CN104313662A - Preparation method for bioactive ceramic membrane on surface of tantalum metal - Google Patents

Preparation method for bioactive ceramic membrane on surface of tantalum metal Download PDF

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Publication number
CN104313662A
CN104313662A CN201410512237.8A CN201410512237A CN104313662A CN 104313662 A CN104313662 A CN 104313662A CN 201410512237 A CN201410512237 A CN 201410512237A CN 104313662 A CN104313662 A CN 104313662A
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tantalum
tantalum metal
preparation
metallic surface
electrolytic solution
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CN201410512237.8A
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赵全明
杨惠林
刘忠堂
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赵全明
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    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25DPROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02Anodisation
    • C25D11/26Anodisation of refractory metals or alloys based thereon

Abstract

The invention discloses a preparation method for a bioactive ceramic membrane on the surface of a tantalum metal, for solving the problem that the tantalum metal cannot generate bone bonding with bone tissues after being implanted in a body due to poor activity and bone induction capacity, and the problems that the prior art is complicated in process and high in cost and bonding strength of an obtained membrane layer and a matrix is weak. The preparation method comprises the following steps: 1, treating the surface of the tantalum metal; 2, preparing electrolyte; 3, with the tantalum metal as an anode and stainless steel as a cathode, setting an electrical parameter and carrying out micro-arc oxidation; and 4, carrying out hydrothermal treatment in a hydrothermal autoclave to obtain the bioactive ceramic membrane. With the adoption of the preparation method, process is simple; the used electrolyte is non-toxic, non-pollution and environmentally friendly, a calcium tantalite-containing coating with high biological activity and binding force is directly prepared on the tantalum metal by virtue of micro-arc oxidation and hydrothermal treatment, and the biological activity of the tantalum metal is well improved.

Description

The preparation method of a kind of tantalum metallic surface bioactive ceramics film
Technical field
The present invention relates to the preparation method of a kind of tantalum metallic surface bioactive ceramics film.
Background technology
Tantalum (tantalum) is a kind of grey, light, hard metal, chemical property is very stable, at present in field of orthopaedics widespread uses such as joint prosthesis, osteonecrosis, backbone, Cranial defect, but it is bio-inert material, biological activity and self-bone grafting ability, easy generation stress concentration causes the adverse consequencess such as bone regeneration around implant bone resorption, after direct implant into body can surround by the encapsulated tunica fibrosa of one deck, be difficult to very fast and matrix and form mortise, this not only extends the cycle that plantation is repaired, and have impact on the success ratio of implantation.Although osseous tissue can be grown into, tantalum metal generation mechanical snap is fixed, and intensity is not high, and required time is long, therefore can not meet clinical needs completely.For making tantalum metal have albumen and cell adhesion growth in inductor, form the bioactive functions of tight bone bonding, the most effective way carries out surface modification to tantalum metal exactly at present.By both having remained the excellent mechanical performances of tantalum metal to tantalum metal surface modification, turn increased the biological activity of tantalum metal.
Differential arc oxidation is a kind of brand-new material process for modifying surface developed rapidly in recent years, and it is a kind of anode oxidation method at metallic surface growth in situ pottery in essence.Can at metallic surface growth in situ porous, coarse ceramic membrane by differential arc oxidization technique, this ceramic membrane not only adds the wear resistance of material, erosion resistance, resistance to fatigue, greatly improve the performance and used life of material, and because ceramic membrane is from matrix growth in situ, have very high bonding strength with matrix, be therefore widely used in the surface modification of biomaterial.
Differential arc oxidation-hydrothermal method is the advantage combining differential arc oxidation and hydrothermal treatment consists, differential arc oxidation film layer is fine and close and have very high rub resistance, impact property, the corrosion of number of chemical material can be resisted, the ion in matrix can be effectively stoped outwards to discharge, toxic action can not be produced to organism, and be conducive to bone growth and implant long-term stability; Differential arc oxidization surface biologically active substance crystalline forming can be made after hydrothermal treatment consists, improve the biological activity of material further.Differential arc oxidation-hydrothermal method required equipment is simple, economical and effective, and prepared thicknesses of layers is even, and matrix has very high bonding force, has important using value in the field of surface modification of biomaterial.
Summary of the invention
The object of the invention is to solve tantalum metal biological activity and self-bone grafting ability, implanting can not produce bone bonding with osseous tissue, and prior art processes is complicated, cost is high, the rete obtained and the problem such as substrate combinating strength is low.The invention provides the preparation method of a kind of tantalum metallic surface bioactive ceramics film.
The preparation method of tantalum metallic surface of the present invention bioactive ceramics film, is characterized in that the preparation method of tantalum metallic surface bioactive ceramics film is realized by following steps: one, carry out deoxidation film, oil removal treatment successively to tantalum metal; Two, prepare the anhydrous acetic acid calcium of electrolytic solution: 8-95g/L, the disodium hydrogen phosphate dodecahydrate of 3-28g/L, 1-5g/L disodium ethylene diamine tetraacetate, solvent are deionized water; Three, the tantalum metal after processing with step one is for anode, fix with fixture in the electrolytic solution immersing step 2 configuration, stainless steel electrolytic liquid bath is negative electrode, adopt the pulse power, arranging electrical parameter is: pulsed voltage 210-460V, pulse-repetition 300-600Hz, dutycycle are 10-50%, carry out differential arc oxidation 5-30min; Four, the tantalum metal after step 3 process is put into hydro-thermal autoclave, then with temperature rise rate intensification 300-600 ° of C of 2-8 ° of C/min, insulation 5-8h, controls hydro-thermal autoclave internal pressure 3-10MPa, is namely prepared into the bioactive coating containing tantalic acid calcium in tantalum metallic surface in insulating process.
In the electrolytic solution of step 2 of the present invention, disodium hydrogen phosphate dodecahydrate can also replace with sodium polyphosphate, and the mass concentration of sodium polyphosphate is 3-20g/L.In the electrolytic solution of step 2, Sodium hexametaphosphate 99 can also replace with five water sodium β-glycerophosphates, and the mass concentration of sodium phosphate is 3-18g/L.
First the present invention adopts differential arc oxidization technique to be rich in the ceramic membrane of calcium phosphorus in the preparation of tantalum metallic surface, and be a kind of metallurgical binding between rete and tantalum metal base, bonding force is high; Then utilize hydrothermal technique to make calcium phosphorus in ceramic film be transformed into tantalic acid calcium, impart tantalum metallic surface biological activity, improve the biocompatibility of tantalum metal.
The present invention breaches the application limitations that differential arc oxidation only realizes on valve metal, simplifies technique, has saved cost, achieves the preparation of tantalum metallic surface tantalic acid calcium rete; By choosing suitable electrolyte component and respective concentration, control differential arc oxidation voltage, frequency and time, in tantalum metallic surface, direct differential arc oxidation generates the ceramic membrane containing higher concentration calcium phosphorus, then by controlling time and the pressure of hydrothermal treatment consists, tantalic acid calcium is separated out in tantalum metallic surface.
Invention increases tantalum biocompatible metal and biological activity, facilitate the combination of tantalum metal implant material and osseous tissue, expand the range of application of tantalum metal.
Accompanying drawing explanation
Fig. 1 is the electron microscope picture of the calcic phosphorus ceramic coating formed by micro-arc oxidation prepared after the oxidation of tantalum differential of arc on metal surface in embodiment one.
Fig. 2 is the scanning electron microscope diagram sheet containing tantalic acid calcium rete prepared after the hydrothermal treatment consists of tantalum metallic surface in embodiment one.
Embodiment
Technical solution of the present invention is not limited to following cited embodiment, also comprises the arbitrary combination between each embodiment.
Embodiment one: present embodiment is realized by following steps in the preparation method of tantalum metallic surface bioactive ceramics film: one, successively deoxidation film, oil removal treatment are carried out to tantalum metal; Two, prepare the anhydrous acetic acid calcium of electrolytic solution: 8-95g/L, the disodium hydrogen phosphate dodecahydrate of 3-28g/L, 1-5g/L disodium ethylene diamine tetraacetate, solvent are deionized water; Three, the tantalum metal after processing with step one is for anode, fix with fixture in the electrolytic solution immersing step 2 configuration, stainless steel electrolytic liquid bath is negative electrode, adopt the pulse power, arranging electrical parameter is: pulsed voltage 210-460V, pulse-repetition 300-600Hz, dutycycle are 10-50%, carry out differential arc oxidation 5-30min; Four, the tantalum metal after step 3 process is put into hydro-thermal autoclave, then with temperature rise rate intensification 300-600 ° of C of 2-8 ° of C/min, insulation 5-8h, controls hydro-thermal autoclave internal pressure 3-10MPa, is namely prepared into the bioactive coating containing tantalic acid calcium in tantalum metallic surface in insulating process.
Embodiment two: present embodiment and embodiment one unlike carrying out deoxidation film successively to tantalum metal in step one, oil removal treatment is: carry out polishing deoxidation film with the sand paper of 100#, 200#, 300#, 500#, 800#, 1000#, 1200#, 1500#, 2000# successively, then surface and oil contaminant is removed with acetone cleaning, use deionized water ultrasonic cleaning again, naturally dry.
The anhydrous acetic acid calcium of embodiment three: present embodiment and embodiment one or two prepare electrolytic solution unlike in step 2: 32-63g/L, the disodium hydrogen phosphate dodecahydrate of 7-15g/L, 2-4g/L disodium ethylene diamine tetraacetate, solvent are deionized water, other step and parameter identical with embodiment one or two.
The anhydrous acetic acid calcium of embodiment four: present embodiment and embodiment one or two prepare electrolytic solution unlike in step 2: 46g/L, the disodium hydrogen phosphate dodecahydrate of 11g/L, 3g/L disodium ethylene diamine tetraacetate, solvent are deionized water, other step and parameter identical with embodiment one or two.
Embodiment five: one of present embodiment and embodiment one to four unlike arranging electrical parameter in step 3 are: pulse-repetition 300-500Hz, dutycycle is 20-40%, other step and parameter identical with one of embodiment one to four.
Embodiment six: one of present embodiment and embodiment one to four unlike arranging electrical parameter in step 3 are: pulse-repetition 400Hz, dutycycle is 30%, other step and parameter identical with one of embodiment one to four.
Embodiment seven: one of present embodiment and embodiment one to six carry out differential arc oxidation 10-20min unlike in step 3.Other step and parameter identical with one of embodiment one to six.
Embodiment eight: one of present embodiment and embodiment one to six carry out differential arc oxidation 15min unlike in step 3.Other step and parameter identical with one of embodiment one to six.
Embodiment nine: one of present embodiment and embodiment one to eight are warming up to 400-500 ° of C unlike in step 4 with the temperature rise rate of 4-6 ° of C/min.Other step and parameter identical with one of embodiment one to eight.
Embodiment ten: one of present embodiment and embodiment one to eight are warming up to 450 ° of C unlike in step 4 with the temperature rise rate of 5 ° of C/min.Other step and parameter identical with one of embodiment one to eight.
Embodiment 11: one of present embodiment and embodiment one to ten are incubated 6-7h unlike in step 4.Other step and parameter identical with one of embodiment one to ten.
Embodiment 12: one of present embodiment and embodiment one to ten are incubated 6.5h unlike in step 4.Other step and parameter identical with one of embodiment one to ten.
Embodiment 13: one of present embodiment and embodiment one to ten two are 5-8MPa unlike controlling hydro-thermal autoclave internal pressure in insulating process in step 4.Other step and parameter identical with one of embodiment one to ten two.
Embodiment 14: one of present embodiment and embodiment one to ten two are 6MPa unlike controlling hydro-thermal autoclave internal pressure in insulating process in step 4.Other step and parameter identical with one of embodiment one to ten two.
Embodiment 15: the electrolytic solution that one of present embodiment and embodiment one to ten four configure unlike step 2 is: the anhydrous acetic acid calcium of 16-79g/L, the sodium polyphosphate of 3-20g/L, 1-3g/L disodium ethylene diamine tetraacetate, solvent is deionized water.Other step and parameter identical with one of embodiment one to ten four.
Embodiment 16: the electrolytic solution that one of present embodiment and embodiment one to ten four configure unlike step 2 is: the anhydrous acetic acid calcium of 39-56g/L, the sodium polyphosphate of 8-13g/L, 1-2g/L disodium ethylene diamine tetraacetate, solvent is deionized water.Other step and parameter are with specifically to implement one of one to ten four identical.
Embodiment 17: the electrolytic solution that present embodiment and embodiment 15 configure unlike step 2 is: the anhydrous acetic acid calcium of 46g/L, the sodium polyphosphate of 10g/L, 2g/L disodium ethylene diamine tetraacetate, and solvent is deionized water.Other step and parameter are with specifically to implement one of one to ten four identical.
Embodiment 18: the electrolytic solution that one of present embodiment and embodiment one to ten seven configure unlike step 2 is: the anhydrous acetic acid calcium of 8-126g/L, the five water sodium β-glycerophosphates of 3-18g/L, 1-5g/L disodium ethylene diamine tetraacetate, solvent is deionized water.Other step and parameter identical with one of embodiment one to ten seven.
Embodiment 19: the electrolytic solution that one of present embodiment and embodiment one to ten seven configure unlike step 2 is: the anhydrous acetic acid calcium of 46-79g/L, the five water sodium β-glycerophosphates of 8-15g/L, 2-4g/L disodium ethylene diamine tetraacetate, solvent is deionized water.Other step and parameter identical with one of embodiment one to ten seven.
Embodiment 20: present embodiment with specifically implement 18 electrolytic solution configured unlike step 2 and be: the electrolytic solution that one of present embodiment and embodiment one to ten seven configure unlike step 2 is: the anhydrous acetic acid calcium of 56g/L, the five water sodium β-glycerophosphates of 12g/L, 3g/L disodium ethylene diamine tetraacetate, solvent is deionized water.Other step and parameter identical with one of embodiment one to ten seven.

Claims (3)

1. a preparation method for tantalum metallic surface bioactive ceramics film, is characterized in that the preparation method of tantalum metallic surface bioactive ceramics film is realized by following steps: one, carry out deoxidation film, oil removal treatment successively to tantalum metal; Two, prepare the anhydrous acetic acid calcium of electrolytic solution: 8-95g/L, the disodium hydrogen phosphate dodecahydrate of 3-28g/L, 1-5g/L disodium ethylene diamine tetraacetate, solvent are deionized water; Three, the tantalum metal after processing with step one is for anode, fix with fixture in the electrolytic solution immersing step 2 configuration, stainless steel electrolytic liquid bath is negative electrode, adopt the pulse power, arranging electrical parameter is: pulsed voltage 210-460V, pulse-repetition 300-600Hz, dutycycle are 10-50%, carry out differential arc oxidation 5-30min; Four, the tantalum metal after step 3 process is put into hydro-thermal autoclave, then with temperature rise rate intensification 300-600 ° of C of 2-8 ° of C/min, insulation 5-8h, controls hydro-thermal autoclave internal pressure 3-10MPa, is namely prepared into the bioactive coating containing tantalic acid calcium in tantalum metallic surface in insulating process.
2. the preparation method of a kind of tantalum metallic surface according to claim 1 bioactive ceramics film, it is characterized in that the electrolytic solution that step 2 configures is: the anhydrous acetic acid calcium of 16-79g/L, the sodium polyphosphate of 3-20g/L, 1-3g/L disodium ethylene diamine tetraacetate, solvent is deionized water.
3. the preparation method of a kind of tantalum metallic surface according to claim 1 bioactive ceramics film, it is characterized in that the electrolytic solution that step 2 configures is: the anhydrous acetic acid calcium of 8-126g/L, the five water sodium β-glycerophosphates of 3-18g/L, 1-5g/L disodium ethylene diamine tetraacetate, solvent is deionized water.
CN201410512237.8A 2014-09-29 2014-09-29 Preparation method for bioactive ceramic membrane on surface of tantalum metal Pending CN104313662A (en)

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104762619A (en) * 2015-04-02 2015-07-08 长沙南方钽铌有限责任公司 Preparation method of matt tantalum coiled strips
CN106222723A (en) * 2016-08-17 2016-12-14 林春梅 A kind of implant composite biological coatings and preparation technology thereof
CN109771695A (en) * 2018-02-09 2019-05-21 河北工业大学 A kind of preparation method of the bioactivity surface with bacteriostasis property
CN109989089A (en) * 2018-01-03 2019-07-09 中国科学院上海硅酸盐研究所 External Osteoblast Differentiation tantalum base coating of a kind of rush with micro-nano structure and preparation method thereof
CN111363995A (en) * 2020-04-21 2020-07-03 王永芝 Preparation method of medical metal bone implant material
CN111481738A (en) * 2020-03-25 2020-08-04 天衍医疗器材有限公司 Preparation method of bioactive porous tantalum implant

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104762619A (en) * 2015-04-02 2015-07-08 长沙南方钽铌有限责任公司 Preparation method of matt tantalum coiled strips
CN104762619B (en) * 2015-04-02 2018-10-12 长沙南方钽铌有限责任公司 A kind of preparation method of matt tantalum coiled strip
CN106222723A (en) * 2016-08-17 2016-12-14 林春梅 A kind of implant composite biological coatings and preparation technology thereof
CN109989089A (en) * 2018-01-03 2019-07-09 中国科学院上海硅酸盐研究所 External Osteoblast Differentiation tantalum base coating of a kind of rush with micro-nano structure and preparation method thereof
CN109989089B (en) * 2018-01-03 2020-09-18 中国科学院上海硅酸盐研究所 Tantalum-based coating with micro-nano structure and capable of promoting in-vitro osteogenic differentiation and preparation method thereof
CN109771695A (en) * 2018-02-09 2019-05-21 河北工业大学 A kind of preparation method of the bioactivity surface with bacteriostasis property
CN111481738A (en) * 2020-03-25 2020-08-04 天衍医疗器材有限公司 Preparation method of bioactive porous tantalum implant
CN111363995A (en) * 2020-04-21 2020-07-03 王永芝 Preparation method of medical metal bone implant material

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