CN103361702A - Method for surface modification of dental implant - Google Patents
Method for surface modification of dental implant Download PDFInfo
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- CN103361702A CN103361702A CN2012100916396A CN201210091639A CN103361702A CN 103361702 A CN103361702 A CN 103361702A CN 2012100916396 A CN2012100916396 A CN 2012100916396A CN 201210091639 A CN201210091639 A CN 201210091639A CN 103361702 A CN103361702 A CN 103361702A
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Abstract
The invention mainly discloses a method for surface modification of a metal titanium dental implant. A titanium dioxide/hydroxyapatite composite coating with biocompatibility and biological activity is prepared on the surface of the dental implant by using a multi-electrode method; and the technology is suitable for modifying most of medical metal surfaces. The method mainly comprises the following steps of: (1) ultrasonically cleaning a mechanical face threaded titanium dental implant through ultrapure water, acetone and absolute ethyl alcohol and then drying; (2) uniformly arranging and distributing a titanium dioxide nanotube array with consistent aperture size on an anodic oxide layer of the implant as a buffer layer by using the multi-electrode method; (3) electrodepositing the hydroxyapatite coating in a calcium phosphate electric deposition solution by using the multi-electrode method to prepare the prepared hydroxyapatite coating which is uniformly distributed and has high purity and better biological activity; and (4) processing the material obtained by the process through high-temperature vacuum sintering. The titanium dioxide/hydroxyapatite composite coating prepared by the steps has better bonding strength and superior biological activity, so that the dental implant subjected to surface modification has a broader and longer-range application prospect.
Description
Technical field
The present invention relates to a kind of a kind of method in the modification of metal titanium dental implant surface, adopt the multi-electrode method to have biocompatibility and bioactive titanium dioxide/carboxy apatite composite coating in its surface preparation, this technology is applicable to the modification on most of medical metals surface.
Background technology
Titanium and alloy thereof have good biocompatibility, are one of topmost medical metal materials, are mainly used in orthopedics and tooth dental repair material, as being used for artificial knee joint, osteoarthrosis and the first-class material of artificial tooth metal finger.But because its titanium itself do not possess biological activity, can not effectively promote the healing of wound and the growth of surrounding bone tissue, next can not be effectively and surrounding tissue shape osteogenic bonding, and is lower with the bonding strength of surrounding tissue, is unfavorable for its life-time service.Hydroxyapatite (Ca
10(PO
4)
6(OH)
2, be the chief component composition of skeleton HA), in human teeth's enamel, surpass 95%, hydroxyapatite has good biocompatibility and osteoinductive, is usually used in bone tissue filling material, but because its fragility of hydroxyapatite is large, intensity is low, has limited its physical application.Now in conjunction with metal titanium and hydroxyapatite both advantages, the hydroxyapatite that has biocompatibility at titanium surface-coated one deck, form the hydroxyapatite/Ti matrix material, not only have the biocompatibility of hydroxyapatite and induce the characteristic of bone growth but also have intensity and the toughness of metal titanium, be expected to become the bio-medical material of a new generation.
Because metal titanium coefficient of surface expansion and hydroxyapatite differ greatly, if directly at metal titanium surface deposition hydroxyapatite, behind sintering, owing to than conference be full of cracks occuring, expansion coefficient difference comes off, therefore we adopt the titania nanotube layer as buffer layer, and can well in conjunction with metal titanium and hydroxyapatite, make it to have excellent bonding properties.Work as simultaneously hydroxyapatite coating layer and corrode in vivo, titanium dioxide still has good erosion resistance and biological activity.The method for preparing at present buffer layer titanium dioxide mainly contains the methods such as plasma spraying, magnetron sputtering and physical chemistry gaseous phase deposition, we adopt at titanium surface anodic oxidation in situ synthesis, prepare arrangement evenly on its surface, Nano tube array of titanium dioxide of the same size, its advantages intensity is high, is evenly distributed in the same size, have certain aperture, can be good at realizing hydroxyapatite coating layer and its physical bond.
The method for preparing at present hydroxyapatite coating layer mainly contains plasma spraying method, magnetron sputtering method, electrophoretic deposition and biomineralization method etc., we adopt electrochemical deposition method to prepare hydroxyapatite coating layer, it is low that electrochemical deposition method has a cost, manufacture craft is simple, the composition purity of preparing is high, the advantages such as mild condition is controlled have certain research and application prospect.
Summary of the invention
The purpose of this invention is to provide a kind of method for preparing titanium dioxide/hydroxylapatite gradient coating on the titanium dental implant surface by the galvanic deposit of many negative electrodes galvanostatic method, the method is intended to obtain having the very fine and close evenly titanium dioxide/hydroxylapatite gradient coating of high bond strength.Adopt many negative electrodes anonizing to prepare titania nanotube and continuous current electrochemical process deposited hydroxyl apatite coating, comprise the steps:
(1) adopt the shape of threads titanium dental implant, after acetone, dehydrated alcohol are ultrasonic, ultrasonic acid etching, with the deionized water ultrasonic cleaning, dry up stand-by;
(2) hydrofluoric acid solution of preparation 5w% is as anodised electrolytic solution, adopt titanium dental implant as working electrode, a plurality of platinum electrodes conducts are uniformly distributed in around the titanium dental implant to electrode, interelectrode distance is 4cm, at the lower potentiostatic method anodic oxidation 1h that adopts of magnetic agitation (80r/min), take out the deionized water ultrasonic cleaning, dry up stand-by.
(3) 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=4.2 with ammoniacal liquor, obtain at last uniform calcium phosphorus electrodeposit liquid;
(4) in above-mentioned calcium phosphorus electrodeposit liquid, take saturated calomel electrode as reference electrode, a plurality of platinized platinums are to electrode, and the titanium dental implant after the oxidation of coating is working electrode, carries out the continuous current electrochemical deposition in the electrolyzer of three-electrode system.The electrode workplace is apart from being 2cm, and electric current 0.007A, depositing time are 2700s.
(5) the titanium implant coated material vacuum sintering to obtaining: be warming up to 600 ℃, temperature rise rate and be 10 ℃/min, insulation 2h, furnace cooling then, obtain having the titanium implant material of titanium dioxide/carboxy apatite composite coating.
Above technique is all carried out under temperature constant state (＜90 ℃).
Compared with prior art, the invention has the beneficial effects as follows: the Nano tube array of titanium dioxide that (1) obtains is evenly distributed, and pore size is consistent, has certain erosion resistance and biological activity; Hydroxyapatite coating layer is careful evenly, and purity is high, has good biological activity.(2) Nano tube array of titanium dioxide has well been alleviated the shortcomings such as hydroxyapatite and titanium base thermal expansivity do not mate as tie coat, and the bonding strength of compound coating is significantly strengthened.(3) compound coating that obtains has good bonding strength, meets the biomaterial Application standard, and has good biological activity, and nontoxicity is conducive to its life-time service.
Description of drawings is as follows
The EDS of figure one embodiment of the invention titania nanotube can spectrogram
The SEM photo of figure two embodiment of the invention titania nanotubes
The EDS of figure three embodiment of the invention titanium dioxide/hydroxylapatite gradient coatings can spectrogram
The SEM photo of figure four embodiment of the invention titanium dioxide/hydroxylapatite gradient coatings.
Figure five embodiment of the invention rear thread shape dental implant surface pattern SEM photo that completes
Figure six embodiment of the invention are utilized the device schematic diagram of 4 platinum electrodes
Embodiment
The invention will be further described below in conjunction with embodiment.
Embodiment 1
(1) mechanical face shape of threads titanium dental implant is cooperated ultrasonic cleaning with dehydrated alcohol, acetone, deionized water respectively, the time is 10min; Then use HF: HNO
3: H
2O=1: 3: 6 acid solution is carried out acid etching; Cooperate ultrasonic cleaning with deionized water at last, the time is 10min.Dry up with the tweezers taking-up, stand-by.
(2) prepare the hydrofluoric acid solution of 5w% under the room temperature as anodised electrolytic solution, adopt titanium implant as working electrode, 4 platinum electrodes are as electrode being uniformly distributed in around the titanium dental implant, electrode workplace distance is 4cm, at the lower 20V voltage that adopts of magnetic agitation (80r/min), potentiostatic method anodic oxidation 1h takes out the deionized water ultrasonic cleaning, dries up stand-by.
(3) take by weighing four water-calcium nitrate 4.9592g, primary ammonium phosphate 1.4379g, use respectively dissolved in distilled water.Above-mentioned two kinds of solution preparations are become the 1000ml mixed solution, beaker is placed on the magnetic stirring apparatus stir, with ammoniacal liquor regulator solution pH=4.2, obtain uniform electrolytic solution.This electrolytic solution is put into electrolyzer, the titanium dental implant that (2) are obtained carries out electrochemical deposition, take saturated calomel electrode as reference electrode, 4 platinized platinums are to electrode, titanium implant after the oxidation of coating is working electrode, carries out continuous current electrochemical deposition (as shown in Figure 6) in the electrolyzer of three-electrode system.The electrode workplace is apart from being 2cm, and electric current 0.007A, depositing time are 2700s, and electrolyte temperature is 65 ℃.
(4) with the coated material that obtains in (3) after the distillation washing, dry 2h in the far-infrared baking oven, then vacuum sintering: be warming up to 600 ℃, temperature rise rate and be 10 ℃/min, insulation 2h, furnace cooling then, obtain having the titanium dental implant material of titanium dioxide/carboxy apatite composite coating.
The distribution of electrodes of the present embodiment as shown in Figure 6; The SEM photo of gained coated material and EDS power spectrum are respectively by shown in Fig. 1,2,3,4,5.
Figure one and figure two are the SEM of titanium dental implant surface titanium dioxide nano-tube array and EDS figure, can find out to prepare on the titanium dental implant surface to be evenly distributed in the same size, the titania nanotube structure of pore size about 100nm.Figure three and figure four are SEM and the EDS figure of titanium dioxide/carboxy apatite composite coating, the SEM photo can find out that this hydroxyapatite coating layer crystal grain is little, distribute evenly fine and close, without agglomeration, and there is certain hole, be fit to the adhesion growth of osteocyte, the EDS power spectrum illustrates that this coating contains Ca, P and a small amount of Ti element.Figure five is the titanium implant surface pattern with titanium dioxide/carboxy apatite composite coating of technique after finishing, and the surface has certain roughness, is conducive to survive adhering to of cell and break up, and coating is even.
Embodiment 2
Can adopt the platinum electrode number in the example 1 more than two or ring electrode as to electrode.
Claims (3)
1. a kind of method of medical tooth implant surface modification adopts the multi-electrode method to have biocompatibility and bioactive titanium dioxide/carboxy apatite composite coating in its surface preparation, and this technology is applicable to the modification on most of medical metals surface.Comprise the steps:
(1) mechanical face shape of threads titanium implant is cooperated ultrasonic cleaning with dehydrated alcohol, acetone, deionized water respectively, the time is 10min; Then use HF: HNO
3: H
2O=1: 3: 6 acid solution is carried out acid etching; Cooperate ultrasonic cleaning with deionized water at last, the time is 10min.Dry up with the tweezers taking-up, stand-by.
(2) prepare the hydrofluoric acid solution of 5w% under the room temperature as anodised electrolytic solution, adopt titanium implant as anode, 4 platinum electrodes are uniformly distributed in around the titanium implant as negative electrode, anode and negative electrode workplace distance are 4cm, at the lower 20V voltage that adopts of magnetic agitation (80r/min), potentiostatic method anodic oxidation 1h takes out the deionized water ultrasonic cleaning, dries up stand-by.
(3) take by weighing four water-calcium nitrate 4.9592g, primary ammonium phosphate 1.4379g, use respectively dissolved in distilled water.Above-mentioned two kinds of solution preparations are become the 1000ml mixed solution, beaker is placed on the magnetic stirring apparatus stir, with ammoniacal liquor regulator solution pH=4.2, obtain uniform electrolytic solution.This electrolytic solution is put into electrolyzer, the titanium implant that (2) are obtained carries out electrochemical deposition, take saturated calomel electrode as reference electrode, 4 platinized platinums are negative electrode, titanium implant after the oxidation of coating is positive electrode, carries out the continuous current electrochemical deposition in the electrolyzer of three-electrode system.Anode and negative electrode workplace are apart from being 2cm, and electric current 0.007A, depositing time are 2700s, and electrolyte temperature is 65 ℃.
(4) with the coated material that obtains in (3) after the distillation washing, dry 2h in the far-infrared baking oven, then vacuum sintering: be warming up to 600 ℃, temperature rise rate and be 10 ℃/min, insulation 2h, furnace cooling then, obtain having titanium dioxide/the titanium implant material of hydroxyapatite composite deposite.
2. described a kind of multiple-electrode electrochemical deposits the method for preparing titanium dioxide/carboxy apatite composite coating according to claim 1, it is characterized in that, in the technique of its anodic oxidation and galvanic deposit, adopts the negative electrode more than or equal to two.
3. described a kind of multiple-electrode electrochemical deposits the method for preparing titanium dioxide/carboxy apatite composite coating according to claim 1, it is characterized in that, the titanium implant for the treatment of coating can be mechanical face shape of threads or cylindric.
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| CN103924278A (en) * | 2014-04-24 | 2014-07-16 | 湘潭大学 | Method for preparing titanium-based titanium dioxide nanotube/nano hydroxyapatite composite coating |
| CN103952744A (en) * | 2014-04-04 | 2014-07-30 | 哈尔滨理工大学 | Dental implant micro-arc oxidation coating layer preparation device |
| EP2925912A4 (en) * | 2012-12-03 | 2016-08-24 | Univ California | Devices, systems and methods for coating surfaces |
| CN106983523A (en) * | 2017-03-15 | 2017-07-28 | 北京科技大学 | A kind of preparation method of dentistry implant and its alkalescent Nanosurface |
| CN107115566A (en) * | 2017-05-17 | 2017-09-01 | 南宁越洋科技有限公司 | The preparation method of titanium-based artificial tooth with PLLA/nHA surface active coatings |
| CN107881544A (en) * | 2017-11-01 | 2018-04-06 | 佛山市安齿生物科技有限公司 | A kind of nano-calcium phosphate inlays the preparation method of orderly TiOx nano array film layer |
| CN109512678A (en) * | 2018-11-28 | 2019-03-26 | 福建工程学院 | A kind of artificial tooth film layer preparation method |
| CN111394766A (en) * | 2020-04-08 | 2020-07-10 | 浙江大学医学院附属口腔医院 | Pure titanium implant with cobalt-doped coating and preparation method thereof |
| CN113373491A (en) * | 2020-12-15 | 2021-09-10 | 北京航空航天大学 | Preparation method of enamel-like structure composite material |
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| US9903035B2 (en) | 2012-12-03 | 2018-02-27 | The Regents Of The University Of California | Devices, systems and methods for coating surfaces |
| EP2925912A4 (en) * | 2012-12-03 | 2016-08-24 | Univ California | Devices, systems and methods for coating surfaces |
| CN103952744A (en) * | 2014-04-04 | 2014-07-30 | 哈尔滨理工大学 | Dental implant micro-arc oxidation coating layer preparation device |
| CN103952744B (en) * | 2014-04-04 | 2016-04-20 | 哈尔滨理工大学 | A kind of differential arc oxidation coating preparation facilities of tooth implant |
| CN103924278A (en) * | 2014-04-24 | 2014-07-16 | 湘潭大学 | Method for preparing titanium-based titanium dioxide nanotube/nano hydroxyapatite composite coating |
| CN106983523A (en) * | 2017-03-15 | 2017-07-28 | 北京科技大学 | A kind of preparation method of dentistry implant and its alkalescent Nanosurface |
| CN106983523B (en) * | 2017-03-15 | 2020-04-10 | 北京科技大学 | Dental implant and preparation method of alkalescent nano surface thereof |
| CN107115566A (en) * | 2017-05-17 | 2017-09-01 | 南宁越洋科技有限公司 | The preparation method of titanium-based artificial tooth with PLLA/nHA surface active coatings |
| CN107115566B (en) * | 2017-05-17 | 2020-01-31 | 南宁越洋科技有限公司 | Preparation method of titanium-based artificial tooth with PLLA/nHA surface active coating |
| CN107881544A (en) * | 2017-11-01 | 2018-04-06 | 佛山市安齿生物科技有限公司 | A kind of nano-calcium phosphate inlays the preparation method of orderly TiOx nano array film layer |
| CN109512678A (en) * | 2018-11-28 | 2019-03-26 | 福建工程学院 | A kind of artificial tooth film layer preparation method |
| CN111394766A (en) * | 2020-04-08 | 2020-07-10 | 浙江大学医学院附属口腔医院 | Pure titanium implant with cobalt-doped coating and preparation method thereof |
| CN111394766B (en) * | 2020-04-08 | 2021-05-04 | 浙江大学医学院附属口腔医院 | Pure titanium implant with cobalt-doped coating and preparation method thereof |
| CN113373491A (en) * | 2020-12-15 | 2021-09-10 | 北京航空航天大学 | Preparation method of enamel-like structure composite material |
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Application publication date: 20131023 |