CN103898591A - Method for directly preparing hydroxyapatite-containing micro-arc oxidation ceramic film - Google Patents
Method for directly preparing hydroxyapatite-containing micro-arc oxidation ceramic film Download PDFInfo
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- CN103898591A CN103898591A CN201410118521.7A CN201410118521A CN103898591A CN 103898591 A CN103898591 A CN 103898591A CN 201410118521 A CN201410118521 A CN 201410118521A CN 103898591 A CN103898591 A CN 103898591A
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Abstract
The invention discloses a method for directly preparing a hydroxyapatite-containing micro-arc oxidation ceramic film. The method comprises the following steps: cutting a titanium alloy Ti6A14V into cylindrical titanium materials, perforating above a test sample, grinding the surface of the titanium alloy till the surface of the test sample is free of scratches, removing oil, washing by using alkali and deionized water, and naturally drying for later use; suspending the cylindrical titanium materials prepared in the step A in electrolyte, performing micro-arc oxidation by using a pulse power supply, wherein the power supply voltage is 450-475V and the frequency is 900-1,200Hz; cleaning the test sample which is subjected to micro-arc oxidation by using deionized water, and drying to obtain the hydroxyapatite-containing micro-arc oxidation ceramic film. The method provided by the invention has the advantages of convenience in operation, simple process, energy saving, environmental friendliness, low request on equipment, short preparation period and low cost.
Description
Technical field
The invention belongs to biological and medicinal implant material technical field of surface, be specifically related to the method for the ceramic coating formed by micro-arc oxidation that a kind of direct preparation contains hydroxyapatite.
Background technology
Titanium or titanium alloy lightweight, specific tenacity is high, Young's modulus little (being about the half of other medical material), relatively mate with the Young's modulus of human body hard tissue, and there is certain biocompatibility, under human body fluid environment, there is good erosion resistance, after its implant into body, there is the advantages such as good mechanical property, corrosion resistance nature and tissue reaction be little, meet the requirement of human-body biological embedded material, one of main raw of being implanted and repair as bone by people always.The bone wound causing along with scientific technological advance, aging population and industry, traffic, physical culture etc. increases, and people are increasing to the demand of bio-medical material and goods thereof.But industrial titanium is metal bio-inert material, and to the healing of body tissue, without obvious promoter action, healing time is longer, and the abrasion resistance properties of titanium and alloy thereof is poor, and the abrasive dust of generation is free near implant, easily causes inflammation.So in order to improve the biocompatibility of titanium alloy material, the normal electrolytic solution that contains calcium phosphoric that adopts carries out differential arc oxidation processing, titanium alloy surface is generated and contain more phosphorus calcium cpd and the microvoid structure of hydroxyapatite, to reduce the formation of platelet adhesion reaction and thrombus, promote the early growth of osseous tissue.
Hydroxyapatite (HAP) is the chief component of vertebrates bone and tooth, and in people's enamel, the content of hydroxyapatite is more than 96%.Hydroxyapatite has good biocompatibility, and can be used as the inducible factor of a kind of bone or tooth, is simultaneously also that skeleton is organized main component, and after implanting, calcium and the phosphorus material surface that can dissociate is absorbed by bodily tissue, and the tissue that makes new advances of growth.
Hydroxyapatite powder preparation method a lot, more common method has the precipitator method, hydrolysis method, hydrothermal method and solid phase method etc.The wherein suitable more complicated of the equipment of hydrothermal method and costliness.Compared to hydrothermal method, precipitation rule be simple to operate, equipment is cheap, production capacity is large, most is taking this kind of method as main.But the precipitator method have some shortcomings, similarly be that powder easily flocks together, quality is unstable etc.For this reason, researching and developing the ceramic coating formed by micro-arc oxidation method tool that a kind of direct preparation contains hydroxyapatite is of great significance.
Summary of the invention
A kind of ceramic coating formed by micro-arc oxidation method that the object of the present invention is to provide direct preparation to contain hydroxyapatite, to improve the bad problem of titanium alloy surface ceramic film biocompatibility.
The object of the present invention is achieved like this, comprises the steps:
A, pre-treatment: by titanium alloy T i
6al
4v cuts into cylindrical titanium material, and above sample, punching, carries out surface finish to titanium alloy and process to specimen surface no marking, and then carries out oil removing, alkali cleaning and deionization washing, natural dry for standby;
B, differential arc oxidation: cylindrical titanium material prepared by the pre-treatment of A step hangs in electrolytic solution, carries out differential arc oxidation, and power supply used is the pulse power, voltage of supply 450 ~ 475V, frequency is 900 ~ 1200HZ;
C, sample after treatment differential arc oxidation is obtained to the ceramic coating formed by micro-arc oxidation that contains hydroxyapatite by washed with de-ionized water post-drying.
Differential arc oxidation film layer of the present invention and titanium alloy-based surface form metallurgical binding, surface ceramic film is the vesicular structure that contains hydroxyapatite, there is good biocompatibility, can promote the early growth of osseous tissue, can be used as one of main raw treatment process of bone implantation and reparation.
Brief description of the drawings
Fig. 1 is process flow sheet of the present invention.
Fig. 2 is experiment XRD detected result figure of the present invention.
Embodiment
Below in conjunction with accompanying drawing, the invention will be further described, but never in any form the present invention is limited, and any conversion of doing based on training centre of the present invention, all falls into protection domain of the present invention.
The present invention adopts differential arc oxidation to prepare the differential arc oxidation porous ceramic film that contains hydroxyapatite, comprises the steps:
A, pre-treatment: by titanium alloy T i
6al
4v cuts into cylindrical titanium material, and above sample, punching, carries out surface finish to titanium alloy and process to specimen surface no marking, and then carries out oil removing, alkali cleaning and deionization washing, natural dry for standby;
B, differential arc oxidation: cylindrical titanium material prepared by the pre-treatment of A step hangs in electrolytic solution, carries out differential arc oxidation, and power supply used is the pulse power, voltage of supply 450 ~ 475V, frequency is 900 ~ 1200HZ;
C, sample after treatment differential arc oxidation is obtained to the ceramic coating formed by micro-arc oxidation that contains hydroxyapatite by washed with de-ionized water post-drying.
The degreaser of described A step is dehydrated alcohol or acetone.
The alkaline wash of described A step is 1g/L sodium hydroxide solution.
The electrolytic solution of described B step consists of: calcic ionogen 0.15mol/L ~ 0.20mol/L, phosphorous ionogen 0.10 mol/L ~ 0.20mol/L, complexing agent 0.01mol/L ~ 0.06mol/L.
The electrolytic solution of described B step wherein calcic ionogen is one or more of calcium acetate, calcium carbonate, monocalcium phosphate, calcium hydroxide or neurosin; Phosphorous ionogen is one or more of phosphoric acid salt, hydrophosphate, dihydrogen phosphate; Complexing agent is selected one or more of EDTA, EDTA-2Na or citric acid.
The pulse power dutycycle of described B step is 30% ~ 40%, and positive pulse number is 1, and negative pulse number is 1.
The oxidization time of described B step is 15 ~ 20min, and temperature is room temperature.
The pre-treatment of A, titanium alloy sample: by titanium alloy T i
6al
4v cuts into cylindrical titanium material, punching above sample; Titanium alloy is carried out to surface finish processing, until specimen surface is without obvious cut, and then with ethanol oil removing, the alkali cleaning of 1g/L sodium hydroxide solution and deionization washing, naturally oven dry;
B, differential arc oxidation: the cylindrical titanium material after aforementioned processing is hung in electrolytic solution, carry out differential arc oxidation; Power supply used is the pulse power, and power parameter is set as: voltage 450V, and dutycycle is 30%, and frequency is 900HZ, and positive pulse number is 1, and negative pulse number is 1, oxidization time is 15min.Electrolyte quota is: lime acetate 0.1 5mol/L, EDETATE SODIUM 0.15mol/L, potassium primary phosphate 0.1 mol/L.
C, aftertreatment: sample after treatment differential arc oxidation is obtained to the differential arc oxidation porous ceramic film titanium material that contains hydroxyapatite with drying up after washed with de-ionized water.
The pre-treatment of A, titanium alloy sample: by titanium alloy T i
6al
4v cuts into cylindrical titanium material, punching above sample; Titanium alloy is carried out to surface finish processing, until specimen surface is without obvious cut, and then with ethanol oil removing, the alkali cleaning of 1g/L sodium hydroxide solution and deionization washing, naturally oven dry;
B, differential arc oxidation: the cylindrical titanium material after aforementioned processing is hung in electrolytic solution, carry out differential arc oxidation; Power supply used is the pulse power, and power parameter is set as: voltage 475V, and dutycycle is 40%, and frequency is 900HZ, and positive pulse number is 1, and negative pulse number is 1, oxidization time is 20min.Electrolyte quota is: lime acetate 0.2 mol/L, EDETATE SODIUM 0.15mol/L, potassium primary phosphate 0.1mol/L.
C, aftertreatment: by sample after treatment differential arc oxidation with drying up the titanium material that obtains the differential arc oxidation porous ceramic film that contains hydroxyapatite after washed with de-ionized water.
embodiment 3
The pre-treatment of A, titanium alloy sample: by titanium alloy T i
6al
4v cuts into cylindrical titanium material, punching above sample; Titanium alloy is carried out to surface finish processing, until specimen surface is without obvious cut, and then with ethanol oil removing, the alkali cleaning of 1g/L sodium hydroxide solution and deionization washing, naturally oven dry;
B, differential arc oxidation: the cylindrical titanium material after aforementioned processing is hung in electrolytic solution, carry out differential arc oxidation; Power supply used is the pulse power, and power parameter is set as: voltage 450V, and dutycycle is 40%, and frequency is 900HZ, and positive pulse number is 1, and negative pulse number is 1, oxidization time is 20min.Electrolyte quota is: lime acetate 0.15 mol/L, EDETATE SODIUM 0.15mol/L, potassium primary phosphate 0.1 mol/L.
C, aftertreatment: by sample after treatment differential arc oxidation with drying up the titanium material that obtains the differential arc oxidation porous ceramic film that contains hydroxyapatite after washed with de-ionized water.
embodiment 4
The pre-treatment of A, titanium alloy sample: by titanium alloy T i
6al
4v cuts into cylindrical titanium material, punching above sample; Titanium alloy is carried out to surface finish processing, until specimen surface is without obvious cut, and then with ethanol oil removing, the alkali cleaning of 1g/L sodium hydroxide solution and deionization washing, naturally oven dry;
B, differential arc oxidation: the cylindrical titanium material after aforementioned processing is hung in electrolytic solution, carry out differential arc oxidation; Power supply used is the pulse power, and power parameter is set as: voltage 475V, and dutycycle is 40%, and frequency is 1200HZ, and positive pulse number is 1, and negative pulse number is 1, oxidization time is 20min.Electrolyte quota is: lime acetate 0.167 mol/L, EDETATE SODIUM 0.15mol/L, potassium primary phosphate 0.1 mol/L.
C, aftertreatment: by sample after treatment differential arc oxidation with drying up the titanium material that obtains the differential arc oxidation porous ceramic film that contains hydroxyapatite after washed with de-ionized water.
embodiment 5
The pre-treatment of A, titanium alloy sample: by titanium alloy T i
6al
4v cuts into cylindrical titanium material, punching above sample; Titanium alloy is carried out to surface finish processing, until specimen surface is without obvious cut, and then with ethanol oil removing, the alkali cleaning of 1g/L sodium hydroxide solution and deionization washing, naturally oven dry;
B, differential arc oxidation: the cylindrical titanium material after aforementioned processing is hung in electrolytic solution, carry out differential arc oxidation; Power supply used is the pulse power, and power parameter is set as: voltage 475V, and dutycycle is 40%, and frequency is 900HZ, and positive pulse number is 1, and negative pulse number is 1, oxidization time is 20min.Electrolyte quota is: lime acetate 0.2 mol/L, EDETATE SODIUM 0.15mol/L, potassium primary phosphate 0.1 mol/L.
C, aftertreatment: by sample after treatment differential arc oxidation with drying up the titanium material that obtains the differential arc oxidation porous ceramic film that contains hydroxyapatite after washed with de-ionized water.
Claims (7)
1. a method for the ceramic coating formed by micro-arc oxidation that directly preparation contains hydroxyapatite, is characterized in that comprising the steps:
A, pre-treatment: by titanium alloy T i
6al
4v cuts into cylindrical titanium material, and above sample, punching, carries out surface finish to titanium alloy and process to specimen surface no marking, and then carries out oil removing, alkali cleaning and deionization washing, natural dry for standby;
B, differential arc oxidation: cylindrical titanium material prepared by the pre-treatment of A step hangs in electrolytic solution, carries out differential arc oxidation, and power supply used is the pulse power, voltage of supply 450 ~ 475V, frequency is 900 ~ 1200HZ;
C, sample after treatment differential arc oxidation is obtained to the ceramic coating formed by micro-arc oxidation that contains hydroxyapatite by washed with de-ionized water post-drying.
2. the method for the ceramic coating formed by micro-arc oxidation that direct preparation according to claim 1 contains hydroxyapatite, the degreaser that it is characterized in that described A step is dehydrated alcohol or acetone.
3. the method for the ceramic coating formed by micro-arc oxidation that direct preparation according to claim 1 contains hydroxyapatite, the alkaline wash that it is characterized in that described A step is 1g/L sodium hydroxide solution.
4. the method for the ceramic coating formed by micro-arc oxidation that direct preparation according to claim 1 contains hydroxyapatite, the electrolytic solution that it is characterized in that described B step consists of: calcic ionogen 0.15mol/L ~ 0.20mol/L, phosphorous ionogen 0.10 mol/L ~ 0.20mol/L, complexing agent 0.01mol/L ~ 0.06mol/L.
5. the method for the ceramic coating formed by micro-arc oxidation that contains hydroxyapatite according to the direct preparation described in claim 1 or 4, the electrolytic solution that it is characterized in that described B step wherein calcic ionogen is one or more of calcium acetate, calcium carbonate, monocalcium phosphate, calcium hydroxide or neurosin; Phosphorous ionogen is one or more of phosphoric acid salt, hydrophosphate, dihydrogen phosphate; Complexing agent is selected one or more of EDTA, EDTA-2Na or citric acid.
6. the method for the ceramic coating formed by micro-arc oxidation that direct preparation according to claim 1 contains hydroxyapatite, the pulse power dutycycle that it is characterized in that described B step is 30% ~ 40%, and positive pulse number is 1, and negative pulse number is 1.
7. the method for the ceramic coating formed by micro-arc oxidation that direct preparation according to claim 1 contains hydroxyapatite, the oxidization time that it is characterized in that described B step is 15 ~ 20min, temperature is room temperature.
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Cited By (6)
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|---|---|---|---|---|
| CN104562145A (en) * | 2014-12-23 | 2015-04-29 | 昆明理工大学 | Method for preparing bioceramic membrane by composite oxidation |
| CN105002546A (en) * | 2015-08-08 | 2015-10-28 | 昆明冶金研究院 | Method for preparing wear-resisting biological ceramic film on surface of titanium alloy through micro-arc oxidation |
| CN107119304A (en) * | 2017-04-20 | 2017-09-01 | 西安交通大学 | A kind of magnetic TiO2The differential arc oxidation preparation method of bioactivity coatings |
| CN107142511A (en) * | 2017-04-11 | 2017-09-08 | 昆明理工大学 | A kind of method that differential arc oxidation prepares porous bio-ceramic film |
| CN108103551A (en) * | 2017-11-23 | 2018-06-01 | 昆明理工大学 | A kind of method of hydroxylapatite crystal in promotion differential arc oxidation film layer |
| CN111733436A (en) * | 2020-06-19 | 2020-10-02 | 浙江大学 | Silver-iodine surface modified titanium alloy implant and preparation method thereof |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104562145A (en) * | 2014-12-23 | 2015-04-29 | 昆明理工大学 | Method for preparing bioceramic membrane by composite oxidation |
| CN105002546A (en) * | 2015-08-08 | 2015-10-28 | 昆明冶金研究院 | Method for preparing wear-resisting biological ceramic film on surface of titanium alloy through micro-arc oxidation |
| CN107142511A (en) * | 2017-04-11 | 2017-09-08 | 昆明理工大学 | A kind of method that differential arc oxidation prepares porous bio-ceramic film |
| CN107142511B (en) * | 2017-04-11 | 2018-11-27 | 昆明理工大学 | A kind of method that differential arc oxidation prepares porous bio-ceramic film |
| CN107119304A (en) * | 2017-04-20 | 2017-09-01 | 西安交通大学 | A kind of magnetic TiO2The differential arc oxidation preparation method of bioactivity coatings |
| CN107119304B (en) * | 2017-04-20 | 2019-05-03 | 西安交通大学 | A kind of magnetism TiO2The differential arc oxidation preparation method of bioactivity coatings |
| CN108103551A (en) * | 2017-11-23 | 2018-06-01 | 昆明理工大学 | A kind of method of hydroxylapatite crystal in promotion differential arc oxidation film layer |
| CN108103551B (en) * | 2017-11-23 | 2019-07-16 | 昆明理工大学 | A kind of method of hydroxylapatite crystal in promotion differential arc oxidation film layer |
| CN111733436A (en) * | 2020-06-19 | 2020-10-02 | 浙江大学 | Silver-iodine surface modified titanium alloy implant and preparation method thereof |
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Address after: 650031 No. 86 Yuantong North Road, Yunnan, Kunming Patentee after: Kunming Metallurgical Research Institute Co., Ltd Address before: 650031 No. 86 Yuantong North Road, Yunnan, Kunming Patentee before: Kunming Metallurgical Research Institute |
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