CN102330086A - Titanium dioxide-hydroxyapatite gradient coating of medical titanium or titanium alloy surface and preparation method - Google Patents
Titanium dioxide-hydroxyapatite gradient coating of medical titanium or titanium alloy surface and preparation method Download PDFInfo
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- CN102330086A CN102330086A CN201110235316A CN201110235316A CN102330086A CN 102330086 A CN102330086 A CN 102330086A CN 201110235316 A CN201110235316 A CN 201110235316A CN 201110235316 A CN201110235316 A CN 201110235316A CN 102330086 A CN102330086 A CN 102330086A
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Abstract
The invention discloses a titanium dioxide-hydroxyapatite gradient coating of a medical titanium or titanium alloy surface and a preparation method. The inner layer of the titanium dioxide-hydroxyapatite gradient coating is a composite layer of the titanium dioxide and the hydroxyapatite while the outer layer of the titanium dioxide-hydroxyapatite gradient coating is a hydroxyapatite coating. The preparation method comprises the following steps of: using titanium or titanium alloy as anode and metal stainless steel as cathode; carrying out microarc oxidation on the titanium or titanium alloy by using a direct current pulse power supply; after forming a porous structure containing titanium dioxide and amorphous calcium and phosphorus on the surface of the titanium or titanium alloy, coating the hydroxyapatite on the surface; and finally obtaining the titanium dioxide-hydroxyapatite gradient coating. The porous structure formed after the microarc oxidation is beneficial for improving the bonding strength of a titanium or titanium alloy substrate and the costing; the titanium dioxide layer formed by the microarc oxidation has a transitional effect on the performance so that the residual stress between the substrate and a hydroxyapatite bioactive coating can be reduced. The preparation method has the advantages of simplicity and convenience in operation.
Description
Technical field
The invention belongs to complex method, be specifically related to titanium dioxide titanium-hydroxylapatite gradient coating of a kind of medical titanium or titanium alloy surface and preparation method thereof at medical titanium or preparing bioactive coating on titanium alloy surface.
Background technology
Titanium or titanium alloy are to have light weight, Young's modulus excellent mechanical property such as low, excellent biological compatibility, higher erosion resistance and with organism good binding property etc., are the most attractive metallic biomaterials at present.But titanium or titanium alloy implant as bio-inert material; Completely different with the composition of natural bone; The bone that between they and the bone is a kind of mechanical embedding company property is integrated, but not strong chemical synostosis, thereby be necessary titanium and alloy thereof are carried out the biological activity modification.Prepare bioactive ceramic coating through process for modifying surface at metal base surface, improve material surface thing phase composition, become Recent study focus and development trend to improve its biological activity.
People carry out modification through different modes and handle on the titanium or titanium alloy surface, the optimal coating that still is complementary in its surface-coated and coenocorrelation.The biological ceramics Win 40350 (is called for short HA, chemical formula Ca
10(PO
4)
6(OH)
2) chemical ingredients similar with the calcium phosphate inorganics in the biological osseous tissue, can form strong chemistry with osseous tissue and be connected, histocyte is easy in its surface growth, and safe, nontoxic, does not have outer precursor reactant behind the implant into body, is ideal human body bone alternate material.Apply the HA coating at titanium or titanium alloy surface; Not only utilize the good characteristics of body material titanium or titanium alloy mechanical property, but also utilized biological activity and the good characteristics of biocompatibility of the HA of synthetic; Having obtained the mutual supplement with each other's advantages of two kinds of materials, is the material of the biological hard tissue planting body that is expected at present.
Method at titanium or titanium alloy surface coating hydroxyapatite coating layer has much at present, like methods such as plasma spraying, ion beam sputtering, sol-gel methodes.Wherein, plasma spraying method is to adopt hydroxyapatite powder, through the plasma high temperature melting, makes particle adhesion on matrix, because particle through heat, volatilizees easily, therefore, the film of formation is formed and is difficult to control.Ion beam sputtering is to prepare Win 40350 through ion beam sputtering, and film integral content is difficult to control.Characteristics such as sol-gel method has that technology is simple, mold temperature is low, be easy to control composition and microtexture, cost is low.The percent crystallinity of phase in the coating, the kind of phase, the microscopic characteristics parameters such as size of hole can be easy to change through changing thermal treatment temp, also the nanocrystal coating can be become more readily available.Sol-gel method is being widely used aspect the preparation of coating; But having a subject matter in this method is that coating and high base strength are low, and coating comes off easily.
Summary of the invention
The object of the invention mainly is in order to overcome the weak point of prior art; Differential arc oxidization technique is combined with sol-gel process; Titanium dioxide titanium-hydroxylapatite gradient coating of a kind of medical titanium or titanium alloy surface and preparation method thereof is provided; Thereby, good stability high in medical titanium or titanium alloy material surface preparation bonding strength, biological activity is good and have no side effect, have TiO
2The titanium of the gradient cladding of-HA (Win 40350) vesicular structure or titanium alloy and preparation method thereof.
Know-why of the present invention
The titanium dioxide titanium-hydroxylapatite gradient coating of a kind of medical titanium of the present invention or titanium alloy surface; Promptly adopt differential arc oxidation method and sol-gel method recombining process to prepare surface of metal titanium bioactive gradient coating; Be earlier titanium or titanium alloy to be carried out the differential arc oxidation processing; Directly apply the hydroxyapatite colloidal sols that adopts sol-gel technology preparing again at titanium or titanium alloy surface; Carry out pyroprocessing then, finally obtain the titanium dioxide titanium-hydroxylapatite gradient coating of medical titanium or titanium alloy surface.
Technical scheme of the present invention
Titanium dioxide titanium-hydroxyapatite (HA) gradient cladding of a kind of medical titanium or titanium alloy surface, the internal layer of described gradient cladding is the composite bed of titanium oxide and Win 40350, skin is a hydroxyapatite layer.
The preparation method of the above-mentioned a kind of medical titanium or the titanium dioxide titanium-hydroxylapatite gradient coating of titanium alloy surface specifically comprises the steps:
(1), titanium or titanium alloy surface pre-treatment
Titanium or titanium alloy surface are used No. 200 successively, and No. 400, No. 600, No. 800 sand paper carries out grinding and polishing, cleans and dry processing then;
(2), the preparation of electrolytic solution
With the biphosphate sodium water solution of the lime acetate aqueous solution of 0.1-0.5mol/L and 0.02-0.1mol/L promptly by volume, the lime acetate aqueous solution: the biphosphate sodium water solution is that 1:1 is mixed and made into electrolytic solution;
(3), be negative electrode with the metal stainless steel, step (1) is anode, places the electrolytic solution of step (2) gained through pretreated titanium or titanium alloy; Adopting direct current pulse power source is 400-500V, time to be that 5-20min carries out differential arc oxidation to titanium or titanium alloy in constant voltage;
(4), adopt sol-gel method to prepare hydroxyapatite colloidal sols solution;
Triethyl phosphate is joined absolute ethyl alcohol dilute, make the triethyl phosphate complete hydrolysis, get solution 1 with magnetic stirrer;
With nitrocalcite be dissolved in absolute ethyl alcohol be stirred well to dissolve solution 2;
With after solution 2 mixes, after magnetic stirrer to dissolving fully, ageing 24hr promptly gets hydroxyapatite colloidal sols solution with solution 1;
Solution 1 is pressed the Ca in solution 1 and the solution 2 with solution 2 blended amounts
2+, P
5-Mol ratio calculate i.e. Ca
2+: P
5-Be 1.67:1;
(5), adopt crystal pulling method or spin-coating method that the hydroxyapatite colloidal sols solution of step (4) gained is coated on titanium or the titanium alloy surface of step (3) through differential arc oxidation;
During crystal pulling method, the control pull rate is 2-10cm/min, lifts 2-10 time;
During spin-coating method, controls revolution rotating speed I is 1500r/min, and the time is 20s, and rotation rotating speed II is 2500r/min, and the time is 10s;
(6), the titanium behind the surface-coated hydroxyapatite coating layer of step (5) gained or titanium alloy be heated to 600 ℃ heat-treat in resistance furnace, finally obtain the titanium dioxide titanium-hydroxylapatite gradient coating of a kind of medical titanium or titanium alloy surface.
Technique effect of the present invention
The titanium dioxide titanium-hydroxylapatite gradient coating of a kind of medical titanium of the present invention or titanium alloy surface; Because the composite preparation process that adopts differential arc oxidization technique to combine with sol-gel method has formed a kind of with base metal oxide TiO on the surface of titanium or titanium alloy behind the differential arc oxidation
2Be main porous coating and form high-intensity metallurgical binding with matrix titanium or titanium alloy.And through the titanium of differential arc oxidation processing or the titanium oxide transition layer of titanium alloy surface formation vesicular structure; The unrelieved stress that this transition layer produces alleviating the difference between the physical and chemical performance between matrix and titanium or the titanium alloy on the composition, thus the problem that causes disbonding because of internal stress greatly can be improved between matrix and the hydroxyapatite coating layer; The vesicular structure on surface helps combining of hydroxyapatite colloidal sols coating and titanium or titanium alloy substrate, thus the bonding properties between raising activity hydroxy apatite coating and the matrix.
Description of drawings
The sem photograph of the titanium dioxide titanium-hydroxylapatite gradient coating of the titanium alloy surface of Fig. 1, embodiment 1 gained;
The end face micro-structure diagram of the titanium dioxide titanium-hydroxylapatite gradient coating of the titanium alloy surface of Fig. 2, embodiment 1 gained;
The XRD figure spectrum of the titanium dioxide titanium-hydroxylapatite gradient coating of the titanium alloy surface of Fig. 3, embodiment 1 gained.
Embodiment
Below through embodiment and combine accompanying drawing that the present invention is further set forth, but do not limit the present invention.
The instrument that the present invention is used
WHD-30 type multifunctional bipolar property mao power source and equipment (development of technical institute of Harbin Institute of Technology);
KQ-100DE Ultrasonic Cleaners (Kunshan ultrasonic instrument ltd);
JJ-1200 magnetic force electric mixer (Jintan City, Jiangsu Province Hong Hua instrument plant);
The desk-top sol evenning machine of KW-4A type (Chinese Academy of Sciences Microelectronics Institute).
The testing method that the present invention is used:
450 launch environment sem of QuantaFEG (Dutch PHILIPS Co.) are observed sample coatingsurface and end face pattern;
Bruker D8 ADVANCEX x ray diffractometer x (German Brooker AXS company) carries out material phase analysis.
Used titanium alloy is the Ti-6Al-4V alloy in the embodiments of the invention, and specification is 25mm * 2mm.
The all ingredients that the present invention is used:
Lime acetate, SODIUM PHOSPHATE, MONOBASIC, nitrocalcite, triethyl phosphate, absolute ethyl alcohol are analytical pure, Chemical Reagent Co., Ltd., Sinopharm Group.
Embodiment 1
A kind of preparation method of titanium dioxide titanium-hydroxylapatite gradient coating of titanium alloy surface specifically comprises the steps:
(1), titanium alloy is carried out surface preparation, use successively No. 200, No. 400, No. 600, No. 800 sand paper carries out grinding and polishing to its surface, cleans and dry processing then;
(2), the lime acetate aqueous solution and the biphosphate sodium water solution of 0.02mol/L of preparation 0.1mol/L, promptly by volume, the lime acetate aqueous solution: the biphosphate sodium water solution is that 1:1 is mixed and made into electrolytic solution;
(3), be that anode, metal stainless steel are negative electrode with the pretreated titanium alloy of step (1), titanium alloy is placed the electrolytic solution of step (2) gained, adopting constant voltage is the direct current pulse power source of 460V, carries out the differential arc oxidation of 5min and handles;
(4), be presoma with nitrocalcite and triethyl phosphate, adopt sol-gel method preparation hydroxyapatite colloidal sols solution;
Concrete preparation method takes by weighing the 18.1g triethyl phosphate, adds the 20ml absolute ethyl alcohol and dilutes, and uses magnetic stirrer 24hr, makes the triethyl phosphate complete hydrolysis, presses Ca in the final solution
2+: P
5-The requirement of=1.67:1 takes by weighing 39.4g nitrocalcite again and is dissolved in the 20ml absolute ethyl alcohol and fully stirs, again its triethyl phosphate with hydrolysis is mixed, with magnetic stirrer 1hr to dissolving fully.Behind the ageing 24hr, promptly get Win 40350 (HA) sol solution;
(5), adopt spin-coating method that the hydroxyapatite colloidal sols of step (4) gained is coated on the titanium alloy surface of step (3) through differential arc oxidation, control rotating speed I is 1500r/min in the coating procedure, rotation 20s, rotating speed II is 2500 r/min, rotates to be 10s;
(6), with the titanium alloy after applying of step (5) gained in resistance furnace, controlled temperature is heat-treated for 600 ℃, finally obtains the titanium dioxide titanium-hydroxylapatite gradient coating on a kind of medical titanium alloy surface.
The ESEM picture of the titanium dioxide titanium-hydroxylapatite gradient coating of the titanium alloy surface of gained is as shown in Figure 1, and as can be seen from Figure 1, the surface of the titanium dioxide titanium-hydroxylapatite gradient coating of gained forms vesicular structure, and the aperture is 1 μ m.
The end face microtexture of the titanium dioxide titanium-hydroxylapatite gradient coating of the titanium alloy surface of gained is as shown in Figure 2, the about 16 μ m of total coating thickness, and this coating internal layer is the composite bed of titanium oxide and Win 40350, skin is a hydroxyapatite layer.
The X-ray diffraction analysis collection of illustrative plates of the titanium dioxide titanium-hydroxylapatite gradient coating of the titanium alloy surface of gained is as shown in Figure 3, as can be seen from Figure 3, has formed titanium dioxide layer at titanium alloy surface when differential arc oxidation is handled.
Embodiment 2
A kind of preparation method of titanium dioxide titanium-hydroxylapatite gradient coating of titanium alloy surface specifically comprises the steps:
(1), titanium alloy is carried out surface preparation, use successively No. 200, No. 400, No. 600, No. 800 sand paper carries out grinding and polishing to its surface, cleans and dry processing then;
(2), the lime acetate aqueous solution and the biphosphate sodium water solution of 0.1mol/L of preparation 0.5mol/L, promptly by volume, the lime acetate aqueous solution: the biphosphate sodium water solution is that 1:1 is mixed and made into electrolytic solution;
(3), be that anode, metal stainless steel are negative electrode with the pretreated titanium alloy of step (1), titanium alloy is placed the electrolytic solution of step (2) gained, adopting constant voltage is the direct current pulse power source of 400V, carries out the differential arc oxidation of 20min and handles;
(4), be presoma with nitrocalcite and triethyl phosphate, adopt sol-gel method preparation hydroxyapatite colloidal sols solution; Concrete preparation method takes by weighing the 18.1g triethyl phosphate, adds absolute ethyl alcohol and dilutes, and uses magnetic stirrer 24hr, makes the triethyl phosphate complete hydrolysis; Press Ca in the final solution
2+: P
5-The requirement of=1.67:1 takes by weighing 39.4g nitrocalcite again and is dissolved in absolute ethyl alcohol and fully stirs, and its triethyl phosphate with hydrolysis is mixed again, and to dissolving fully, behind the ageing 24hr, promptly gets hydroxyapatite colloidal sols solution with magnetic stirrer 1hr;
(5), adopt spin-coating method that the hydroxyapatite colloidal sols of step (4) gained is coated on the titanium alloy surface of step (3) through differential arc oxidation; Control rotating speed I is 1500r/min in the coating procedure; Time is 20s, and rotating speed II is 2500 r/min, and the time is 10s;
(6), with the titanium alloy after applying of step (5) gained in resistance furnace, controlled temperature is heat-treated for 600 ℃, finally obtains the titanium dioxide titanium-hydroxylapatite gradient coating on a kind of medical titanium alloy surface.
The about 16 μ m of the total coating thickness of the titanium dioxide titanium-hydroxylapatite gradient coating of the titanium alloy surface of gained.
Embodiment 3
A kind of preparation method of titanium dioxide titanium-hydroxylapatite gradient coating of titanium alloy surface specifically comprises the steps:
(1), titanium alloy is carried out surface preparation, use successively No. 200, No. 400, No. 600, No. 800 sand paper carries out grinding and polishing to its surface, cleans and dry processing then;
(2), the lime acetate aqueous solution and the biphosphate sodium water solution of 0.1mol/L of preparation 0.5mol/L, promptly by volume, the lime acetate aqueous solution: the biphosphate sodium water solution is that 1:1 is mixed and made into electrolytic solution;
(3), be that anode, metal stainless steel are negative electrode with the pretreated titanium alloy of step (1), titanium alloy is placed the electrolytic solution of step (2) gained, adopting constant voltage is the direct current pulse power source of 500V, carries out the differential arc oxidation of 5min and handles;
(4), be presoma with nitrocalcite and triethyl phosphate, adopt sol-gel method preparation hydroxyapatite colloidal sols solution;
Concrete preparation method takes by weighing the 18.1g triethyl phosphate, adds absolute ethyl alcohol and dilutes, and makes the triethyl phosphate complete hydrolysis with magnetic stirrer 24hr, presses Ca in the final solution
2+: P
5-The requirement of=1.67:1 takes by weighing 39.4g nitrocalcite again and is dissolved in absolute ethyl alcohol and fully stirs, again its triethyl phosphate with hydrolysis is mixed, with magnetic stirrer 1hr to dissolving fully, behind the ageing 24hr, hydroxyapatite colloidal sols solution;
(5), adopt crystal pulling method that step (3) is applied through in the hydroxyapatite colloidal sols of titanium alloy surface with step (4) gained of differential arc oxidation, controlling pull rate in the coating procedure is 2 cm/min, lifts 2 times;
(6), with the titanium alloy after applying of step (5) gained in resistance furnace, controlled temperature is heat-treated for 600 ℃, finally obtains the titanium dioxide titanium-hydroxylapatite gradient coating on a kind of medical titanium alloy surface.
The about 16 μ m of the total coating thickness of the titanium dioxide titanium-hydroxylapatite gradient coating of the titanium alloy surface of gained.
Embodiment 4
A kind of preparation method of titanium dioxide titanium-hydroxylapatite gradient coating of titanium alloy surface specifically comprises the steps:
(1), titanium alloy is carried out surface preparation, use successively No. 200, No. 400, No. 600, No. 800 sand paper carries out grinding and polishing to its surface, cleans and dry processing then;
(2), the lime acetate aqueous solution and the biphosphate sodium water solution of 0.1mol/L of preparation 0.5mol/L, promptly by volume, the lime acetate aqueous solution: the biphosphate sodium water solution is that 1:1 is mixed and made into electrolytic solution;
(3), be that anode, metal stainless steel are negative electrode with the pretreated titanium alloy of step (1), titanium alloy is placed the electrolytic solution of step (2) gained, adopting constant voltage is the direct current pulse power source of 430V, carries out the differential arc oxidation of 10min and handles;
(4), be presoma with nitrocalcite and triethyl phosphate, adopt sol-gel method preparation hydroxyapatite colloidal sols solution;
Concrete preparation method takes by weighing the 18.1g triethyl phosphate, adds absolute ethyl alcohol and dilutes, and makes the triethyl phosphate complete hydrolysis with magnetic stirrer 24hr, presses Ca in the final solution
2+: P
5-The requirement of=1.67:1 takes by weighing 39.4g nitrocalcite again and is dissolved in absolute ethyl alcohol and fully stirs, again its triethyl phosphate with hydrolysis is mixed, with magnetic stirrer 1hr to dissolving fully, behind the ageing 24hr, hydroxyapatite colloidal sols solution;
(5), adopt to revolve to lift step (3) applied through in the hydroxyapatite colloidal sols solution of titanium alloy surface with step (4) gained of differential arc oxidation, in the coating procedure, the control pull rate is 10cm/min, lifts 10 times;
(6), with the titanium alloy after applying of step (5) gained in resistance furnace, controlled temperature is heat-treated for 600 ℃, finally obtains the titanium dioxide titanium-hydroxylapatite gradient coating on a kind of medical titanium alloy surface.
The about 16 μ m of the total coating thickness of the titanium dioxide titanium-hydroxylapatite gradient coating of the titanium alloy surface of gained.
The above content is merely the basic explanation of the present invention under conceiving, and according to any equivalent transformation that technical scheme of the present invention is done, all should belong to protection scope of the present invention.
Claims (4)
1. the titanium dioxide titanium-hydroxylapatite gradient coating of medical titanium or titanium alloy surface, the internal layer that it is characterized in that gradient cladding is the composite bed of titanium oxide and Win 40350, skin is a hydroxyapatite layer.
2. the titanium dioxide titanium-hydroxylapatite gradient coating of a kind of medical titanium as claimed in claim 1 or titanium alloy surface, the total thickness that it is characterized in that described titanium dioxide titanium-hydroxylapatite gradient coating are 16 μ m.
3. according to claim 1 or claim 2 the preparation method of titanium dioxide titanium-hydroxylapatite gradient coating of a kind of medical titanium or titanium alloy surface is characterized in that comprising the steps:
(1), titanium or titanium alloy surface pre-treatment
Titanium or titanium alloy surface are used No. 200 successively, and No. 400, No. 600, No. 800 sand paper carries out grinding and polishing, cleans and dry processing then;
(2), the preparation of electrolytic solution
With the biphosphate sodium water solution of the lime acetate aqueous solution of 0.1-0.5mol/L and 0.02-0.1mol/L promptly by volume, the lime acetate aqueous solution: the biphosphate sodium water solution is that 1:1 is mixed and made into electrolytic solution;
(3), be negative electrode with the metal stainless steel; Step (1) is the electrolytic solution that anode places step (2) gained through pretreated titanium or titanium alloy, and adopting direct current pulse power source is 400-500V, time to be that 5-20min carries out differential arc oxidation to titanium or titanium alloy in constant voltage;
(4), adopt sol-gel method to prepare hydroxyapatite colloidal sols solution;
Triethyl phosphate is joined absolute ethyl alcohol dilute, make the triethyl phosphate complete hydrolysis, get solution 1 with magnetic stirrer;
With nitrocalcite be dissolved in absolute ethyl alcohol be stirred well to dissolve solution 2;
With after solution 2 mixes, after magnetic stirrer to dissolving fully, ageing 24hr promptly gets hydroxyapatite colloidal sols solution with solution 1;
Solution 1 is pressed the Ca in solution 1 and the solution 2 with solution 2 blended amounts
2+, P
5-Mol ratio calculate i.e. Ca
2+: P
5-Be 1.67:1;
(5), adopt crystal pulling method or spin-coating method that the hydroxyapatite colloidal sols solution of step (4) gained is coated on titanium or titanium alloy surface behind step (3) differential arc oxidation;
(6), the titanium behind step (5) the surface-coated hydroxyapatite coating layer or titanium alloy be heated to 600 ℃ heat-treat in resistance furnace, finally obtain the titanium dioxide titanium-hydroxylapatite gradient coating of a kind of medical titanium or titanium alloy surface.
4. the preparation method of the titanium dioxide titanium-hydroxylapatite gradient coating of a kind of medical titanium as claimed in claim 3 or titanium alloy surface is characterized in that in the step (5):
When adopting crystal pulling method, the control pull rate is 2-10cm/min; Lifting number of times is 2~10 times;
Rotating speed I is 1500r/min when adopting spin-coating method, and the time is 20s, and rotating speed II is 2500 r/min, and the time is 10s.
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Cited By (10)
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CN102605411A (en) * | 2012-03-31 | 2012-07-25 | 大连理工大学 | Preparation process of pleated hole-slot shaped titanium dioxide thin film with super wetting ability |
CN105401203A (en) * | 2015-11-24 | 2016-03-16 | 上海理工大学 | Preparation method for medical material of similar bone bioactive gradient coating |
CN105506709A (en) * | 2015-12-11 | 2016-04-20 | 广州医科大学 | Preparation method of bioactive coatings on surfaces of titanium metals |
CN106109059A (en) * | 2016-08-05 | 2016-11-16 | 北京爱康宜诚医疗器材有限公司 | Borrowed structure |
CN106581744A (en) * | 2016-12-31 | 2017-04-26 | 芜湖孙杨信息咨询有限公司 | Production method of titanium implant surface composite coating used for stomatology department |
CN106822994A (en) * | 2016-12-30 | 2017-06-13 | 浙江工业大学 | A kind of stainless steel is implanted into composite material and its preparation and application |
CN108478857A (en) * | 2018-03-07 | 2018-09-04 | 广州创尔生物技术股份有限公司 | A kind of POROUS TITANIUM surface collagen protein coating and preparation method thereof |
CN109939909A (en) * | 2019-03-29 | 2019-06-28 | 西安理工大学 | A kind of preparation method of titanium or titanium alloy surface biology Piezoelectric anisotropy gradient coating |
CN112522734A (en) * | 2020-11-17 | 2021-03-19 | 广东省科学院新材料研究所 | Porous electrode for electrolytic gas production in liquid environment and preparation method thereof |
CN115068677A (en) * | 2022-06-22 | 2022-09-20 | 北京市春立正达医疗器械股份有限公司 | Multifunctional biological filler and kit |
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CN102605411A (en) * | 2012-03-31 | 2012-07-25 | 大连理工大学 | Preparation process of pleated hole-slot shaped titanium dioxide thin film with super wetting ability |
CN102605411B (en) * | 2012-03-31 | 2014-08-13 | 大连理工大学 | Preparation process of pleated hole-slot shaped titanium dioxide thin film with super wetting ability |
CN105401203A (en) * | 2015-11-24 | 2016-03-16 | 上海理工大学 | Preparation method for medical material of similar bone bioactive gradient coating |
CN105506709A (en) * | 2015-12-11 | 2016-04-20 | 广州医科大学 | Preparation method of bioactive coatings on surfaces of titanium metals |
CN106109059A (en) * | 2016-08-05 | 2016-11-16 | 北京爱康宜诚医疗器材有限公司 | Borrowed structure |
CN106822994A (en) * | 2016-12-30 | 2017-06-13 | 浙江工业大学 | A kind of stainless steel is implanted into composite material and its preparation and application |
CN106581744A (en) * | 2016-12-31 | 2017-04-26 | 芜湖孙杨信息咨询有限公司 | Production method of titanium implant surface composite coating used for stomatology department |
CN108478857A (en) * | 2018-03-07 | 2018-09-04 | 广州创尔生物技术股份有限公司 | A kind of POROUS TITANIUM surface collagen protein coating and preparation method thereof |
CN109939909A (en) * | 2019-03-29 | 2019-06-28 | 西安理工大学 | A kind of preparation method of titanium or titanium alloy surface biology Piezoelectric anisotropy gradient coating |
CN109939909B (en) * | 2019-03-29 | 2021-10-22 | 西安理工大学 | Preparation method of biological piezoelectric composite gradient coating on titanium or titanium alloy surface |
CN112522734A (en) * | 2020-11-17 | 2021-03-19 | 广东省科学院新材料研究所 | Porous electrode for electrolytic gas production in liquid environment and preparation method thereof |
CN115068677A (en) * | 2022-06-22 | 2022-09-20 | 北京市春立正达医疗器械股份有限公司 | Multifunctional biological filler and kit |
CN115068677B (en) * | 2022-06-22 | 2024-03-15 | 北京市春立正达医疗器械股份有限公司 | Multifunctional biological filler and kit |
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