CN109440153A - Microwave-electrochemical preparation method of CuHA/GO/ dopamine composite coating - Google Patents

Microwave-electrochemical preparation method of CuHA/GO/ dopamine composite coating Download PDF

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CN109440153A
CN109440153A CN201811422423.7A CN201811422423A CN109440153A CN 109440153 A CN109440153 A CN 109440153A CN 201811422423 A CN201811422423 A CN 201811422423A CN 109440153 A CN109440153 A CN 109440153A
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dopamine
titanium
microwave
cuha
composite coating
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黄勇
张雪姣
乔海霞
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Hebei North University
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    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/34—Pretreatment of metallic surfaces to be electroplated
    • C25D5/38—Pretreatment of metallic surfaces to be electroplated of refractory metals or nickel
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    • A61L27/06—Titanium or titanium alloys
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    • 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
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    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
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    • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/28—Materials for coating prostheses
    • A61L27/30—Inorganic materials
    • A61L27/306—Other specific inorganic materials not covered by A61L27/303 - A61L27/32
    • 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
    • A61L27/28—Materials for coating prostheses
    • A61L27/34—Macromolecular materials
    • 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
    • C25D17/00—Constructional parts, or assemblies thereof, of cells for electrolytic coating
    • C25D17/10—Electrodes, e.g. composition, counter electrode
    • C25D17/12—Shape or form
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
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    • 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
    • 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
    • A61L2420/00—Materials or methods for coatings medical devices
    • A61L2420/02—Methods for coating medical devices
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
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    • A61L2420/00—Materials or methods for coatings medical devices
    • A61L2420/04—Coatings containing a composite material such as inorganic/organic, i.e. material comprising different phases
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    • 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
    • A61L2420/00—Materials or methods for coatings medical devices
    • A61L2420/06—Coatings containing a mixture of two or more compounds

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Abstract

The present invention relates to microwave-electrochemical preparing methods of coating for metal surfaces method field, especially CuHA/GO/ dopamine composite coating.The preparation method is the following steps are included: titanium substrate surface is successively carried out acetone ultrasound, EtOH Sonicate, alkali heat-treatment by (1)；Poly-dopamine coating is deposited on the titanium surface of alkali heat-treatment；(2) uniform electrolyte is obtained through ultrasonic wave and magnetic agitation；(3) electrochemical deposition is carried out in the electrolytic solution, obtains the titanium-based piece with copper-loaded hydroxyapatite/graphene oxide/dopamine composite coating.The present invention constructs HA complex function coating by microwave-electrochemical appliance to improve its comprehensive performance, by electrolysis the pH value of electrolyte near cathode is locally increased, the hydroxy combining generated with the electrolysis of titanium surface, directly form amorphous HA precursor, to deposit calcium phosphate coating on cathode, deposition efficiency is greatlyd improve.

Description

Microwave-electrochemical preparation method of CuHA/GO/ dopamine composite coating
Technical field
The present invention relates to microwave-electricity of coating for metal surfaces method field, especially CuHA/GO/ dopamine composite coating Chemical preparation process.
Background technique
Although commercial pure titanium (CP-Ti) and its alloy are widely used in dentistry and plastic surgery, they are only showed Limited physiological stability and Integrated implant ability out, numerous studies are found after it implants often because infection leads to implantation pine The postoperative complications such as dynamic.Solve these problems the comprehensive performance for needing to be improved titanium surface.Hydroxyapatite (HA) and human teeth It is approximate with the inorganic constituents of bone, because its excellent osteoacusis and self-bone grafting characteristic are used for thin-film material, titanium implant surface HA Film has entered the clinical application stage.But since the good cell compatibility of HA coating similarly serves to favor the adherency and life of bacterium It is long, infection is easy around such implant and causes inflammation, so that HA coating loses the ability of Integrated implant and implant is caused to be sent out It is raw to loosen.In addition, the wearability and low fracture toughness of HA difference are still difficult to meet the mechanical property requirements of natural bone tissue, this Hinder its clinical application as film material on main load bearing equipment.To sum up, develop that a kind of wearability is good and biocidal property It is excellent to facilitate bone functional coating to become currently being badly in need of the problem to be solved.
Summary of the invention
The technical problem to be solved by the present invention is in order to solve technical problem described in background technique, the present invention is provided It is multiple to construct HA by microwave-electrochemical appliance for a kind of microwave-electrochemical preparation method of CuHA/GO/ dopamine composite coating Functional coating is closed to improve its comprehensive performance.Under the action of electric field force, Ca2+ and PO43-promptly gathers titanium surface, leads to Crossing electrolysis increases the pH value of electrolyte near cathode locally, increase the calcium microcosmic salt degree of supersaturation in the region, with this Electrolyte is according to itself dielectric properties electromagnetic wave absorption energy simultaneously, Ca2+ and PO43-be not necessarily to undergo the gradually nucleation of crystal, Growth and the stage of ripeness, the hydroxy combining generated with the electrolysis of titanium surface, directly formation amorphous HA precursor, to be deposited on cathode Calcium phosphate coating out greatlys improve deposition efficiency.
The technical solution adopted by the present invention to solve the technical problems is:
A kind of microwave-electrochemical preparation method of CuHA/GO/ dopamine composite coating, the method includes the steps of:
(1) titanium substrate surface is successively carried out to acetone ultrasound, EtOH Sonicate, alkali heat-treatment；On the titanium surface of alkali heat-treatment Poly-dopamine coating is deposited, prepared sample is marked with Ti/PDA；
(2) it after taking analytically pure four water-calcium nitrate, copper nitrate and ammonium di-hydrogen phosphate to be dissolved respectively with distilled water, is mixed It closes, graphene oxide is added into mixed liquor, adjust pH=4.4 with ammonium hydroxide, obtain uniform electricity through ultrasonic wave and magnetic agitation Solve liquid；
(3) in the electrolytic solution, using saturated calomel electrode as reference electrode, large area platinized platinum is to electrode, and Ti/PDA is work Make electrode, electrochemical deposition is carried out in the electrolytic cell of three-electrode system, obtains that there is copper-loaded hydroxyapatite/graphite oxide Alkene/dopamine composite coating titanium-based piece.
Specifically, in step (3), the deposition current of the electrochemical deposition is 0.95mA, sedimentation time 1500s, is sunk Accumulated temperature degree is 60 DEG C.
Specifically, in step (1), the method for the acetone ultrasound and EtOH Sonicate is, by titanium-based piece be cut into 1mm × 10mm × 10mm specification, respectively with the two sides of 280,800,2000 mesh sand paper polishing titanium-based piece to obtain uniform roughness, so Afterwards respectively with 99.5% acetone and 99.7% EtOH Sonicate 10 minutes.
Specifically, in step (1), the method for the alkali heat-treatment is, after acetone ultrasound and EtOH Sonicate ultrasound Titanium-based piece be soaked in 5M Na OH solution 24 hours, make its surface passivation, it is small to place into Muffle furnace 150 DEG C of heat treatments 1 When.
Specifically, it is characterised in that: in step (1), the deposition poly-dopamine coating deposition method is, by DOPA amine salt Hydrochlorate and 10m M Tris are protected from light under the conditions of PH=8.5 shakes up preparation dopamine solution, and the titanium-based piece after alkali heat-treatment is existed Be protected from light it is aerobic be soaked in the dopamine hydrochloride solution of 2mg/ml under room temperature, overnight deposition form poly-dopamine film.
Specifically, in step (3), working electrode is 1.5cm to the spacing between electrode, reference electrode.
Specifically, in step (3), the method for the electrochemical deposition is, by 2.2 × 10_2M four water-calcium nitrate, 2.5 × 10_2M ammonium dihydrogen phosphate and 2 × 10_2M copper nitrate are dissolved in the beaker of 1L, become mother liquor, are added 2 × 10_4M's into mother liquor GO, ultrasonication 1 hour；Then it places it on magnetic stirring apparatus and stirs evenly, after GO is completely dispersed, adjusted with ammonium hydroxide PH value of solution=4.4 obtain uniform electrolyte, which is put into 200ml beaker, carry out electro-deposition.
The beneficial effects of the present invention are: the present invention provides a kind of microwave-electrifications of CuHA/GO/ dopamine composite coating Length of schooling Preparation Method constructs HA complex function coating by microwave-electrochemical appliance to improve its comprehensive performance.In the work of electric field force Under, Ca2+ and PO43-promptly gather titanium surface, by electrolysis the pH value of electrolyte near cathode are locally increased Greatly, increase the calcium microcosmic salt degree of supersaturation in the region, electrolyte is according to itself dielectric properties electromagnetic wave absorption energy at the same time Amount, Ca2+ and PO43-are not necessarily to undergo gradually nucleation, growth and the stage of ripeness of crystal, the hydroxyl knot generated with the electrolysis of titanium surface It closes, directly formation amorphous HA precursor greatlys improve deposition efficiency to deposit calcium phosphate coating on cathode.
Specific embodiment
A kind of microwave-electrochemical preparation method of CuHA/GO/ dopamine composite coating, the method includes the steps of:
(1) titanium substrate surface is successively carried out to acetone ultrasound, EtOH Sonicate, alkali heat-treatment；On the titanium surface of alkali heat-treatment Poly-dopamine coating is deposited, prepared sample is marked with Ti/PDA；
(2) it after taking analytically pure four water-calcium nitrate, copper nitrate and ammonium di-hydrogen phosphate to be dissolved respectively with distilled water, is mixed It closes, graphene oxide is added into mixed liquor, adjust pH=4.4 with ammonium hydroxide, obtain uniform electricity through ultrasonic wave and magnetic agitation Solve liquid；
(3) in the electrolytic solution, using saturated calomel electrode as reference electrode, large area platinized platinum is to electrode, and Ti/PDA is work Make electrode, electrochemical deposition is carried out in the electrolytic cell of three-electrode system, obtains that there is copper-loaded hydroxyapatite/graphite oxide Alkene/dopamine composite coating titanium-based piece.
In step (3), the deposition current of the electrochemical deposition is 0.95mA, sedimentation time 1500s, and depositing temperature is 60℃.In step (1), the method for the acetone ultrasound and EtOH Sonicate is that titanium-based piece is cut into 1mm × 10mm × 10mm and is advised Then lattice are used with the two sides of 280,800,2000 mesh sand paper polishing titanium-based piece with obtaining uniform roughness respectively respectively 99.5% acetone and 99.7% EtOH Sonicate 10 minutes.In step (1), the method for the alkali heat-treatment is, by acetone ultrasound with Titanium-based piece after EtOH Sonicate ultrasound is soaked in 5M Na OH solution 24 hours, is made its surface passivation, is placed into Muffle It is heat-treated 1 hour for 150 DEG C in furnace.In step (1), the deposition poly-dopamine coating deposition method is, by dopamine hydrochloride And 10m M Tris is protected from light under the conditions of PH=8.5 and shakes up preparation dopamine solution, and the titanium-based piece after alkali heat-treatment is being protected from light Aerobic to be soaked in the dopamine hydrochloride solution of 2mg/ml under room temperature, deposition forms poly-dopamine film overnight.Step (3) in, working electrode is 1.5cm to the spacing between electrode, reference electrode.In step (3), the side of the electrochemical deposition Method is, by 2.2 × 10_2 M four water-calcium nitrate, 2.5 × 10_2M ammonium dihydrogen phosphate and 2 × 10_2M copper nitrate are dissolved in the beaker of 1L In, become mother liquor, the GO of 2 × 10_4M of addition into mother liquor, ultrasonication 1 hour；Then it places it on magnetic stirring apparatus It stirs evenly, after GO is completely dispersed, adjusts pH value of solution=4.4 with ammonium hydroxide, obtain uniform electrolyte, which is put into In 200ml beaker, electro-deposition is carried out.
Graphene oxide (GO) lamella edge is connected to a large amount of polar functional group such as epoxy group, carbonyl, hydroxyl etc., these officials The presence that can be rolled into a ball can not only enhance its affinity between bioactie agent, but also provide advantageous knot for the formation of HA Coincidence point.GO has good wearability and differentiation of stem cells potentiality, and intensity height, fracture toughness index are also above other All toughening materials, so that GO becomes the ideal filler for improving HA material mechanical performance.Dopamine is that a kind of biological neural is passed Matter, biocompatibility is preferable, can prepare close poly-dopamine composite coating in connection in any material surface, can be used as micro- Wave-electrochemical process template, which is adhered to titanium alloy substrate and carries out secondary response using its catechol active function groups, combines electricity Solve the calcium and phosphorus ions in liquid.The amine-modified bond strength that can significantly improve between HA coating and Ti matrix of DOPA.Cu is as people The essential trace element of body content second can promote vascular endothelial cell growth, be conducive to revascularization；Meanwhile Cu can promote Collagen is formed, and then safeguards the normal the Nomenclature Composition and Structure of Complexes of bone, is inhibited osteoporosis [21].In particular, Cu have in vitro it is outstanding Antibacterial and fungistatic effect, CuHA coating all have significant inhibitory effect to Escherichia coli and staphylococcus aureus.
The present invention combines the respective advantage of both microwave-assisted coating and conventional electrodeposition method, and use is micro- Wave-electrochemical appliance building HA complex function coating is to improve its comprehensive performance.Under the action of electric field force, Ca2+ and PO43- Titanium surface can be promptly gathered, by electrolysis the pH value of electrolyte near cathode is locally increased, makes the region Calcium microcosmic salt degree of supersaturation rise, electrolyte is according to itself dielectric properties electromagnetic wave absorption energy at the same time, Ca2+ and PO43-is not necessarily to undergo gradually nucleation, growth and the stage of ripeness of crystal, the hydroxy combining generated with the electrolysis of titanium surface, direct shape At amorphous HA precursor, to deposit calcium phosphate coating on cathode, this will greatly improve deposition efficiency.
Mentality of designing of the invention is: Cu element introduces HA lattice, and the anti-microbial property of titanium alloy can be improved, substantially reduce plant Enter a possibility that infecting around body；GO introduces HA, can improve the mechanical mechanics property of HA coating；Meanwhile DOPA is amine-modified can be with Significantly improve the bond strength between HA coating and Ti matrix.The present invention using microwave-electrochemical process prepare wearability it is good and The excellent CuHA/GO/ dopamine biological composite coating of biocidal property.This preparation technology of coating is simple, economy, ring mirror are friendly, have compared with Big business promotion value.
Embodiment:
(1) titanium-based piece is cut into 1mm × 10mm × 10mm specification, respectively with 280,800,2000 mesh sand paper polishing base The two sides of piece is to obtain uniform roughness, then respectively with 99.5% acetone and 99.7% EtOH Sonicate 10 minutes.Then, Titanium-based piece, which is soaked in 5M Na OH solution, makes its surface passivation in 24 hours；150 DEG C heat treatment 1 hour in Muffle furnace, finally It is put into spare in sealing container.
(2) the titanium surface of alkali heat-treatment deposits poly-dopamine coating: by dopamine hydrochloride and 10m M Tris in PH= It is protected from light under the conditions of 8.5 and preparation dopamine solution is shaken up with certain revolving speed.Titanium-based piece aerobic is impregnated under room temperature being protected from light Deposition forms poly-dopamine film overnight in the dopamine hydrochloride solution of 2mg/ml.Prepared sample is marked with Ti/PDA Note.
(3) Ti/PDA piece is working electrode, and large area platinized platinum is to electrode, and saturated calomel electrode is reference electrode, electrode Spacing is 1.5cm.
(4) 2.2 × 10_2M four water-calcium nitrate, 2.5 × 10_2M ammonium dihydrogen phosphate and 2 × 10_2M copper nitrate are dissolved in 1L Beaker in, become mother liquor.The GO of 2 × 10_4M of addition into mother liquor, ultrasonication 1 hour；Then magnetic force is placed it in It is stirred evenly on blender, after GO is completely dispersed, adjusts pH value of solution=4.4 with ammonium hydroxide, obtain uniform electrolyte.By the electricity Solution liquid is put into 200ml beaker, carries out electro-deposition, relevant parameter are as follows: deposition current: 0.95mA, sedimentation time 1400s；Electrolysis Liquid temperature: 60 DEG C.Obtain the medical metal implanted material with CuHA/GO/ dopamine composite coating.
Microwave-electrochemical process that medical titanium surface provided by the invention prepares CuHA/GO/ dopamine composite coating can be with Applied in the design of other functional coatings.This preparation technology of coating is simple, economy, ring mirror are friendly, and there is biggish business to push away Wide value.
Taking the above-mentioned ideal embodiment according to the present invention as inspiration, through the above description, relevant staff is complete Various changes and amendments can be carried out without departing from the scope of the technological thought of the present invention' entirely.The technology of this invention Property range is not limited to the contents of the specification, it is necessary to which the technical scope thereof is determined according to the scope of the claim.

Claims (7)

1. a kind of microwave-electrochemical preparation method of CuHA/GO/ dopamine composite coating, characterized in that this method includes following Step:
(1) titanium substrate surface is successively carried out to acetone ultrasound, EtOH Sonicate, alkali heat-treatment；It is deposited on the titanium surface of alkali heat-treatment Poly-dopamine coating, prepared sample are marked with Ti/PDA；
(2) it after taking analytically pure four water-calcium nitrate, copper nitrate and ammonium di-hydrogen phosphate to be dissolved respectively with distilled water, is mixed, to Graphene oxide is added in mixed liquor, adjusts pH=4.4 with ammonium hydroxide, obtains uniform electrolyte through ultrasonic wave and magnetic agitation；
(3) in the electrolytic solution, using saturated calomel electrode as reference electrode, large area platinized platinum is to electrode, and Ti/PDA is work electricity Pole carries out electrochemical deposition in the electrolytic cell of three-electrode system, obtains having copper-loaded hydroxyapatite/graphene oxide/more The titanium-based piece of bar amine composite coating.
2. microwave-electrochemical preparation method of CuHA/GO/ dopamine composite coating according to claim 1, feature exist In: in step (3), the deposition current of the electrochemical deposition is 0.95mA, and sedimentation time 1500s, depositing temperature is 60 DEG C.
3. microwave-electrochemical preparation method of CuHA/GO/ dopamine composite coating according to claim 1, feature exist In: in step (1), the method for the acetone ultrasound and EtOH Sonicate is that titanium-based piece is cut into 1mm × 10mm × 10mm and is advised Then lattice are used with the two sides of 280,800,2000 mesh sand paper polishing titanium-based piece with obtaining uniform roughness respectively respectively 99.5% acetone and 99.7% EtOH Sonicate 10 minutes.
4. microwave-electrochemical preparation method of CuHA/GO/ dopamine composite coating according to claim 1, feature exist In: in step (1), the method for the alkali heat-treatment is to impregnate the titanium-based piece after acetone ultrasound and EtOH Sonicate ultrasound 24 hours in 5MNaOH solution, make its surface passivation, places into Muffle furnace and be heat-treated 1 hour for 150 DEG C.
5. microwave-electrochemical preparation method of CuHA/GO/ dopamine composite coating according to claim 1, feature exist In: in step (1), the deposition poly-dopamine coating deposition method is, by dopamine hydrochloride and 10mMTris in PH=8.5 Under the conditions of be protected from light and shake up preparation dopamine solution, by the titanium-based piece after alkali heat-treatment be protected from light it is aerobic under room temperature, be soaked in In the dopamine hydrochloride solution of 2mg/ml, deposition forms poly-dopamine film overnight.
6. microwave-electrochemical preparation method of CuHA/GO/ dopamine composite coating according to claim 1, feature exist In: in step (3), working electrode is 1.5cm to the spacing between electrode, reference electrode.
7. microwave-electrochemical preparation method of CuHA/GO/ dopamine composite coating according to claim 1 or 2, special Sign is: in step (3), the method for the electrochemical deposition is, by 2.2 × 10-2M four water-calcium nitrate, 2.5 × 10-2M phosphoric acid Ammonium dihydrogen and 2 × 10-2M copper nitrate are dissolved in the beaker of 1L, become mother liquor, and the GO of 2 × 10-4M, ultrasonic wave are added into mother liquor Processing 1 hour；Then place it on magnetic stirring apparatus and stir evenly, after GO is completely dispersed, with ammonium hydroxide adjust pH value of solution= 4.4, uniform electrolyte is obtained, which is put into 200ml beaker, carries out electro-deposition.
CN201811422423.7A 2018-11-27 2018-11-27 Microwave-electrochemical preparation method of CuHA/GO/ dopamine composite coating Pending CN109440153A (en)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110183850A (en) * 2019-05-31 2019-08-30 西北工业大学 Copper oxide/poly-dopamine/redox graphene CuO/PDA/rGO preparation method
CN113908331A (en) * 2021-11-03 2022-01-11 浙江理工大学 Preparation method of calcium-loaded micro-nano structure intravascular stent capable of resisting hyperplasia and promoting endothelium
CN114481264A (en) * 2022-02-15 2022-05-13 上海市第一人民医院 Multifunctional titanium alloy coating and preparation method and application thereof
CN115591012A (en) * 2022-06-16 2023-01-13 厦门大学（Cn） Method for preparing bioactive film on surface of 3D printed titanium implant
CN117661063A (en) * 2024-01-31 2024-03-08 四川大学 Lead-free piezoelectric nano coating modified titanium alloy bracket and preparation method thereof

Citations (4)

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Publication number Priority date Publication date Assignee Title
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