CN100557087C - Differential arc oxidation prepares K 2Ti 6O 13Coating and K 2Ti 6O 13The method of/HAp bioceramic film - Google Patents

Differential arc oxidation prepares K 2Ti 6O 13Coating and K 2Ti 6O 13The method of/HAp bioceramic film Download PDF

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CN100557087C
CN100557087C CNB2006100323554A CN200610032355A CN100557087C CN 100557087 C CN100557087 C CN 100557087C CN B2006100323554 A CNB2006100323554 A CN B2006100323554A CN 200610032355 A CN200610032355 A CN 200610032355A CN 100557087 C CN100557087 C CN 100557087C
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solution
arc oxidation
hap
titanium
film
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CN101153408A (en
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赵中伟
陈星宇
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Central South University
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Central South University
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Abstract

The invention belongs to bio-medical material and metal surface treatment technology, relate to a kind of the implantation and prepare K with metal material surface at bone 2Ti 6O 13The method of/HAp bioceramic film.The present invention as anode, carries out differential arc oxidation with titanium or titanium alloy substrate in containing the solution of potassium ion, the used potassium solution that contains adopts KOH, K 2CO 3, KCl, KNO 3, CH 3COOK, K 2SO 4, K 2C 2O 4Water-soluble and prepare etc. one or more of chemical substance.The differential arc oxidation current density is controlled at 5～1000mA/cm 2, after handling in 0.5～300 minute, form K on the surface 2Ti 6O 13Bioceramic film.Soak in the solution of calcium ions, phosphate anion, growth HAp rete forms K again 2Ti 6O 13/ HAp bioceramic film.The inventive method technology is simple, and cost is low, and bioceramic film has very high biological activity.

Description

Differential arc oxidation prepares K 2Ti 6O 13Coating and K 2Ti 6O 13The method of/HAp bioceramic film
Technical field
The invention belongs to bio-medical material and field of metal surface treatment technology, particularly K 2Ti 6O 13The preparation method of/HAp bioceramic film.
Background technology
Titanium or titanium alloy is because of having good mechanical property and biocompatibility, and by widely as the planting material of human body.But because this material does not have biological activity, can't combine, therefore need carry out surface modification treatment, make it have superior bioactive this material with body bone tissue is good.Material after the surface treatment not only has original excellent mechanical properties and biocompatibility, also will have superior bioactive, can well combine with osseous tissue, makes it become good human body planting material.
K 2Ti 6O 13Special construction form and physicochemical property, make it have good biocompatibility and biological activity.So K 2Ti 6O 13/ Ti alloy composite materials can become a kind of outstanding body implanting material.
Prepare K at present 2Ti 6O 13/ Ti alloy composite materials method has had report: disclose at titanium substrate surface K as Chinese patent CN200510013523.0 2Ti 6O 13The preparation method of coating, this method need experience the high temperature program twice, and the firstth, the preparation of potassium titanate crystal whisker powder will mix salt of wormwood, titanium dioxide to be placed on being heated to 800～1100 ℃ in the high temperature cabinet-type electric furnace, reacts 0.5～1.5 hour.The secondth, carry out coating at the titanium substrate surface, with titanium substrate embedding, in the high temperature cabinet-type electric furnace, be heated to 700～1000 ℃ with the potassium titanate crystal whisker powder again, be incubated 10～60 minutes, obtain K 2Ti 6O 13Coating.Also have the United States Patent (USP) of the Kokubo registration of Japan, the patent No. is 5609633, also discloses K 2Ti 6O 13The preparation method of coating, this process earlier are immersed in the titanium substrate in 60 ℃ the KOH solution 24 hours, and the product that will soak is heat-treated under 400-800 ℃ high temperature afterwards, obtains K at last 2Ti 6O 13Coating.These two kinds of methods need be carried out in the pyroprocess kind, and the process complexity, and to the equipment requirements height, cost is very high.Particularly, the structure and the performance of titanium or titanium alloy change unavoidably after the process pyroprocessing, and this will influence its performance as the medical human embedded material.
Summary of the invention
It is simple to the invention provides a kind of technology, low for equipment requirements, and cost is low, directly prepares K in the titanium substrate 2Ti 6O 13The method of coating, the K that this method prepares 2Ti 6O 13Bioceramic film combines closely with the titanium substrate, and has very high biological activity.And can go out one deck hydroxyapatite film layer at the growth from solution of calcium ions, phosphate anion, form K 2Ti 6O 13/ HAp bioceramic film.
Preparation method of the present invention and step are as follows:
(1) surface preparation of titanium matrix
With titanium or the polishing of titanium alloy-based body and function water-proof abrasive paper, perhaps rinse well earlier with deionized water.
(2) differential arc oxidation prepares K 2Ti 6O 13Coating
Pretreated titanium substrate is placed on contains in the potassium solution, contain potassium solution and can adopt KOH, K 2CO 3, KCl, KNO 3, CH 3COOK, K 2SO 4, K 2C 2O 4Water-soluble and prepare etc. one or more of chemical substance, according to each solubility of substances, fully regulating the concentration that contains potassium in the potassium solution under the dissolved situation at each material is 0.001～20mol/L.During differential arc oxidation, current density is controlled at 5～1000mA/cm 2, after handling in 0.5～300 minute, form K on the surface 2Ti 6O 13Bioceramic film.Then product with deionized water is rinsed well, dried standby.
(3) K 2Ti 6O 13The preparation of/HAp bioceramic film
The solution that the product that differential arc oxidation is obtained is put into calcium ions and phosphate anion respectively soaks.Earlier the product behind the differential arc oxidation is cleaned with distilled water, immersed the CaCl that concentration is 3～1800mmol/L then 2In the solution 5-30 minute, and then take out the Na that immerses 2～1200mmol/L after cleaning again 3PO 4In the solution 5～30 minutes.So alternately for several times, up at K 2Ti 6O 13The surface of film forms one deck HAp film.
The mixing solutions that the product that differential arc oxidation is obtained is put into calcium ions and phosphate anion soaks.The calcic phosphorus solution is to be made into deionized water earlier to contain CaCl 20.003～0.03mol/L, contain H 3PO 40.002 the mixing solutions of～0.02mol/L is then with NaOH or NaHCO 3Regulating pH is 4.2～7.3.Not occur muddiness degree of being in the solution,, also can filter the back rapidly and use when pH adjusts if a little precipitation is arranged.Carry out in shaking bath during immersion, temperature is 15～60 ℃, and the time is 30～10000 minutes, after deposition finishes, shows at K through XRD and SEM detection 2Ti 6O 13The surface of coating forms one deck HAp film.
Adopt present method directly in containing potassium solution, can prepare K in the short period of time once the step by differential arc oxidation 2Ti 6O 13, in the solution of calcium ions and phosphate anion, form K then 2Ti 6O 13/ HAp bioceramic film.The inventive method technology is simple, and cost is low, and the bioceramic film for preparing by this method has very high biological activity.
Description of drawings
Fig. 1 is the K of differential arc oxidation preparation 2Ti 6O 13Coating and in the calcic phosphorus solution, soak the SEM figure of different time;
Fig. 2 is the K of differential arc oxidation preparation 2Ti 6O 13Coating and in the calcic phosphorus solution, soak after XRD figure.
The present invention is described in further detail below in conjunction with accompanying drawing.
Embodiment
Embodiment 1
(1) surface preparation of titanium matrix
Use pure titanium sheet as the coated substrate material, with water-proof abrasive paper (No.360) polishing, with the abrasive paper for metallograph polishing, rinse well then more earlier, dry.
(2) differential arc oxidation prepares K 2Ti 6O 13Coating
With the KOH solution of deionized water preparation 0.001mol/L, the good titanium sheet of will polishing again is placed in the solution as anode earlier, and current density is 1000mA/cm 2, energising begins experiment, and oxidization time is 0.5 minute.Take out with deionized water after differential arc oxidation is finished and rinse well, dry, detecting the surface through XRD is by K 2Ti 6O 13Form.
(3) K 2Ti 6O 13The preparation of/HAp bioceramic film
Earlier be made into 0.03mol/L CaCl with deionized water 2With 0.02mol/L H 3PO 4Mixing solutions, again with NaHCO 3Slowly join in the solution, stir simultaneously, it is muddy to prevent that solution from occurring, and the pH value of solution value is adjusted to 7.2.The K that differential arc oxidation is prepared again 2Ti 6O 13Coating is immersed in the Plastic Bottle of the solution that fills calcium ions and phosphate anion, is put in the shaking bath and soaks, and the temperature of water-bath is controlled at 37 ℃, and depositing time is 240 hours.After deposition finishes, take out product, rinse well with deionized water, dry, detecting the surface through XRD is by K 2Ti 6O 13Form with HAp.
Embodiment 2
(1) surface preparation of titanium matrix
, directly rinse well as the coated substrate material with titanium alloy (Ti-6Al-4V), dry without polishing with deionized water.
(2) differential arc oxidation prepares K 2Ti 6O 13Coating
With the KOH of deionized water preparation 20mol/L, the titanium alloy of will not polish is placed in the solution as anode more earlier, and current density is 5mA/cm 2, energising begins experiment, and oxidization time is 5 minutes.Take out with deionized water after differential arc oxidation is finished and rinse well, dry, detecting the surface through XRD is by K 2Ti 6O 13Form.
(3) K 2Ti 6O 13The preparation of/HAp bioceramic film
Earlier be made into 0.003mol/L CaCl with deionized water 2With 0.002mol/L H 3PO 4Mixing solutions, again with NaHCO 3Slowly join in the solution, stir simultaneously, it is muddy to prevent that solution from occurring, and the pH value of solution value is adjusted to 7.2.The K that differential arc oxidation is prepared again 2Ti 6O 13Coating is immersed in the Plastic Bottle of the solution that fills calcium ions and phosphate anion, is put in the shaking bath and soaks, and the temperature of water-bath is controlled at 37 ℃, and depositing time is 240 hours.After deposition finishes, take out product, rinse well with deionized water, dry, detecting the surface through XRD is by K 2Ti 6O 13Form with HAp.
Embodiment 3
(1) surface preparation of titanium matrix
Use pure titanium sheet as the coated substrate material, with water-proof abrasive paper (No.360) polishing, with the abrasive paper for metallograph polishing, rinse well then more earlier, dry.
(2) differential arc oxidation prepares K 2Ti 6O 13Coating
With the KOH solution of deionized water preparation 1.0mol/L, the good titanium sheet of will polishing again is placed in the solution as anode earlier, and current density is 200mA/cm 2, energising begins experiment, and oxidization time is 15 minutes.Take out with deionized water after differential arc oxidation is finished and rinse well, dry, detecting the surface through XRD is by K 2Ti 6O 13Form.
(3) K 2Ti 6O 13The preparation of/HAp bioceramic film
Earlier be made into 0.005mol/L CaCl with deionized water 2With 0.005mol/L H 3PO 4Mixing solutions, again with NaHCO 3Slowly join in the solution, stir simultaneously, it is muddy to prevent that solution from occurring, and the pH value of solution value is adjusted to 7.2.The K that differential arc oxidation is prepared again 2Ti 6O 13Coating is immersed in the Plastic Bottle of the solution that fills calcium ions and phosphate anion, is put in the shaking bath and soaks, and the temperature of water-bath is controlled at 37 ℃, and depositing time is 240 hours.After deposition finishes, take out product, rinse well with deionized water, dry, detecting the surface through XRD is by K 2Ti 6O 13Form with HAp.
The K of differential arc oxidation preparation 2Ti 6O 13Coating and in the calcic phosphorus solution, soak after SEM figure and XRD figure spectrum, (A) is for soaking, (B) for soaking 2 days, (C) for soaking 4 days and (D) scheming for the SEM that soaked 12 days and XRD figure is composed among Fig. 1, Fig. 2.
Embodiment 4
(1) surface preparation of titanium matrix
, directly rinse well as the coated substrate material with pure titanium sheet, dry without polishing with deionized water.
(2) differential arc oxidation prepares K 2Ti 6O 13Coating
Prepare the K of 0.8mol/L earlier with deionized water 2CO 3, the titanium sheet of will not polish again is placed in the solution as anode, and current density is 500mA/cm 2, energising begins experiment, and oxidization time is 300 minutes.Take out with deionized water after differential arc oxidation is finished and rinse well, dry, detecting the surface through XRD is by K 2Ti 6O 13Form.
(3) K 2Ti 6O 13The preparation of/HAp bioceramic film
The product that differential arc oxidation is obtained is clean with distilled water flushing, is dipped into the CaCl that concentration is 1.5mol/L earlier 2In the solution, soak time is 30 minutes; Take out the Na that is immersed in 1.2mol/L then 3PO 4Middle soak time is 30 minutes.Take out the CaCl that is immersed in 1.5mol/L once more 2In the solution 30 minutes, be immersed in the Na of 1.2mol/L then 3PO 4Middle soak time is 30 minutes, so alternately soaks 3 times, takes out product, and is clean with distilled water flushing, dries, and detecting the surface through XRD is by K 2Ti 6O 13Form with HAp.
Embodiment 5
(1) surface treatment of titanium substrate
Use titanium alloy (Ti-6Al-4V) as the coated substrate material, with water-proof abrasive paper (No.360) polishing, with the abrasive paper for metallograph polishing, rinse well with deionized water at last more earlier, dry.
(2) differential arc oxidation prepares K 2Ti 6O 13Coating
All be KOH, the K of 0.1mol/L with the deionized water compound concentration earlier 2CO 3, KNO 3, CH 3COOK and K 2SO 4Mixing solutions, the titanium alloy that polishing is good is placed in the solution as anode, and current density is 300mA/cm 2, energising begins experiment, and oxidization time is 20 minutes.Take out with deionized water after differential arc oxidation is finished and rinse well, dry, detecting the surface through XRD is by K 2Ti 6O 13Forming, do not detect the diffraction peak of aluminium and vanadium compound, may be because their amount is less or exist with unformed oxide form.
(3) K 2Ti 6O 13The preparation of/HAp bioceramic film
Earlier be made into 0.005mol/L CaCl with deionized water 2With 0.005mol/L H 3PO 4Mixing solutions, again NaOH is slowly joined in the solution, stir simultaneously, it is muddy to prevent that solution from occurring, and the pH value of solution value is adjusted to 5.5 is.The K that differential arc oxidation is prepared 2Ti 6O 13Coating is put in the Plastic Bottle of the solution that fills calcium ions and phosphate anion, is put in the shaking bath and soaks, and the temperature of water-bath is controlled at 37 ℃, and depositing time is 240 hours.After deposition finishes, take out product, rinse well with deionized water, dry, detecting the surface through XRD is by K 2Ti 6O 13Form with HAp.

Claims (4)

1. a titanium-based micro-arc oxidation prepares K 2Ti 6O 13Coating and K 2Ti 6The preparation method of Ox/HAp bioceramic film is characterized in that: may further comprise the steps:
(1) surface preparation of titanium matrix:
With titanium or the polishing of titanium alloy-based body and function water-proof abrasive paper, rinse well with deionized water;
(2) differential arc oxidation prepares K 2Ti 6O 13Coating:
Pretreated titanium substrate is placed on contains differential arc oxidation in the potassium solution, the concentration that contains potassium solution is 0.001～20mol/L, and current density is controlled at 5～1000mA/cm 2, after handling in 0.5～300 minute, form K on the surface 2Ti 6O 13Bioceramic film is rinsed well with deionized water then, dries;
(3) K 2Ti 6O 13The preparation of/HAp bioceramic film:
With the K behind the differential arc oxidation 2Ti 6O 13Bioceramic film is cleaned with distilled water, immerses the CaCl that concentration is 3～1800mmol/L then 2In the solution 5-30 minute, take out the Na that immerses 2～1200mmol/L after cleaning again 3PO 4In the solution 5～30 minutes, alternately for several times, up at K 2Ti 6O 13The surface of film forms one deck HAp film.
2. preparation method according to claim 1 is characterized in that: the described K of step (3) 2Ti 6O 13The preparation process of/HAp bioceramic film is:
The K that differential arc oxidation is obtained 2Ti 6O 13The mixing solutions that bioceramic film is put into calcium ions and phosphate anion soaks; The calcic phosphorus solution is to be made into earlier to contain CaCl in deionized water 20.003～0.03mol/L, contain H 3PO 40.002 the mixing solutions of～0.02mol/L is then with NaOH or NaHCO 3Regulating pH is 4.2～7.3; Not occur muddiness degree of being in the solution,, also can filter the back rapidly and use when pH adjusts if a little precipitation is arranged; Carry out in shaking bath during immersion, temperature is 15～60 ℃, and the time is 30～10000 minutes, after deposition finishes, then at K 2Ti 6O 13The surface of coating forms one deck HAp film.
3. method according to claim 1, the used potassium solution that contains is to adopt KOH, K 2CO 3, KCl, KNO 3, CH 3COOK, K 2SO 4, K 2C 2O 4One or more are water-soluble and prepare.
4. preparation method according to claim 1 is characterized in that: in the surface preparation of the described titanium matrix of step (1) titanium or titanium alloy substrate are directly rinsed well with deionized water.
CNB2006100323554A 2006-09-30 2006-09-30 Differential arc oxidation prepares K 2Ti 6O 13Coating and K 2Ti 6O 13The method of/HAp bioceramic film Expired - Fee Related CN100557087C (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102230206A (en) * 2011-06-02 2011-11-02 西安理工大学 Surface treatment method of titanium implant suitable for bone growth

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102677121A (en) * 2012-03-31 2012-09-19 四川大学 Preparation of multi-stage pore structure layer on surface of medical titanium by using one-step anodic oxidation method
CN103046100B (en) * 2013-01-29 2015-05-20 哈尔滨工业大学 Method for preparing twin-stage pore micro-arc oxidation ceramic coating through three steps

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
无机晶须研究进展Ⅱ：钛酸钾晶须在复合材料中的应用. 魏明等.盐湖研究，第13卷第1期. 2005 *
生物医用钛合金的表面改性. 刘华等.河北工业大学学报，第32卷第5期. 2003 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102230206A (en) * 2011-06-02 2011-11-02 西安理工大学 Surface treatment method of titanium implant suitable for bone growth
CN102230206B (en) * 2011-06-02 2014-01-08 西安理工大学 Surface treatment method of titanium implant suitable for bone growth

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