CN102560590B - Anode in-situ electrochemical method for preparing hydroxyapatite coating - Google Patents
Anode in-situ electrochemical method for preparing hydroxyapatite coating Download PDFInfo
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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
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.
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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 |
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