrolytic solution with powder type, thus ZrO
2Particle is bad in the coating dispersiveness, thereby has influenced the mechanical property of coating, and each component particles agglomeration very easily appears in coating, and the over-all properties of final coating is relatively poor.The magnetron sputtering main drawback is that the coating that obtains is too thin, can dissolve very soon in vivo.
Prepare and have good mechanical performance and bioactive HA/ZrO concurrently
2Composite ceramics has become the new direction of bioceramic material research to satisfy biomedical aspect carrying higher requirement.In view of the above shortcoming of prior art, the present invention adopt electrochemical method prepare the tool densification, evenly, the HA/ZrO of high bond strength
2Complex gradient coating.Zirconium white of the present invention, hydroxyapatite coating layer respectively by ionic species successively galvanic deposit to titanium alloy surface, the coating even compact that obtains does not exist ion dispersion inequality and agglomeration, finally obtains the good new bio medical material of over-all properties.Zirconium white has well been alleviated shortcomings such as HA and titanium base thermal expansivity do not match as tie coat, and the bonding strength of compound coating is significantly strengthened.Even the HA on top layer is because biological action all dissolves remaining ZrO
2Layer still has erosion resistance and biocompatibility preferably.
The main mechanical property of table 1. hydroxyapatite, titanium six aluminium, four vanadium and zirconia alloy
Summary of the invention
The purpose of this invention is to provide a kind of method of passing through continuous current prepared by electrodeposition HA/ZrO 2 (hydroxylapatite/zirconia) gradient coating on the bio-medical material surface, this method is intended to obtain having the very fine and close evenly HA/ZrO of high bond strength
2Gradient cladding.Adopt continuous current electrochemical deposition and ionic species deposition, comprise the steps:
(1) bio-medical metallic surface, after acetone, dehydrated alcohol are ultrasonic, ultrasonic acid etching;
(2) get analytically pure Zircosol ZN and obtain uniform zirconium solution, regulate PH=2.3 with ammoniacal liquor then and obtain even electrolytic solution A at last with dilute nitric acid dissolution; Get four water-calcium nitrate, ammonium di-hydrogen phosphate and obtain uniform calcium phosphorus solution with remix behind the dissolved in distilled water respectively, regulate PH=4.1, obtain even electrolytic solution B at last with ammoniacal liquor;
(3) in described electrolytic solution, be reference electrode with the saturated calomel electrode, platinized platinum is a counter electrode, the bio-medical metal for the treatment of coating is a working electrode, carries out electrochemical deposition in the electrolyzer of three-electrode system;
The processing parameter of electrochemical deposition is: deposit electric current earlier in electrolytic solution A: 20mA, depositing time 600s; In electrolytic solution B, deposit electric current subsequently: 1.5mA, depositing time 900s.
(4) the bio-medical metal coating layer material vacuum sintering to obtaining: be warming up to 650 ℃, temperature rise rate and be 10 ℃/min, insulation 2h, furnace cooling then, obtain having HA/ZrO
2The bio-medical metallic substance of composite deposite.
Electrodeposition process is all finished under the condition of constant temperature (below 90 ℃).
Compared with prior art, the invention has the beneficial effects as follows: (1) zirconium white, hydroxyapatite respectively by ionic species successively galvanic deposit to the medical titanium surface, the coating even compact that obtains.(2) zirconium white has well been alleviated shortcomings such as HA and titanium base thermal expansivity do not match as tie coat, and the bonding strength of compound coating is significantly strengthened.(3) even the HA on top layer is because biological action all dissolves remaining ZrO
2Layer still has erosion resistance and biocompatibility preferably.(4) whole electrochemical process does not relate to HA and ZrO in earlier stage
2Step such as powder fining and dispersion, the gentle facility investment of reaction conditions is few, raw material availability is high, technology is simple to operation.
The bio-medical metal that need are handled carries out being polished in its surface successively to 1200# sand paper with 200# earlier before the above step operation, polishing machine polishing, and remove surperficial greasy dirt, and making can be in conjunction with tightr between coating and the titanium base.
Description of drawings is as follows
The SEM photo of figure one embodiment of the invention zirconia coating.
The EDS of figure two embodiment of the invention zirconia coatings can spectrogram.
The SEM photo of figure three embodiment of the invention HA/ZrO 2 (hydroxylapatite/zirconia) gradient coatings.
The EDS of figure four embodiment of the invention HA/ZrO 2 (hydroxylapatite/zirconia) gradient coatings can spectrogram.
The SEM photo of figure five embodiment of the invention HA/ZrO 2 (hydroxylapatite/zirconia) gradient coating sections.
Embodiment
The invention will be further described below in conjunction with embodiment.
Embodiment 1
(1), is cut into the titanium sheet of 1 * 1 * 0.1cm with medical pure titanium wire cutting processing; Sand paper is with the polishing of titanium sheet, till smooth surface does not have machining marks; Cooperate ultrasonic cleaning with dehydrated alcohol, acetone, deionized water respectively, the time is 8min; Use HF: HNO then
3: H
2O=1: 1: 8 acid solution is carried out acid etching; Cooperate ultrasonic cleaning with deionized water at last, the time is 8min.With tweezers sample is put in the sample bag, preparing experiment is used.
(2) the Ti sheet is the negative electrode working electrode, and platinum electrode is a counter electrode, and saturated calomel is a reference electrode, and interelectrode distance is 3cm.
(3) take by weighing anhydrous nitric acid oxygen zirconium 0.5781g, use the 100ml dilute nitric acid dissolution, constant volume is to 200ml then, beaker placed on the magnetic stirring apparatus stir, and with ammoniacal liquor regulator solution pH=2.3, obtains uniform electrolytic solution at last.This electrolytic solution is put into electrolyzer carry out electrochemical deposition, correlation parameter is: electric current: 20mA, depositing time 600s; Electrolyte temperature: 25 ℃.The titanium sheet is taken out nature to be dried stand-by.
(4) take by weighing four water-calcium nitrate 4.9592g, primary ammonium phosphate 1.4379g, use dissolved in distilled water respectively.Above-mentioned two kinds of solution are mixed with the 1000ml mixed solution, beaker are placed on the magnetic stirring apparatus stir,, obtain uniform electrolytic solution with ammoniacal liquor regulator solution pH=4.1.This electrolytic solution is put into electrolyzer, and the titanium sheet that (3) are obtained carries out electrochemical deposition, and correlation parameter is: electric current: 1.5mA, depositing time 900s; Electrolyte temperature: 65 ℃.
(5) with the coated material that obtains in (4) after the distillation washing, dry 2h in the far infrared baking oven, then vacuum sintering: be warming up to 650 ℃, temperature rise rate and be 10 ℃/min, insulation 2h, furnace cooling then, obtain having HA/ZrO
2The bio-medical metallic substance of composite deposite.
The SEM photo of present embodiment gained coated material and EDS power spectrum are respectively by shown in Fig. 1,2,3,4,5.
Figure one and figure two are single Zr (OH)
4The SEM of coating and EDS figure one deck Zr (OH) in the even branch of Ti primary surface as can be seen
4Coating.Figure three and figure four are Zr (OH)
4The SEM of/HA compound coating and EDS figure, SEM photo this coated grains as can be seen is little, and it is evenly fine and close to distribute, no agglomeration, and have certain hole, and being fit to the adhesion growth of osteocyte, the EDS power spectrum illustrates that this coating contains Ca, P and Zr element.Figure five is ZrO behind the sintering
2The sectional drawing of/HA compound coating can see that the titanium surface is successively by ZrO
2Cover with the HA coating.Comprehensive priority by the success of galvanostatic deposition method as can be known is at zirconium ion electrolytic solution and contain in the electrolytic solution of calcium, phosphate anion and prepare ZrO
2The medical compound coating of/HA gradient.
Embodiment 2
(1), is cut into the titanium sheet of 1 * 1 * 0.1cm with medical pure titanium wire cutting processing; Sand paper is with the polishing of titanium sheet, till smooth surface does not have machining marks; Cooperate ultrasonic cleaning with dehydrated alcohol, acetone, deionized water respectively, the time is 8min; Use HF: HNO then
3: H
2O=1: 1: 8 acid solution is carried out acid etching; Cooperate ultrasonic cleaning with deionized water at last, the time is 8min.With tweezers sample is put in the sample bag, preparing experiment is used.
(2) the Ti sheet is the negative electrode working electrode, and platinum electrode is a counter electrode, and saturated calomel is a reference electrode, and interelectrode distance is 3cm.
(3) take by weighing anhydrous nitric acid oxygen zirconium 1.1562g, use the 100ml dilute nitric acid dissolution, constant volume is to 200ml then, beaker placed on the magnetic stirring apparatus stir, and with ammoniacal liquor regulator solution pH=2.3, obtains uniform electrolytic solution at last.This electrolytic solution is put into electrolyzer carry out electrochemical deposition, correlation parameter is: electric current: 20mA, depositing time 600s; Electrolyte temperature: 25 ℃.The titanium sheet is taken out nature to be dried stand-by.
(4) take by weighing four water-calcium nitrate 4.9592g, primary ammonium phosphate 1.4379g, use dissolved in distilled water respectively.Above-mentioned two kinds of solution are mixed with the 1000ml mixed solution, beaker are placed on the magnetic stirring apparatus stir,, obtain uniform electrolytic solution with ammoniacal liquor regulator solution pH=4.1.This electrolytic solution is put into electrolyzer, and the titanium sheet that (3) are obtained carries out electrochemical deposition, and correlation parameter is: electric current: 1.5mA, depositing time 900s; Electrolyte temperature: 65 ℃.
(5) with the coated material that obtains in (4) after the distillation washing, dry 2h in the far infrared baking oven, then vacuum sintering: be warming up to 650 ℃, temperature rise rate and be 10 ℃/min, insulation 2h, furnace cooling then, obtain having HA/ZrO
2The bio-medical metallic substance of gradient coating.
Embodiment 3
(1), is cut into the titanium sheet of 1 * 1 * 0.1cm with medical pure titanium wire cutting processing; Sand paper is with the polishing of titanium sheet, till smooth surface does not have machining marks; Cooperate ultrasonic cleaning with dehydrated alcohol, acetone, deionized water respectively, the time is 8min; Use HF: HNO then
3: H
2O=1: 1: 8 acid solution is carried out acid etching; Cooperate ultrasonic cleaning with deionized water at last, the time is 8min.With tweezers sample is put in the sample bag, preparing experiment is used.
(2) the Ti sheet is the negative electrode working electrode, and platinum electrode is a counter electrode, and saturated calomel is a reference electrode, and interelectrode distance is 3cm.
(3) take by weighing anhydrous nitric acid oxygen zirconium 1.7343g, use the 100ml dilute nitric acid dissolution, constant volume is to 200ml then, beaker placed on the magnetic stirring apparatus stir, and with ammoniacal liquor regulator solution pH=2.3, obtains uniform electrolytic solution at last.This electrolytic solution is put into electrolyzer carry out electrochemical deposition, correlation parameter is: electric current: 20mA, depositing time 600s; Electrolyte temperature: 25 ℃.The titanium sheet is taken out nature to be dried stand-by.
(4) take by weighing four water-calcium nitrate 4.9592g, primary ammonium phosphate 1.4379g, use dissolved in distilled water respectively.Above-mentioned two kinds of solution are mixed with the 1000ml mixed solution, beaker are placed on the magnetic stirring apparatus stir,, obtain uniform electrolytic solution with ammoniacal liquor regulator solution pH=4.1.This electrolytic solution is put into electrolyzer, and the titanium sheet that (3) are obtained carries out electrochemical deposition, and correlation parameter is: electric current: 1.5mA, depositing time 900s; Electrolyte temperature: 65 ℃.
(5) with the coated material that obtains in (4) after the distillation washing, dry 2h in the far infrared baking oven, then vacuum sintering: be warming up to 650 ℃, temperature rise rate and be 10 ℃/min, insulation 2h, furnace cooling then, obtain having HA/ZrO
2The bio-medical metallic substance of gradient coating.
Embodiment 4
Volumetric molar concentrations such as the anhydrous nitric acid oxygen zirconium among the embodiment 1,2,3 changes into are got two water Zircosol ZNs, carry out electrochemical deposition, other condition is constant.
Change the medical pure titanium base material among the embodiment 1,2,3 into Ti6Al4V, carry out electrochemical deposition, other condition is constant.
More than the preparation process of each embodiment under 25 ℃ of waters bath with thermostatic control and 65 ℃ of conditions, finish respectively, and to prepare homodisperse electrolytic solution before the deposition.Preparation also can be finished at thermostatically heating (below 90 ℃).Other each embodiment has comparable EDS power spectrum and SEM microtexture relation with embodiment 1.
HA/ZrO provided by the invention
2The method of gradient cladding can also be applied in other the electrochemical deposition.Zirconium white of the present invention, hydroxyapatite coating layer respectively by ionic species successively galvanic deposit to titanium alloy surface, the coating even compact that obtains.Zirconium white has well been alleviated shortcomings such as HA and titanium base thermal expansivity do not match as tie coat, and the bonding strength of complex gradient coating is significantly strengthened.Even the HA on top layer is because biological action all dissolves remaining ZrO
2Layer still has good erosion resistance and biocompatibility.
Claims (3)
1. a medical titanium surface electrochemistry deposits the method for preparing HA/ZrO 2 (hydroxylapatite/zirconia) gradient coating, is that raw material prepares the very high HA/ZrO of bonding strength through being electrochemically-deposited in the bio-medical metallic surface with Zircosol ZN, phosphoric acid salt and calcium salt
2Anticorrosive biological complex gradient coating comprises the steps:
(1) bio-medical metallic surface, after acetone, dehydrated alcohol are ultrasonic, ultrasonic acid etching;
(2) get analytically pure Zircosol ZN and obtain uniform zirconium solution, regulate PH=2.3 with ammoniacal liquor then and obtain even electrolytic solution A at last with dilute nitric acid dissolution; Get four water-calcium nitrate, ammonium di-hydrogen phosphate and obtain uniform calcium phosphorus solution with remix behind the dissolved in distilled water respectively, regulate PH=4.1, obtain even electrolytic solution B at last with ammoniacal liquor;
(3) in described electrolytic solution, be reference electrode with the saturated calomel electrode, platinized platinum is a counter electrode, the bio-medical metal for the treatment of coating is a working electrode, carries out electrochemical deposition in the electrolyzer of three-electrode system; The processing parameter of electrochemical deposition is: when in electrolytic solution A, depositing earlier, and electric current: 20mA, depositing time 600s; When in electrolytic solution B, depositing subsequently, electric current: 1.5mA, depositing time 900s;
(4) the bio-medical metal coating layer material vacuum sintering to obtaining: be warming up to 650 ℃, temperature rise rate and be 10 ℃/min, insulation 2h, furnace cooling then, obtain having HA/ZrO
2The bio-medical metallic substance of gradient coating.
2. prepare the method for HA/ZrO 2 (hydroxylapatite/zirconia) gradient coating according to the described a kind of electrochemical deposition of claim 1, it is characterized in that ZrO in the described zirconyl nitrate solution
2+Root at least can be by obtaining in following a kind of material: ZrO (NO
3)
2, ZrO (NO
3)
22H
2O.
3. prepare the method for HA/ZrO 2 (hydroxylapatite/zirconia) gradient coating according to the described a kind of electrochemical deposition of claim 1, it is characterized in that, the bio-medical metal for the treatment of coating at least can be by following a kind of material: pure titanium, Ti6Al4V.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103184497A (en) * | 2011-12-30 | 2013-07-03 | 电子科技大学 | Electrochemical method for preparing fluorine-containing hydroxyapatite/zirconia transition coating on surface of medical titanium |
| CN103561787A (en) * | 2011-06-03 | 2014-02-05 | 新特斯有限责任公司 | Surgical implant |
| CN104762645A (en) * | 2015-02-28 | 2015-07-08 | 深圳大学 | Medical implant material and preparation method thereof |
| CN105074056A (en) * | 2013-02-22 | 2015-11-18 | 海德罗-魁北克公司 | Techniques for production of chlorated products and prefabricated cathode structures |
| CN108434518A (en) * | 2018-05-25 | 2018-08-24 | 林振 | Traditional Chinese medicine monomer sequence is sustained preparation method of the skeletonization at blood vessel calcium phosphorus timbering material |
| CN114525488A (en) * | 2022-04-21 | 2022-05-24 | 中南大学湘雅医院 | Magnetron sputtering zirconium oxide doped hydroxyapatite coating and application thereof |
| CN114712555A (en) * | 2022-04-12 | 2022-07-08 | 四川亿诺森生物科技有限公司 | Hard tissue repair material and preparation method and application thereof |
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2010
- 2010-07-08 CN CN 201010220366 patent/CN101880890A/en active Pending
Non-Patent Citations (4)
| Title |
|---|
| 《J Mater Sci: Mater Med》 20091231 Hsueh-Chuan Hsu等 ZrO2/hydroxyapatite coating on titanium by electrolytic deposition 615-619 1-3 第20卷, 2 * |
| 《Materials Science and Engineering》 20061231 S.K. Yen等 Characterization of electrolytic HA/ZrO2 double layers coatings on Ti-6Al-4V implant alloy 65-77 1-3 第26卷, 2 * |
| 《生命科学仪器》 20100630 黄勇等 羟基磷灰石/氧化锆生物活性复合涂层的研究 30-33 1-3 第8卷, 2 * |
| 《稀有金属材料与工程》 20090630 王英波等 脉冲电化学沉积制备n-HA/ZrO2 复合涂层 1071-1075 1-3 第38卷, 第6期 2 * |
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| CN103561787A (en) * | 2011-06-03 | 2014-02-05 | 新特斯有限责任公司 | Surgical implant |
| US9283303B2 (en) | 2011-06-03 | 2016-03-15 | DePuy Synthes Products, Inc. | Surgical implant |
| CN103561787B (en) * | 2011-06-03 | 2016-08-17 | 新特斯有限责任公司 | Surgical implant |
| US9702037B2 (en) | 2011-06-03 | 2017-07-11 | DePuy Synthes Products, Inc. | Surgical implant |
| CN103184497A (en) * | 2011-12-30 | 2013-07-03 | 电子科技大学 | Electrochemical method for preparing fluorine-containing hydroxyapatite/zirconia transition coating on surface of medical titanium |
| CN105074056A (en) * | 2013-02-22 | 2015-11-18 | 海德罗-魁北克公司 | Techniques for production of chlorated products and prefabricated cathode structures |
| EP2959037A4 (en) * | 2013-02-22 | 2016-09-07 | Hydro Québec | Techniques for production of chlorated products and prefabricated cathode structures |
| CN104762645A (en) * | 2015-02-28 | 2015-07-08 | 深圳大学 | Medical implant material and preparation method thereof |
| CN108434518A (en) * | 2018-05-25 | 2018-08-24 | 林振 | Traditional Chinese medicine monomer sequence is sustained preparation method of the skeletonization at blood vessel calcium phosphorus timbering material |
| CN114712555A (en) * | 2022-04-12 | 2022-07-08 | 四川亿诺森生物科技有限公司 | Hard tissue repair material and preparation method and application thereof |
| CN114525488A (en) * | 2022-04-21 | 2022-05-24 | 中南大学湘雅医院 | Magnetron sputtering zirconium oxide doped hydroxyapatite coating and application thereof |
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