CN103898591B - The method of the ceramic coating formed by micro-arc oxidation that a kind of direct preparation contains hydroxyapatite - Google Patents
The method of the ceramic coating formed by micro-arc oxidation that a kind of direct preparation contains hydroxyapatite Download PDFInfo
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Abstract
The method that the invention discloses a kind of micro-arc oxidation ceramic coating formed by micro-arc oxidation that directly preparation contains hydroxyapatite, comprises titanium alloy T i6Al4V 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; Cylindrical titanium material prepared by the pretreatment of A step hangs in electrolyte, carries out differential arc oxidation, and power supply used is the pulse power, supply voltage 450 ~ 475V, and frequency is 900 ~ 1200Hz; 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. Method provided by the invention is easy to operate, and technique is simple, energy-conserving and environment-protective, and equipment requirement is low, and manufacturing cycle is short, with 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 strength is high, elastic modelling quantity little (being about the half of other medical material), relatively mate with the elastic modelling quantity of human body hard tissue, and there is certain biocompatibility, under human body fluid environment, there is good corrosion resistance, after its implant into body, there is the advantages such as good mechanical property, decay resistance and tissue reaction be little, meet the requirement of human-body biological embedded material, one of main material 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 facilitation, 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 electrolyte that contains calcium P elements that adopts carries out differential arc oxidation processing, titanium alloy surface is generated and contain more phosphorus calcium compound and the microcellular structure of hydroxyapatite, to reduce the formation of platelet adhesion reaction and thrombus, promote the early growth of bone tissue.
Hydroxyapatite (HAP) is the chief component of vertebrate 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 precipitation method, Hydrolyze method, hydro-thermal method and solid phase method etc. The wherein suitable more complicated of the equipment of hydro-thermal method and costliness. Compared to hydro-thermal 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 precipitation 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, pretreatment: by titanium alloy T i6Al4V 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 pretreatment of A step hangs in electrolyte, carries out differential arc oxidation, and power supply used is the pulse power, supply voltage 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 loose structure that contains hydroxyapatite, there is good biocompatibility, can promote the early growth of bone tissue, can be used as one of main material processing method of bone implantation and reparation.
Brief description of the drawings
Fig. 1 is process chart of the present invention.
Fig. 2 is experiment XRD testing result figure of the present invention.
Detailed description of the invention
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, pretreatment: by titanium alloy T i6Al4V 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 pretreatment of A step hangs in electrolyte, carries out differential arc oxidation, and power supply used is the pulse power, supply voltage 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 absolute ethyl alcohol or acetone.
The alkali wash water of described A step is 1g/L sodium hydroxide solution.
The electrolyte of described B step consists of: calcic electrolyte 0.15mol/L ~ 0.20mol/L, phosphorous electrolyte 0.10mol/L ~ 0.20mol/L, complexing agent 0.01mol/L ~ 0.06mol/L.
The electrolyte of described B step wherein calcic electrolyte is one or more of calcium acetate, calcium carbonate, calcium dihydrogen phosphate, calcium hydroxide or calcium glycerophosphate; Phosphorous electrolyte is one or more of phosphate, hydrophosphate, dihydric 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.
Embodiment 1
The pretreatment of A, titanium alloy sample: by titanium alloy T i6Al4V 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 electrolyte, 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: calcium acetate 0.15mol/L, EDETATE SODIUM 0.15mol/L, potassium dihydrogen phosphate 0.1mol/L.
C, post processing: 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.
Embodiment 2
The pretreatment of A, titanium alloy sample: by titanium alloy T i6Al4V 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 electrolyte, 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: calcium acetate 0.2mol/L, EDETATE SODIUM 0.15mol/L, potassium dihydrogen phosphate 0.1mol/L.
C, post processing: 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 pretreatment of A, titanium alloy sample: by titanium alloy T i6Al4V 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 electrolyte, 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: calcium acetate 0.15mol/L, EDETATE SODIUM 0.15mol/L, potassium dihydrogen phosphate 0.1mol/L.
C, post processing: 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 pretreatment of A, titanium alloy sample: by titanium alloy T i6Al4V 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 electrolyte, 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: calcium acetate 0.167mol/L, EDETATE SODIUM 0.15mol/L, potassium dihydrogen phosphate 0.1mol/L.
C, post processing: 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 pretreatment of A, titanium alloy sample: by titanium alloy T i6Al4V 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 electrolyte, 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: calcium acetate 0.2mol/L, EDETATE SODIUM 0.15mol/L, potassium dihydrogen phosphate 0.1mol/L.
C, post processing: 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 (3)
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, pretreatment: by titanium alloy T i6Al4V 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 pretreatment of A step hangs in electrolyte, carries out differential arc oxidation, and power supply used is the pulse power, supply voltage 450 ~ 475V, frequency is 900 ~ 1200Hz; Pulse power dutycycle is 30% ~ 40%, and positive pulse number is 1, and negative pulse number is 1; Oxidization time is 15 ~ 20min, and temperature is room temperature; Electrolyte is calcium acetate 0.15mol/L ~ 0.20mol/L, potassium dihydrogen phosphate 0.10mol/L ~ 0.20mol/L, EDETATE SODIUM 0.01mol/L ~ 0.06mol/L;
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 absolute ethyl 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 alkali wash water that it is characterized in that described A step is 1g/L sodium hydroxide solution.
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| CN104562145B (en) * | 2014-12-23 | 2018-05-11 | 昆明理工大学 | A kind of method that combined oxidation prepares bioceramic film |
| 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 |
| 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 |
| 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 |
| 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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| EP2212453B1 (en) * | 2007-10-25 | 2012-07-04 | Plasma Coatings Limited | Method of forming a bioactive coating |
| WO2013072576A1 (en) * | 2011-11-14 | 2013-05-23 | Obl (Société Anonyme) | Method for the surface treatment of titanium bone implants using, in order, a sodium hydroxide bath and anodization |
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| CN102605410A (en) * | 2012-03-21 | 2012-07-25 | 西安理工大学 | Method for preparing bioactive composite film layer containing hydroxyapatite on titanium metal surface |
| CN103572346B (en) * | 2012-07-27 | 2015-11-25 | 北京纳通科技集团有限公司 | Hydroxyapatite surface film and preparation method thereof |
| CN103451706B (en) * | 2013-09-02 | 2016-01-27 | 吉林大学 | A kind of titanium surface directly generates the preparation method of hydroxyl apatite bioceramic film |
| CN103498183A (en) * | 2013-10-17 | 2014-01-08 | 赵全明 | Preparation technology of hydroxyapatite-containing composite biological film on titanium-base surface |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| EP2212453B1 (en) * | 2007-10-25 | 2012-07-04 | Plasma Coatings Limited | Method of forming a bioactive coating |
| WO2013072576A1 (en) * | 2011-11-14 | 2013-05-23 | Obl (Société Anonyme) | Method for the surface treatment of titanium bone implants using, in order, a sodium hydroxide bath and anodization |
Non-Patent Citations (1)
| Title |
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| "Preparation of hydroxyapatite-containing titania coating on titanium substrate by micro-arc oxidation";Jia-Hua Ni，et al.;《Materials Research Bulletin》;20070213;第43卷(第1期);第45-53页 * |
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