CN102560590B - Anode in-situ electrochemical method for preparing hydroxyapatite coating - Google Patents

Anode in-situ electrochemical method for preparing hydroxyapatite coating Download PDF

Info

Publication number
CN102560590B
CN102560590B CN201210032099.4A CN201210032099A CN102560590B CN 102560590 B CN102560590 B CN 102560590B CN 201210032099 A CN201210032099 A CN 201210032099A CN 102560590 B CN102560590 B CN 102560590B
Authority
CN
China
Prior art keywords
coating
anode
dcpd
electrochemical deposition
sample
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201210032099.4A
Other languages
Chinese (zh)
Other versions
CN102560590A (en
Inventor
赵雪妮
李贺军
任威
雷静
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shaanxi University of Science and Technology
Original Assignee
Shaanxi University of Science and Technology
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Shaanxi University of Science and Technology filed Critical Shaanxi University of Science and Technology
Priority to CN201210032099.4A priority Critical patent/CN102560590B/en
Publication of CN102560590A publication Critical patent/CN102560590A/en
Application granted granted Critical
Publication of CN102560590B publication Critical patent/CN102560590B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Landscapes

  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
  • Electroplating Methods And Accessories (AREA)

Abstract

The invention relates to an anode in-situ electrochemical method for preparing a hydroxyapatite coating, which is characterized in that in an aqueous alkali electrolyte, a biomedical implantation material sample possessing a CaHPO4.2H2O(DCPD) coating is taken as anode, graphite electrode is taken as cathode, power supply is provided by using direct current source, under the effect of an electric field, OH<-> continuously moves to anode, an original DCPD coating is continuously dissolved, calcium and phosphorus ions are provided, then HA is in-situ deposed on the surface of the electrochemical implantation material. According to the invention, a nano and nano micrometer HA biological coatings with different surface morphology can be prepared according to different practical requirements; no hydrogen foam is generated near the anode during the preparation process, thereby the coating possesses high uniformity and compactness. Strong combination force is provided between the prepared coating and a matrix, the shearing bonding strength of the coating and the matrix can reach 8.0-8.9 MPa which is greater than the shearing bonding strength between plasma spraying HA and C/C of 7.4 MPa; and the thickness of the prepared coating is 35-45 mum.

Description

A kind of Anode in-situ electrochemical method preparing hydroxyapatite coating layer
Technical field
The invention belongs to the preparation field of bioactive ceramics hydroxyapatite (HA) coating, be specifically related to a kind of Anode in-situ electrochemical method preparing hydroxyapatite coating layer.
Background technology
Carbon/carbon (C/C) matrix material is a kind of new structural material that international field of new is given priority to, and has function and structure characteristic concurrently, excellent combination property.Meanwhile, C/C has excellent biocompatibility, stablizes in vivo, is not corroded; Good biomechanical compatibility, very close with the Young's modulus of bone; Its intensity is high, antifatigue, good toughness, density are little, and have certain pseudo-plasticity, micropore is conducive to tissue growth.Therefore C/C is as Bone Defect Repari and bone alternate material, has application prospect.But C/C matrix material is bio-inert material, surface hydrophobicity, does not there is conduction or induction osteanagenesis function, in order to make C/C matrix material have certain biological activity, surface modification must be carried out to it, preparing biological coating.
Calcium phosphate series pottery has good biocompatibility and biological activity, has successfully been applied to clinical.Especially HA receives much concern.In C/C surface-coated, there is bioactive calcium phosphate ceramic and can give the good mechanical property of hard tissue biomaterial and suitable biological property, extensively studied in recent years.Existing coating process comprises plasma spraying method, laser covers molten method, powder slurry coating sintering process, sol-gel method, electrophoretic method, electrochemical deposition method etc.
Wherein electrochemical deposition technique belongs to nonlinear process, and have more controllable process parameters to control the thickness of coating, chemical constitution, structure and porosity, production cost is low, and technique is simple, easy handling.Processing condition, pattern etc. that employing electrochemical deposition method prepares HA coating are as shown in the table.
Sum up and get up to have following deficiency: when (1) matrix is as cathode electrodeposition HA coating, because the electrolytic reaction of water generates bubble hydrogen near negative electrode, prepared coating is loosened, and bonding strength between matrix is not high; (2) matrix is as anode, and in containing the alkaline electrolyte of calcium and phosphorus ions during galvanic deposit HA coating, prepared HA pattern is single, poor controllability; (3) when matrix is as male or female galvanic deposit, coat-thickness less (< 19 μm).These deficiencies constrain electrochemical deposition method and prepare further developing of HA coating.
Summary of the invention
The object of the present invention is to provide a kind of Anode in-situ electrochemical method preparing hydroxyapatite coating layer, the defect that the bonding strength of coating and the matrix produced because of bubble hydrogen in electrochemical cathode method deposition process is not high can be solved, obtain pattern variation, controlled HA coating simultaneously.
For achieving the above object, the technical solution used in the present invention is:
Step 1: pre-treat biological medical implant sample:
First get after biomedical implant is processed into thin slice and polish flat, use tap water, acetone, ethanol, distilled water ultrasonic cleaning 15-30min successively, dry in air;
Step 2: adopt cathodic electrochemical deposition method or ultrasonic wave added cathodic electrochemical deposition legal system for the precursor-CaHPO of HA 42H 2o (DCPD) coating:
Pretreated biomedical implant sample and flake graphite electrode are placed in NH 4h 2pO 4with Ca (NO 3) 2in the electrolytic solution that mixed solution forms, wherein NH 4h 2pO 4concentration is (2.00 ~ 2.50) × 10 -2mol/L, and the calcium in electrolytic solution is 1.67 with phosphorus concentration ratio, the pH regulating electrolytic solution is 4.5 ~ 4.8, with pretreated biomedical implant sample for negative electrode, with flake graphite electrode for anode, cathodic electrochemical deposition method or ultrasonic wave added cathodic electrochemical deposition method biomedical implant specimen surface is after the pre-treatment adopted to prepare DCPD coating, the processing parameter of cathodic electrochemical deposition method is: temperature is 50 ~ 60 DEG C, depositing time is 60 ~ 120min, and current density is 1.6 ~ 3.0mA/cm 2; The processing parameter of ultrasonic wave added cathodic electrochemical deposition method is: temperature is 50 ~ 60 DEG C, and depositing time is 60 ~ 120min, and current density is 1.6 ~ 3.0mA/cm 2, ultrasonic frequency is 25 ~ 60KHz, and hyperacoustic power is 100W;
Step 3, drying has the biomedical implant sample of DCPD coating; 60 ~ 120 DEG C of dryings 24 ~ 48 hours;
Step 4, the preparation of HA coating; With the dried biomedical implant sample with DCPD coating for anode, with flake graphite electrode for negative electrode, be placed in alkaline solution, Anode in-situ electrochemical method is adopted to prepare HA coating, during preparation, processing parameter is: the temperature of alkaline aqueous solution is 80 ~ 100 DEG C, and current density is 1.6 ~ 10.0mA/cm 2, preparation time is 120 ~ 240min.
Described biomedical implant is C/C matrix material, titanium and titanium alloys, stainless steel or Magnuminium.
Described alkaline solution is NaOH or NH of 0.5 ~ 2.0mol/L 3h 2the aqueous solution of O.
The present invention adopts Anode in-situ electrochemical method to prepare HA, and in alkaline solution electrolytic solution, to have the biomedical implant sample of DCPD coating for anode, Graphite Electrodes is negative electrode, adopts DC power supply.Under electric field action, OH -continuous anode moves, and original DCPD coating is constantly dissolved simultaneously, provides calcium and phosphorus ions, then at biomedical implant surface in situ deposition HA.Method of the present invention can prepare the nanometer with different surface morphology, a micron HA biological coating of receiving according to different actual needs; Because near preparation process Anodic, no hydrogen bubble produces, so coating has higher homogeneity, compactness.Obtained coating and matrix have stronger bonding force, coating and matrix shearing bond strength reach 8.0 ~ 8.9MPa, be greater than shearing bond strength 7.4MPa (the Sui Jinling between plasma spraying HA and C/C, Li Musen, Peng Yu.The Effect of Plasma Spraying Power on the Structure and Mechanical Properties of Deposited on Carbon/Carbon Composites [J] .Surface and Coatings Technology, 2005,190:287 ~ 292); The coat-thickness prepared is 35 ~ 45 μm.
Accompanying drawing explanation
Fig. 1 is the XRD figure spectrum of the DCPD coating prepared of the present invention and HA coating;
Fig. 2 is the SEM photo of DCPD coating prepared by the present invention;
Fig. 3 is the SEM photo of HA coating prepared by the present invention.
Embodiment
Below in conjunction with drawings and Examples, the present invention is described in further detail.
Embodiment 1:
Step 1: pre-treatment C/C composite sample:
First get after C/C matrix material is processed into thin slice and polish flat, use tap water, acetone, ethanol, distilled water ultrasonic cleaning 15min successively, dry in air;
Step 2: adopt ultrasonic wave added cathodic electrochemical deposition legal system to obtain the precursor-DCPD coating of HA:
Pretreated C/C composite sample and flake graphite electrode are placed in NH 4h 2pO 4with Ca (NO 3) 2in the electrolytic solution that mixed solution forms, wherein NH 4h 2pO 4concentration is 2.00 × 10 -2mol/L, and the calcium in electrolytic solution is 1.67 with phosphorus concentration ratio, the pH regulating electrolytic solution is 4.8, with pretreated C/C composite sample for negative electrode, with flake graphite electrode for anode, adopt ultrasonic wave added cathodic electrochemical deposition method C/C composite sample surface preparation DCPD coating after the pre-treatment, the processing parameter of ultrasonic wave added cathodic electrochemical deposition method is: temperature is 50 DEG C, depositing time is 120min, and current density is 1.6mA/cm 2, ultrasonic frequency is 40KHz, and hyperacoustic power is 100W; Obtain DCPD coating, the XRD figure of DCPD coating and SEM figure are as shown in Fig. 1 (a), Fig. 2;
Step 3, drying has the C/C composite sample of DCPD coating; 60 DEG C of dryings 48 hours;
Step 4, the preparation of HA coating; With the dried C/C composite sample with DCPD coating for anode, with flake graphite electrode for negative electrode, be placed in the aqueous solution of the NaOH of 0.5mol/L, Anode in-situ electrochemical method is adopted to prepare HA coating, during preparation, processing parameter is: the temperature of alkaline solution is 95 DEG C, and current density is 1.6mA/cm 2, preparation time is 120min.
The XRD figure of gained HA coating and SEM photo respectively as Fig. 1 (b), 3 (a, b), be nano whiskers and micron HA crystal.8.9MPa can be reached with the bonding strength of C/C matrix material.
Embodiment 2:
Step 1: pre-treatment C/C composite sample:
First get after C/C matrix material is processed into thin slice and polish flat, use tap water, acetone, ethanol, distilled water ultrasonic cleaning 15min successively, dry in air;
Step 2: adopt ultrasonic wave added cathodic electrochemical deposition legal system to obtain the precursor-DCPD coating of HA:
Pretreated C/C composite sample and flake graphite electrode are placed in NH 4h 2pO 4with Ca (NO 3) 2in the electrolytic solution that mixed solution forms, wherein NH 4h 2pO 4concentration is 2.25 × 10 -2mol/L, and the calcium in electrolytic solution is 1.67 with phosphorus concentration ratio, the pH regulating electrolytic solution is 4.6, with pretreated C/C composite sample for negative electrode, with flake graphite electrode for anode, adopt ultrasonic wave added cathodic electrochemical deposition method C/C composite sample surface preparation DCPD coating after the pre-treatment, the processing parameter of ultrasonic wave added cathodic electrochemical deposition method is: temperature is 60 DEG C, depositing time is 90min, and current density is 2.0mA/cm 2, ultrasonic frequency is 25KHz, and hyperacoustic power is 100W; Obtain DCPD coating,
Step 3, dry; 90 DEG C of dryings 36 hours;
Step 4, the preparation of HA coating; With the dried C/C composite sample with DCPD coating for anode, with flake graphite electrode for negative electrode, be placed on the NH of 2.0mol/L 3h 2in the aqueous solution of O, adopt anode electrochemical in-situ method to prepare HA coating, during preparation, processing parameter is: the temperature of alkaline solution is 80 DEG C, and current density is 10.0mA/cm 2, preparation time is 240min.
The XRD figure of gained HA coating and SEM photo, respectively as shown in Fig. 1 (c), 3 (c), are nano-sheet HA crystal.8.5MPa can be reached with the bonding strength of C/C matrix material.
Embodiment 3:
Step 1: pre-treatment C/C composite sample:
First get after C/C matrix material is processed into thin slice and polish flat, use tap water, acetone, ethanol, distilled water ultrasonic cleaning 25min successively, dry in air;
Step 2: adopt ultrasonic wave added cathodic electrochemical deposition legal system to obtain the precursor-DCPD coating of HA:
Pretreated C/C composite sample and flake graphite electrode are placed in NH 4h 2pO 4with Ca (NO 3) 2in the electrolytic solution that mixed solution forms, wherein NH 4h 2pO 4concentration is 2.50 × 10 -2mol/L, and the calcium/phosphorus concentration ratio in electrolytic solution is 1.67, the pH regulating electrolytic solution is 4.6, with pretreated C/C composite sample for negative electrode, with flake graphite electrode for anode, adopt ultrasonic wave added cathodic electrochemical deposition method C/C composite sample surface preparation DCPD coating after the pre-treatment, the processing parameter of ultrasonic wave added cathodic electrochemical deposition method is: temperature is 60 DEG C, depositing time is 60min, and current density is 3.0mA/cm 2, ultrasonic frequency is 60KHz, and hyperacoustic power is 100W;
Step 3, drying has the C/C composite sample of DCPD coating; 120 DEG C of dryings 24 hours;
Step 4, the preparation of HA coating; With the dried C/C composite sample with DCPD coating for anode, with flake graphite electrode for negative electrode, be placed on the NH of 1.0mol/L 3h 2in the aqueous solution of O, adopt anode electrochemical in-situ method to prepare HA coating, during preparation, processing parameter is: the temperature of alkaline aqueous solution is 90 DEG C, and current density is 5.0mA/cm 2, preparation time is 180min.
The XRD figure of gained HA coating and SEM photo are respectively as shown in Fig. 1 (d), 3 (d), and be nano whiskers HA crystal, its length-to-diameter ratio is greater than the nano whiskers HA crystal of gained in example one.8.0MPa can be reached with the bonding strength of C/C matrix material.
Embodiment 4:
Step 1: pre-processing titanium sample:
First get after titanium is processed into thin slice and polish flat, use tap water, acetone, ethanol, distilled water ultrasonic cleaning 20min successively, dry in air;
Step 2: adopt cathodic electrochemical deposition legal system to obtain the precursor-DCPD coating of HA:
Pretreated titanium sample and flake graphite electrode are placed in NH 4h 2pO 4with Ca (NO 3) 2in the electrolytic solution that mixed solution forms, wherein NH 4h 2pO 4concentration is 2.10 × 10 -2mol/L, and the calcium/phosphorus concentration ratio in electrolytic solution is 1.67, the pH regulating electrolytic solution is 4.5, with pretreated titanium sample for negative electrode, with flake graphite electrode for anode, adopt cathodic electrochemical deposition method titanium specimen surface after the pre-treatment to prepare DCPD coating, processing parameter during deposition is: temperature is 52 DEG C, depositing time is 80min, and current density is 1.8mA/cm 2; ;
Step 3, drying has the titanium sample of DCPD coating; 100 DEG C of dryings 40 hours;
Step 4, the preparation of HA coating; With the dried titanium sample with DCPD coating for anode, with flake graphite electrode for negative electrode, be placed on 0.8mol/L NH 3h 2in the aqueous solution of O, adopt anode electrochemical in-situ method to prepare HA coating, during preparation, processing parameter is: the temperature of alkaline solution is 100 DEG C, and current density is 3.0mA/cm 2, preparation time is 160min.
Embodiment 5:
Step 1: pre-processing titanium alloy sample:
First get after titanium alloy is processed into thin slice and polish flat, use tap water, acetone, ethanol, distilled water ultrasonic cleaning 28min successively, dry in air;
Step 2: adopt cathodic electrochemical deposition legal system to obtain the precursor-DCPD coating of HA:
Pretreated titanium alloy sample and flake graphite electrode are placed in NH 4h 2pO 4with Ca (NO 3) 2in the electrolytic solution that mixed solution forms, wherein NH 4h 2pO 4concentration is 2.30 × 10 -2mol/L, and the calcium/phosphorus concentration ratio in electrolytic solution is 1.67, the pH regulating electrolytic solution is 4.7, with pretreated titanium alloy sample for negative electrode, with flake graphite electrode for anode, adopt ultrasonic wave added cathodic electrochemical deposition method titanium alloy specimen surface after the pre-treatment to prepare DCPD coating, processing parameter during deposition is: temperature is 55 DEG C, depositing time is 100min, and current density is 2.5mA/cm 2;
Step 3, drying has the titanium alloy sample of DCPD coating; 80 DEG C of dryings 40 hours;
Step 4, the preparation of HA coating; With the dried titanium alloy sample with DCPD coating for anode, with flake graphite electrode for negative electrode, be placed in the aqueous solution of 1.0mol/L NaOH, anode electrochemical in-situ method is adopted to prepare HA coating, during preparation, processing parameter is: the temperature of alkaline solution is 85 DEG C, and current density is 6.0mA/cm 2, preparation time is 130min.
Embodiment 6:
Step 1: pre-treatment stainless steel sample:
First get after stainless steel is processed into thin slice and polish flat, use tap water, acetone, ethanol, distilled water ultrasonic cleaning 30min successively, dry in air;
Step 2: adopt ultrasonic wave added cathodic electrochemical deposition legal system to obtain the precursor-DCPD coating of HA:
Pretreated stainless steel sample and flake graphite electrode are placed in NH 4h 2pO 4with Ca (NO 3) 2in the electrolytic solution that mixed solution forms, wherein NH 4h 2pO 4concentration is 2.40 × 10 -2mol/L, and the calcium/phosphorus concentration ratio in electrolytic solution is 1.67, the pH regulating electrolytic solution is 4.8, with pretreated stainless steel sample for negative electrode, with flake graphite electrode for anode, adopt ultrasonic wave added cathodic electrochemical deposition method stainless steel specimen surface after the pre-treatment to prepare DCPD coating, processing parameter during deposition is: temperature is 58 DEG C, depositing time is 70min, and current density is 2.3mA/cm 2, ultrasonic frequency is 45KHz, and hyperacoustic power is 100W;
Step 3, drying has the stainless steel sample of DCPD coating; 110 DEG C of dryings 30 hours;
Step 4, the preparation of HA coating; With the dried stainless steel sample with DCPD coating for anode, with flake graphite electrode for negative electrode, be placed on 1.5mol/L NH 3h 2in the aqueous solution of O, adopt anode electrochemical in-situ method to prepare HA coating, during preparation, processing parameter is: the temperature of alkaline solution is 93 DEG C, and current density is 8.0mA/cm 2, preparation time is 200min.
Embodiment 7:
Step 1: pre-treatment Magnuminium sample:
First get after Magnuminium is processed into thin slice and polish flat, use tap water, acetone, ethanol, distilled water ultrasonic cleaning 23min successively, dry in air;
Step 2: adopt ultrasonic wave added cathodic electrochemical deposition legal system to obtain the precursor-DCPD coating of HA:
Pretreated Magnuminium sample and flake graphite electrode are placed in NH 4h 2pO 4with Ca (NO 3) 2in the electrolytic solution that mixed solution forms, wherein NH 4h 2pO 4concentration is 2.35 × 10 -2mol/L, and the calcium/phosphorus concentration ratio in electrolytic solution is 1.67, the pH regulating electrolytic solution is 4.5, with pretreated Magnuminium sample for negative electrode, with flake graphite electrode for anode, adopt ultrasonic wave added cathodic electrochemical deposition method Magnuminium specimen surface after the pre-treatment to prepare DCPD coating, processing parameter during deposition is: temperature is 53 DEG C, depositing time is 110min, and current density is 2.8mA/cm 2; The ultrasonic frequency of ultrasonic wave added cathodic electrochemical deposition method is 38KHz, and hyperacoustic power is 100W;
Step 3, drying has the Magnuminium sample of DCPD coating; 70 DEG C of dryings 45 hours;
Step 4, the preparation of HA coating; With the dried Magnuminium sample with DCPD coating for anode, with flake graphite electrode for negative electrode, be placed in the aqueous solution of 1.8mol/L NaOH, anode electrochemical in-situ method is adopted to prepare HA coating, during preparation, processing parameter is: the temperature of alkaline solution is 96 DEG C, and current density is 10.0mA/cm 2, preparation time is 220min.

Claims (2)

1. prepare an Anode in-situ electrochemical method for hydroxyapatite coating layer, it is characterized in that comprising the following steps:
Step 1: pre-treat biological medical implant sample:
First get after biomedical implant is processed into thin slice and polish flat, use tap water, acetone, ethanol, distilled water ultrasonic cleaning 15-30min successively, dry in air;
Step 2: adopt cathodic electrochemical deposition method or ultrasonic wave added cathodic electrochemical deposition legal system for the precursor-CaHPO of HA 42H 2o (DCPD) coating:
Pretreated biomedical implant sample and flake graphite electrode are placed in NH 4h 2pO 4with Ca (NO 3) 2in the electrolytic solution that mixed solution forms, wherein NH 4h 2pO 4concentration is (2.00 ~ 2.50) × 10 -2mol/L, and the calcium in electrolytic solution is 1.67 with phosphorus concentration ratio, the pH regulating electrolytic solution is 4.5 ~ 4.8, with pretreated biomedical implant sample for negative electrode, with flake graphite electrode for anode, cathodic electrochemical deposition method or ultrasonic wave added cathodic electrochemical deposition method biomedical implant specimen surface is after the pre-treatment adopted to prepare DCPD coating, the processing parameter of cathodic electrochemical deposition method is: temperature is 50 ~ 60 DEG C, depositing time is 60 ~ 120min, and current density is 1.6 ~ 3.0mA/cm 2; The processing parameter of ultrasonic wave added cathodic electrochemical deposition method is: temperature is 50 ~ 60 DEG C, and depositing time is 60 ~ 120min, and current density is 1.6 ~ 3.0mA/cm 2, ultrasonic frequency is 25 ~ 60KHz, and hyperacoustic power is 100W;
Step 3, drying has the biomedical implant sample of DCPD coating; 60 ~ 120 DEG C of dryings 24 ~ 48 hours;
Step 4, the preparation of HA coating; With the dried biomedical implant sample with DCPD coating for anode, with flake graphite electrode for negative electrode, be placed in alkaline solution, Anode in-situ electrochemical method is adopted to prepare HA coating, during preparation, processing parameter is: the temperature of alkaline aqueous solution is 80 ~ 100 DEG C, and current density is 1.6 ~ 10.0mA/cm 2, preparation time is 120 ~ 240min;
Described alkaline solution is NaOH or NH of 0.5 ~ 2.0mol/L 3h 2the aqueous solution of O;
HA coat-thickness is 35 ~ 45 μm;
HA coating and biomedical implant shearing bond strength reach 8.0 ~ 8.9MPa.
2. prepare the Anode in-situ electrochemical method of hydroxyapatite coating layer as claimed in claim 1, it is characterized in that, described biomedical implant is C/C matrix material, titanium and titanium alloys, stainless steel or Magnuminium.
CN201210032099.4A 2012-02-14 2012-02-14 Anode in-situ electrochemical method for preparing hydroxyapatite coating Active CN102560590B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201210032099.4A CN102560590B (en) 2012-02-14 2012-02-14 Anode in-situ electrochemical method for preparing hydroxyapatite coating

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201210032099.4A CN102560590B (en) 2012-02-14 2012-02-14 Anode in-situ electrochemical method for preparing hydroxyapatite coating

Publications (2)

Publication Number Publication Date
CN102560590A CN102560590A (en) 2012-07-11
CN102560590B true CN102560590B (en) 2015-01-28

Family

ID=46407139

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201210032099.4A Active CN102560590B (en) 2012-02-14 2012-02-14 Anode in-situ electrochemical method for preparing hydroxyapatite coating

Country Status (1)

Country Link
CN (1) CN102560590B (en)

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102787339A (en) * 2012-07-30 2012-11-21 同济大学 Method for preparing magnesium alloy - calcium phosphorus coating composite material by electrochemical deposition
CN102786321B (en) * 2012-08-20 2013-12-25 西北工业大学 Preparation method of nanowire reinforced hydroxyapatite coating
CN104947097B (en) * 2015-06-30 2017-08-25 山东大学 A kind of preparation method of pure titanium surface phosphoric acid hydrogen calcium micro nanometer fiber conversion film
CN108939163A (en) * 2018-07-19 2018-12-07 浙江大学 It is a kind of to mix magnesium hydroxyapatite silk fibroin composite membrane coating preparation method with rush osteogenesis function
CN109758605B (en) * 2019-02-25 2022-12-06 青岛科技大学 Magnesium alloy surface fine needle-shaped hydroxyapatite micro-nano structure coating and preparation method thereof
CN112811936B (en) * 2021-01-12 2022-11-11 西北工业大学 CaP biological coating with fine crystal particles on surface of C/C composite material and preparation method thereof
CN113088896B (en) * 2021-04-01 2022-09-02 西北工业大学 Hydroxyapatite nanobelt on surface of C/C composite material, hydroxyapatite coating and one-step intergrowth preparation method

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5458863A (en) * 1994-11-25 1995-10-17 Klassen; Robert D. Cold process for hydroxyapatite coatings
CN101156963A (en) * 2007-11-08 2008-04-09 浙江大学 Method for preparing similar bone bioactivity coatings medical material by galvano-chemistry method
CN101485901A (en) * 2008-11-25 2009-07-22 西南交通大学 Method for preparing hydroxyapatite/nano silver antimicrobial composite coating by pulse electrochemical deposition
CN101643929A (en) * 2009-08-31 2010-02-10 郑州大学 Pulse electrodeposition preparation method of hydroxyapatite coating on surface of pure magnesium or magnesium alloy

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5458863A (en) * 1994-11-25 1995-10-17 Klassen; Robert D. Cold process for hydroxyapatite coatings
CN101156963A (en) * 2007-11-08 2008-04-09 浙江大学 Method for preparing similar bone bioactivity coatings medical material by galvano-chemistry method
CN101485901A (en) * 2008-11-25 2009-07-22 西南交通大学 Method for preparing hydroxyapatite/nano silver antimicrobial composite coating by pulse electrochemical deposition
CN101643929A (en) * 2009-08-31 2010-02-10 郑州大学 Pulse electrodeposition preparation method of hydroxyapatite coating on surface of pure magnesium or magnesium alloy

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
Characterization and stability of hydroxyapatite coatings prepared by an electrodeposition and alkaline-treatment process;Yong Han等;《Journal of Biomedical Materials Research》;20001106;第54卷;说明书第96页右栏最后1段 *

Also Published As

Publication number Publication date
CN102560590A (en) 2012-07-11

Similar Documents

Publication Publication Date Title
CN102560590B (en) Anode in-situ electrochemical method for preparing hydroxyapatite coating
CN109487323B (en) Electrolyte for preparing porous membrane containing bioactive elements on titanium metal surface by micro-arc oxidation
CN104562145A (en) Method for preparing bioceramic membrane by composite oxidation
CN102641522B (en) Method for preparing medical three-dimensional gradient netlike carbon fiber/ hydroxyapatite (HA)/ medical stone composite material
Xuhui et al. Hydroxyapatite coatings on titanium prepared by electrodeposition in a modified simulated body fluid
CN104611699B (en) Preparation method of magnesium alloy surface micro-arc oxidation-electrophoresis composite coating
CN101302638A (en) Preparation of nano-HAP coating/magnesium alloy composite biological material
CN106637346B (en) A kind of preparation method with the electroactive planting body of multistage composite structure-biological
CN103556204B (en) Magnesium surface ultrasonic microarc oxidation-HF-silane coupling agent multistage composite bioactive coating preparation method
CN110438546B (en) Electrolyte for preparing hierarchical porous coating on titanium alloy surface by micro-arc oxidation
CN101537208A (en) Biological active coating on surface of titanium or titanium alloy and preparation method thereof
CN105624753A (en) Technology for uniform deposition of HA (hydroxyapatite) coatings on medical porous titanium and titanium alloy
Lin et al. Preparation of hydroxyapatite coating on smooth implant surface by electrodeposition
CN101991879A (en) Preparation method of carbon-carbon composite material/hydroxyapatite/polylactic acid biological material
CN105274603A (en) Compound modified coating of magnesium or magnesium alloy surface carbon-containing nano tube and preparation method of compound modified coating
Zhao et al. Fabrication of Al2O3 by anodic oxidation and hydrothermal synthesis of strong-bonding hydroxyapatite coatings on its surface
CN103924278A (en) Method for preparing titanium-based titanium dioxide nanotube/nano hydroxyapatite composite coating
CN111360265A (en) Preparation method of 3D printing porous metal three-dimensional surface electroactive nanoscale bioelectricity active coating and electropolymerization potential device
CN108950651A (en) A kind of preparation method of the magnesium alloy surface micro-arc electrophoresis layer of biological composite membrane containing HA
CN101928974A (en) Preparation method and application of magnesium-doped porous nano titanium oxide coating
CN107142511B (en) A kind of method that differential arc oxidation prepares porous bio-ceramic film
CN102181904B (en) Titanium surface activation method
CN104911674B (en) A kind of bioactivity coatings on porous metal material surface and preparation method thereof
CN102560599A (en) Preparation method for in-situ growth of oxide film on titanium alloy surface
CN105420786A (en) Preparation method for nano-sodium silicotitanate/titanium dioxide bio-coatings on titanium surfaces

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant