CN107881544A - A kind of nano-calcium phosphate inlays the preparation method of orderly TiOx nano array film layer - Google Patents
A kind of nano-calcium phosphate inlays the preparation method of orderly TiOx nano array film layer Download PDFInfo
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- CN107881544A CN107881544A CN201711055750.9A CN201711055750A CN107881544A CN 107881544 A CN107881544 A CN 107881544A CN 201711055750 A CN201711055750 A CN 201711055750A CN 107881544 A CN107881544 A CN 107881544A
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/26—Anodisation of refractory metals or alloys based thereon
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/02—Inorganic materials
- A61L27/04—Metals or alloys
- A61L27/06—Titanium or titanium alloys
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/28—Materials for coating prostheses
- A61L27/30—Inorganic materials
- A61L27/32—Phosphorus-containing materials, e.g. apatite
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/50—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D15/00—Electrolytic or electrophoretic production of coatings containing embedded materials, e.g. particles, whiskers, wires
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D9/00—Electrolytic coating other than with metals
- C25D9/04—Electrolytic coating other than with metals with inorganic materials
- C25D9/08—Electrolytic coating other than with metals with inorganic materials by cathodic processes
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L2400/00—Materials characterised by their function or physical properties
- A61L2400/18—Modification of implant surfaces in order to improve biocompatibility, cell growth, fixation of biomolecules, e.g. plasma treatment
Abstract
The invention discloses the preparation method that a kind of nano-calcium phosphate inlays orderly TiOx nano array film layer, comprise the following steps：Blasting treatment, pickling impurity elimination, anodic oxidation and electrochemical deposition.When carrying out electrochemical deposition reaction, whole three-electrode system is placed in ultrasonic equipment, ultrasonic disperse can be played to act on and avoid reuniting in reaction, contribute to deposit to be embedded in titania nanotube inner surface with nano-scale dimension, form nano-calcium phosphate and inlay orderly TiOx nano array film layer；Anodic oxidation and progress electro-chemical deposition process step, effectively nano-calcium phosphate is inlayed to titanium substrate surface, solves the defects of titanium itself does not possess bioactivity and can not effectively facilitate wound healing and the growth of bone tissue, make titanium-based material that there is biomineralization characteristic, also improve the microscopic appearance characteristic of titanium substrate surface, the surface-active and stability of titanium-based material are improved, there is important bio-medical to be worth, can be applicable to biological and medicinal implant material field.
Description
Technical field
The present invention relates to a kind of method that bio-medical metal implant material surface is modified, more particularly to a kind of nanometer phosphoric acid
Calcium inlays the preparation method of orderly TiOx nano array film layer, category biological and medicinal implant material field.
Background technology
In order to improve the bioactivity of medical titanium, it is promoted to be combined with body bone tissue, to medical titanium metal watch
Face modification, preparing the titanium face coat with bioactivity turns into study hotspot.Hydroxyapatite (HA) is used as bone tissue
Main component, there is good biocompatibility, and bone cell growth can be induced as bone or the inducible factor of tooth.
But HA and matrix material nature difference are larger, and bond strength is low and easy to fall off.Conventional method is plasma spraying method, and electrophoresis sinks
Product technology etc., but the hydroxyapatite prepared using these methods is substantially in micron order or the film layer structure of submicron order, by titanium
The influence of base surface roughness and microstructure, it is low with basal body interface bond strength, easy to crack, peeling, leverage it
Using effect.
The content of the invention
It is an object of the invention to for above-mentioned the deficiencies in the prior art, there is provided a kind of nano-calcium phosphate inlays orderly oxidation
The preparation method of titanium nano-array film layer, by carrying out bioactivation to titanium substrate surface, i.e., by titanium-based material through anodic oxidation and
It electro-chemical deposition process, can lure that hydroxyapatite layer is deposited on the surface of titanium into, form nano-calcium phosphate and inlay orderly titanium oxide
Nano-array film layer, it is chemically bonded so as to promote titanium to be realized with body bone tissue.
The technical solution used in the present invention is：A kind of nano-calcium phosphate inlays the system of orderly TiOx nano array film layer
Preparation Method, it is characterised in that comprise the following steps：
(1) blasting treatment：Blasting treatment is carried out to titanium substrate surface using the material spray of 40-80 mesh, compressed air pressure is
2-8bar, jet length 30-200mm, a length of 10-60s during injection, by blasting treatment by titanium specimen surface cut or attachment
Semi-molten shape titanium pearl remove；
(2) pickling impurity elimination：Titanium-based material after step (1) processing is placed in pickle and carries out pickling, acid cleaning process will
A small amount of the abrasive material fragment and oxidation film layer that sandblasting procedures introduce remove；；
(3) anodic oxidation：Titanium-based material after step (2) processing is placed in two electrode electrolytic pools, wherein, electrolyte is
Mass percent is 0.25%~1% HF solution, by the titanium-based material after step (2) processing as anode, titanium plate, copper coin or
Platinum electrode is as negative electrode, and distance is 2-8cm between two electrodes, provides 20-80V voltage using D.C. regulated power supply at room temperature
Anodic oxidation is carried out, film of Nano tube array of titanium dioxide Rotating fields are formed in titanium substrate surface；
(4) electrochemical deposition：Electrolyte is the calcium salt and phosphatic mixed solution configured under 1-8 DEG C of environment, wherein, Ca
Mol ratio with P is 1.67, and the pH for adjusting electrolyte is 5.5-7.5；Using titanium-based material as negative electrode, platinum electrode as to electrode,
Saturated calomel electrode builds the three-electrode system of electrochemical workstation connection, and provide 1-5mA perseverance for it as reference electrode
Determine electric current or+1.5~-1.5V constant voltage, carry out electrochemical deposition reaction, inlayed in the inner surface of titania nanotube
Nano-calcium phosphate is inlayed, and is formd nano-calcium phosphate and is inlayed orderly TiOx nano array film layer.
As the further improvement of such scheme, the additional step of repetition is also inserted between step (1)~(4) respectively
(a), the additional step (a)：Titanium-based material be sequentially placed into 95% ethanol solution and deionized water in be cleaned by ultrasonic respectively, then
Dry, treat to use in next step.
As the further improvement of such scheme, the material spray is zirconium oxide or titanium oxide or corundum.
As the further improvement of such scheme, the pickle by concentrated hydrochloric acid, hydrofluoric acid and deionized water by volume
4:1:5 compositions.
As the further improvement of such scheme, a length of 15-20s during pickling processes in the step (2).
As the further improvement of such scheme, a length of 15-60min during anodic oxidation in the step (3).
As the further improvement of such scheme, when carrying out step (3), electrolyte is placed in magnetic agitation shape simultaneously
State, because anode oxidation process is exothermic process, electrolyte is placed in magnetic agitation state simultaneously, thermolysis is played, can keep away
Exempt from hot-spot in anode oxidation process.
As the further improvement of such scheme, in the electrochemical deposition reaction in carrying out step (4), by whole three electricity
Polar body system is placed in ultrasonic equipment, can play ultrasonic disperse effect, avoids reuniting in reaction, also can be by deposit nanometer
Calcium phosphate particles are embedded in the inner surface of titania nanotube with nano-scale dimension, form nano-calcium phosphate and inlay orderly titanium oxide
Nano-array film layer.
As the further improvement of such scheme, the titanium-based material is forging molding or 3D printing powder compacting.
The beneficial effects of the invention are as follows：The present invention is by carrying out anodic oxidation to titanium-based material and carrying out at electrochemical deposition
Reason, and when carrying out electrochemical deposition reaction, whole three-electrode system is placed in ultrasonic equipment, ultrasonic disperse can be played
Effect, avoid reuniting in reaction, contribute to deposit nano-calcium phosphate particle to be received with nano-scale dimension insertion titanium dioxide
The inner surface of mitron, inlay orderly TiOx nano array film layer so as to form nano-calcium phosphate；Anodic oxidation and progress electrification
Deposition process step is learned, has effectively reached and has inlayed nano-calcium phosphate to the purpose of titanium substrate surface, solved titanium itself and do not have
The defects of for bioactivity and wound healing and the growth of bone tissue can not be effectively facilitated, make titanium-based material that there is biomineralization
Characteristic, the microscopic appearance characteristic of titanium substrate surface is also improved, improve the surface-active and stability of titanium-based material, and the present invention
Employ the surface treatment method for being combined physical method with electrochemical method, it is simple for process, production cost is low, there is weight
The bio-medical value wanted, can be applicable to biological and medicinal implant material field, suitable for Industry Promotion and large-scale production.
Brief description of the drawings
Fig. 1 is the preparation technology flow chart of the present invention；
Fig. 2 is the SEM pictures of 3D printing powder compacting titanium-based material in embodiment 1；
Fig. 3 is the SEM pictures of the 3D printing powder compacting titanium-based material after anodic oxidation in embodiment 1；
Fig. 4 is the SEM of the 3D printing powder compacting titanium-based material after anodic oxidation and electro-chemical deposition process in embodiment 1
Picture；
Fig. 5 is the electricity of the 3D printing powder compacting titanium-based material after anodic oxidation and electro-chemical deposition process in embodiment 1
Sub- energy spectrum diagram.
Embodiment
In order to be better understood from the present invention, the present invention is specifically described with reference to embodiment, in order to affiliated skill
Personnel's the understanding of the present invention in art field.Be necessary herein it is emphasized that embodiment be only intended to be the present invention into
One step explanation, it is impossible to be interpreted as limiting the scope of the invention, art person skilled in the art, according in foregoing invention
Hold the modifications and adaptations for the non-intrinsically safe made to the present invention, protection scope of the present invention should be still fallen within.It is simultaneously following mentioned
Raw material it is unspecified, be commercially available prod；It is this area skill that the processing step or preparation method not referred in detail, which are,
The processing step or preparation method that art personnel are known.
With reference to Figure of description 1-5, and the present invention is further illustrated with the following embodiments, it is thus understood that specification is attached
Fig. 1-5 and following embodiments are merely to illustrate the present invention, are not intended to limit the present invention.
Embodiment 1
A kind of nano-calcium phosphate inlays the preparation method of orderly TiOx nano array film layer, comprises the following steps：
(1) blasting treatment：Sandblasting is carried out to the titanium base material surface of 3D printing powder compacting using the zirconium oxide of 60 mesh
Processing, compressed air pressure 6bar, jet length 40mm, injecting time 40s, and titanium-based material is sequentially placed into 95%
It is cleaned by ultrasonic respectively in ethanol solution and deionized water, then dries, treats to use in next step；
(2) pickling impurity elimination：Titanium-based material after step (1) processing is inserted into pickle (VConcentrated hydrochloric acid:VHydrofluoric acid:VDeionized water=4:1:
5) in, pickling 15s, and by titanium-based material be sequentially placed into 95% ethanol solution and deionized water in be cleaned by ultrasonic respectively, Ran Hougan
It is dry, treat to use in next step；
(3) anodic oxidation：Titanium-based material after step (2) processing is inserted in two electrode electrolytic pools, electrolyte is quality
Fraction is 0.25%HF solution, and anode is pretreated titanium-based material, and negative electrode is titanium plate, and distance is 4cm between two electrodes, room temperature
Lower D.C. regulated power supply provides 20V voltages and carries out anodic oxidation 45min, and electrolyte is placed in into magnetic agitation state, and by titanium
Base material be sequentially placed into 95% ethanol solution and deionized water in be cleaned by ultrasonic respectively, then dry, treat in next step use；
(4) electrochemical deposition：Electrolyte is the 0.1mmol calcium nitrate and 0.167mmol phosphorus configured under 4 DEG C of environment of ice bath
Sour hydrogen ammonia mixed solution, wherein, Ca and P's mole is 1.67, and the pH for adjusting electrolyte is 6.5, builds electrochemical workstation company
The three-electrode system connect：Titanium-based material after step (3) processing is used as to electrode, saturated calomel electrode as negative electrode, platinum electrode
As reference electrode；Electrochemical workstation provides 2mA constant currents, reaction duration 30min；, will be whole when electrochemical deposition reacts
Individual three-electrode system is placed in ultrasonic equipment, is taken out whole three-electrode system immediately after the completion of electrochemical deposition reaction and is used in combination
Deionized water is thoroughly cleaned.
Titanium-based material used in embodiment 1 is 3D printing powder compacting, and the microscopic appearance SEM figures on its surface are as shown in Fig. 2 whole
Surface is the coarse surface of micron order, mainly due to " half melting " titanium pearl in 3D printing process in pickling impurity elimination
Removed in journey.
Fig. 3 is in embodiment 1, in the regular titania nanotube of titanium substrate surface formation after anodized
The SEM of array microstructure film layer schemes, between the aperture about 75-120nm of titania nanotube.
Fig. 4 is the SEM pictures of titanium-based material after anodic oxidation and electrochemical deposition reaction, in titanium dioxide in embodiment 1
The inner surface deposition of nanotube has nano level calcium phosphate material, and a small amount of " nanoneedle " series of calcium phosphate material, forms
Nano-calcium phosphate inlays orderly TiOx nano array film layer.
Fig. 5 is in embodiment 1, is tested through anodic oxidation and the reacted titanium-based material electron spectrum of electrochemical deposition, by scheming
Understand there is the appearance of the element such as Ca, P, O peak value, further confirms through in anodic oxidation and the reacted titanium-based material of electrochemical deposition
Deposit series of calcium phosphate material.
Embodiment 2
A kind of nano-calcium phosphate inlays the preparation method of orderly TiOx nano array film layer, comprises the following steps：
(1) blasting treatment：Blasting treatment is carried out to titanium substrate surface using the corundum of 40 mesh, compressed air pressure is
4bar, jet length 30mm, injecting time 30s；
(2) pickling impurity elimination：Titanium-based material after step (1) processing is inserted into pickle (VConcentrated hydrochloric acid：VHydrofluoric acid：VDeionized water=4:1:
5) in, pickling 20s；
(3) anodic oxidation：Titanium-based material after step (2) processing is inserted in two electrode electrolytic pools, electrolyte is quality
Fraction is 0.35%HF solution, and anode is pretreated titanium-based material, and negative electrode is copper coin, and distance is 6cm between two electrodes, room temperature
Lower D.C. regulated power supply provides 30V voltages and carries out anodic oxidation 30min, and electrolyte is in magnetic agitation；
(4) electrochemical deposition：Electrolyte is the 0.05mmol calcium chloride that is configured under 4 DEG C of environment of ice bath, 0.0835mmol
Phosphoric acid hydrogen ammonia mixed solution, wherein, Ca and P's mole is 1.67, and the pH for adjusting electrolyte is 5.5.Build electrochemical workstation
The three-electrode system of connection：It will be used as through the titanium-based material after step (3) processing as negative electrode, platinum electrode to electrode, saturation calomel
Electrode is as reference electrode；Electrochemical workstation provides 1mA constant currents, reaction duration 25min.When electrochemical deposition reacts,
Whole three-electrode system is placed in ultrasonic equipment.Whole three-electrode system is taken out immediately after the completion of electrochemical deposition reaction
And thoroughly cleaned with deionized water.
Embodiment 3
A kind of nano-calcium phosphate inlays the preparation method of orderly TiOx nano array film layer, comprises the following steps：
(1) blasting treatment：Blasting treatment is carried out to titanium substrate surface using the titanium oxide of 40 mesh, compressed air pressure is
4bar, jet length 30mm, injecting time 30s；
(2) pickling impurity elimination：Titanium-based material after step (1) processing is inserted into pickle (VConcentrated hydrochloric acid：VHydrofluoric acid：VDeionized water=4:1:
5) in, pickling 20s；
(3) anodic oxidation：Titanium-based material after step (2) processing is inserted in three-electrode cell, electrolyte is quality
Fraction is 0.35%HF solution, and anode is pretreated titanium-based material, and negative electrode is platinum electrode, and distance is 6cm between two electrodes, room
The lower D.C. regulated power supply of temperature provides 30V voltages and carries out anodic oxidation 30min, and electrolyte is in magnetic agitation；
(4) electrochemical deposition：Electrolyte is the 0.05mmol calcium chloride and 0.0835mmol configured under 4 DEG C of environment of ice bath
Phosphoric acid hydrogen ammonia mixed solution, wherein, Ca and P's mole is 1.67, and the pH for adjusting electrolyte is 5.5.Build electrochemical workstation
The three-electrode system of connection：To be negative electrode through the titanium-based material after step (4) processing, platinum electrode is used as to electrode, saturation calomel electricity
Pole is as reference electrode；Electrochemical workstation provides 1mA constant currents, reaction duration 25min., will when electrochemical deposition reacts
Whole three-electrode system is placed in ultrasonic equipment.Whole three-electrode system is taken out simultaneously immediately after the completion of electrochemical deposition reaction
Thoroughly cleaned with deionized water.
Above-described embodiment is the preferred embodiments of the present invention, all with similar technique of the invention and the equivalence changes made,
The protection category of the present invention all should be belonged to.
Claims (9)
1. a kind of nano-calcium phosphate inlays the preparation method of orderly TiOx nano array film layer, it is characterised in that including following
Step：
(1) blasting treatment：Blasting treatment, compressed air pressure 2- are carried out to titanium substrate surface using the material spray of 40-80 mesh
8bar, jet length 30-200mm, a length of 10-60s during injection；
(2) pickling impurity elimination：Titanium-based material after step (1) processing is placed in pickle and carries out pickling；
(3) anodic oxidation：Titanium-based material after step (2) processing is placed in two electrode electrolytic pools, wherein, electrolyte is quality
Percentage is 0.25%~1% HF solution, will be through the titanium-based material after step (2) processing as anode, titanium plate, copper coin or platinum electricity
Pole is as negative electrode, and distance is 2-8cm between two electrodes, and the voltage for being provided 20-80V using D.C. regulated power supply at room temperature is carried out
Anodic oxidation；
(4) electrochemical deposition：Electrolyte is the calcium salt and phosphatic mixed solution configured under 1-8 DEG C of environment, wherein, Ca and P
Mol ratio be 1.67, the pH for adjusting electrolyte is 5.5-7.5；Using titanium-based material as negative electrode, platinum electrode as to electrode, saturation
Calomel electrode builds the three-electrode system of electrochemical workstation connection, and provide 1-5mA constant electricity for it as reference electrode
The constant voltage of stream or+1.5~-1.5V, electrochemical deposition reaction is carried out, forming nano-calcium phosphate in titanium substrate surface is inlaid with
Sequence TiOx nano array film layer.
2. nano-calcium phosphate according to claim 1 inlays the preparation method of orderly TiOx nano array film layer, it is special
Sign is：The additional step (a) of repetition, the additional step (a) are also inserted between step (1)~(4) respectively：Titanium-based material according to
The secondary ethanol solution for being placed in 95% and it is cleaned by ultrasonic respectively in deionized water, then dries, treats to use in next step.
3. nano-calcium phosphate according to claim 1 inlays the preparation method of orderly TiOx nano array film layer, it is special
Sign is：The material spray is zirconium oxide or titanium oxide or corundum.
4. nano-calcium phosphate according to claim 1 inlays the preparation method of orderly TiOx nano array film layer, it is special
Sign is：The pickle is by concentrated hydrochloric acid, hydrofluoric acid and deionized water by volume 4:1:5 compositions.
5. nano-calcium phosphate according to claim 1 inlays the preparation method of orderly TiOx nano array film layer, it is special
Sign is：A length of 5-30s during pickling processes in the step (2).
6. nano-calcium phosphate according to claim 1 inlays the preparation method of orderly TiOx nano array film layer, it is special
Sign is：A length of 15-60min during anodic oxidation in the step (3).
7. nano-calcium phosphate according to claim 1 inlays the preparation method of orderly TiOx nano array film layer, it is special
Sign is：When carrying out step (3), electrolyte is placed in magnetic agitation state simultaneously.
8. nano-calcium phosphate according to claim 1 inlays the preparation method of orderly TiOx nano array film layer, it is special
Sign is：In the electrochemical deposition reaction in carrying out step (4), whole three-electrode system is placed in ultrasonic equipment.
9. nano-calcium phosphate according to claim 1 inlays the preparation method of orderly TiOx nano array film layer, it is special
Sign is：The titanium-based material is forging molding or 3D printing powder compacting.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109589454A (en) * | 2018-11-13 | 2019-04-09 | 佛山市安齿生物科技有限公司 | It is a kind of for dental implant or the construction method of the antibacterials slow-released system of orthopedic instrument |
| CN110092449A (en) * | 2019-05-10 | 2019-08-06 | 生态环境部环境规划院 | A kind of SnO2The preparation method and its usage of electrode |
| CN110724991A (en) * | 2019-11-11 | 2020-01-24 | 苏州微创关节医疗科技有限公司 | Method for depositing hydroxyapatite on metal surface and metal implant |
| CN112048749A (en) * | 2020-09-09 | 2020-12-08 | 西北有色金属研究院 | Method for preparing bioactive coating on surface of 3D printed titanium or titanium alloy |
| CN112605039A (en) * | 2020-12-08 | 2021-04-06 | 富乐德科技发展（天津）有限公司 | Cleaning method for removing metal conductive film on surface of molybdenum material |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109589454A (en) * | 2018-11-13 | 2019-04-09 | 佛山市安齿生物科技有限公司 | It is a kind of for dental implant or the construction method of the antibacterials slow-released system of orthopedic instrument |
| CN110092449A (en) * | 2019-05-10 | 2019-08-06 | 生态环境部环境规划院 | A kind of SnO2The preparation method and its usage of electrode |
| CN110724991A (en) * | 2019-11-11 | 2020-01-24 | 苏州微创关节医疗科技有限公司 | Method for depositing hydroxyapatite on metal surface and metal implant |
| CN112048749A (en) * | 2020-09-09 | 2020-12-08 | 西北有色金属研究院 | Method for preparing bioactive coating on surface of 3D printed titanium or titanium alloy |
| CN112048749B (en) * | 2020-09-09 | 2021-10-26 | 西北有色金属研究院 | Method for preparing bioactive coating on surface of 3D printed titanium or titanium alloy |
| CN112605039A (en) * | 2020-12-08 | 2021-04-06 | 富乐德科技发展（天津）有限公司 | Cleaning method for removing metal conductive film on surface of molybdenum material |
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