CN102586837A - Method for directly preparing Ca/P biomedical ceramic membrane on surface of magnesium alloy - Google Patents
Method for directly preparing Ca/P biomedical ceramic membrane on surface of magnesium alloy Download PDFInfo
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- CN102586837A CN102586837A CN2011100067775A CN201110006777A CN102586837A CN 102586837 A CN102586837 A CN 102586837A CN 2011100067775 A CN2011100067775 A CN 2011100067775A CN 201110006777 A CN201110006777 A CN 201110006777A CN 102586837 A CN102586837 A CN 102586837A
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Abstract
The invention discloses a method for directly preparing a Ca/P biomedical ceramic membrane on the surface of magnesium alloy and relates to a magnesium alloy surface processing technology. The method comprises a pretreatment step and a microarc oxidation process step. In the microarc oxidation process step, deionized water is used as a solvent; electrolyte consists of 10 to 30g/L of sodium metaaluminate, 1 to 5g/L of potassium hydroxide, 1 to 5g/L of disodium hydrogen phosphate or sodium phosphite or sodium hexametaphosphate and 1 to 10g/L of EDTA (ethylene diamine tetraacetic acid) -Ca; and the microarc oxidation process step is carried out in a constant-current mode. The biomedical ceramic membrane prepared by the method has nontoxicity and high corrosion resistance and wear resistance. The phase transformation and embrittlement of a matrix which are caused by preparation by adopting a conventional high temperature coating technology, are overcome. The idea of forming the uniform ceramic membrane on the metal matrix with a complex shape or a porous surface is implemented. The membrane layer is firmly combined with the matrix. The Ca/P biomedical ceramic membrane also has the advantages that process equipment is simple; an operating method is easy to control; the product has low cost and excellent effect; the Ca/P biomedical ceramic membrane is safe and reliable to use in a human body, is suitable to clinical and medical popularization, has wide application development prospect, and the like.
Description
Technical field:The present invention relates to a kind of surface treatment method of Mg alloy, specifically utilize differential arc oxidization technique directly to prepare the treatment process of bio-medical ceramic membrane at Mg alloy surface.
Background technology:Magnesium and magnesiumalloy base biomaterial are most possibly to become metal-based body implanting material of future generation.Magnesium and magnesiumalloy have the performance that much is superior to other metallic biomaterials as hard tissue implanting material.For example, (1) magnesium resource is abundant, and is cheap; (2) density (1.74g/cm of magnesiumalloy
3) with the density (1.75g/cm of people's bone
3) very close, lighter by about 25% than aluminium, far below Ti
6Al
4Density (the 4.47g/cm of V
3); (3) magnesiumalloy has very high specific tenacity and specific rigidity, and processing characteristics is good, the specific tenacity 133GPa/ (g/cm of pure magnesium
3), and the specific tenacity 480GPa/ (g/cm of superhigh strength magnesium alloy
3) compare Ti
6Al
4260GPa/ (the g/cm of V
3) also Gao Jinyi times; (4) when with the metallic substance implant into body, because of two kinds of elasticity modulus of materials stress-shielding effect that produces that do not match is one of negative factor that influence osteogenesis, the application magnesiumalloy can be alleviated this stress-shielding effect effectively; (5) magnesium is the interior positive ion of cell that is only second to potassium in the human body, and its participates in a series of metabolic activity in cell, comprises the formation of osteocyte, accelerated bone cell healing ability etc.Magnesium is also in close relations with nerve, muscle and heart function.Make hard tissue implanting material with magnesium and magnesiumalloy, not only need not consider the toxicity of trace metal ion pair cell, and the mg ion in the embedded material trace of human body is discharged still is useful.This shows that magnesiumalloy is superior to other metallic substance in medically application.
But corrosion stability of magnesium alloy is poor; Make magnesium and magnesiumalloy as there being very big gap between the application potential of bio-medical material and its feasibility, greatly limited its application, and the physiological environment of human body is that embedded material is required harsh corrosive environment at biomedical aspect; Therefore; In order to bring into play the high-performance of magnesiumalloy better, it is more widely used, must handle its surface.At present, the main method of Mg alloy surface being handled has: chemical conversion, laser surface modification, physical vapor deposition, electrochemical surface modification etc.Though these methods can effectively overcome the shortcoming that magnesiumalloy is anti-corrosion, wear no resistance; But consider that final surface-treated magnesiumalloy is as embedded material; Except having good anti-corrosion, wear resistance, also must guarantee the nontoxicity of coating, so how infeasible aforesaid method is.Adopt the conventional high-temperature paint-on technique can contain the bioceramic film of Ca/P according to the pertinent data report in the Ti-Ni alloy surface preparation; But be prone to cause matrix phase transformation and embrittlement; And be difficult to defective in complex-shaped alloy substrate surface preparation, still there is the low problem of rete and substrate combinating strength
.
The differential arc oxidization technique that on the anodizing technology basis, grows up in recent years can be used for Magnesiumalloy surface modifying.But existing technology of preparing about the magnesium alloy surface micro-arc oxidation ceramic membrane mainly still is applied to industrial production; For example " composite ceramic film on surface of magnesium alloy and the generation method " of the Chinese patent of Shanghai Metal Corrosion &. Protection Techn Co., Ltd application number 02111521.4 is exactly to utilize differential arc oxidization technique that Mg alloy surface is carried out modification; They utilize the electrolytic solution that contains materials such as ethyl silicate, aluminum fluosilicate, Sodium Silicofluoride 98min or potassium silicofluoride to generate the ceramic layer that contains silicon and fluorine at Mg alloy surface; The solidity to corrosion and the wear resistance of magnesiumalloy have been improved effectively; But fluorine that contains in this composite film and silicon are harmful materials, can not use as bioceramic film at all.
Summary of the invention:Task of the present invention provides a kind of method that directly prepares Ca/P bio-medical ceramic membrane at Mg alloy surface.Purpose is to solve in the existing Mg alloy surface processing rete and contains poisonous objectionable impurities; And the bioceramic film that conventional high-temperature paint-on technique preparation contains Ca/P is prone to cause matrix phase transformation and embrittlement; Be difficult in complex-shaped alloy substrate surface preparation and rete and the low problem
of substrate combinating strength.
The method that directly prepares Ca/P bio-medical ceramic membrane at Mg alloy surface of the present invention is made up of pre-treatment, micro-arc oxidation process step.Wherein said differential arc oxidation is to be solvent with the deionized water; A kind of 1 ~ 5g/L of sodium metaaluminate 10 ~ 30g/L, Pottasium Hydroxide 1 ~ 5g/L, Sodium phosphate, dibasic or inferior sodium phosphate or Sodium hexametaphosphate 99, EDTA-Ca 1 ~ 10g/L form electrolytic solution, and are 15 ~ 45mA/cm in the direct impulse current density
2, forward work ratio is 15 ~ 45%, the negative-going pulse current density is 5 ~ 15mA/cm
2, negative sense work ratio is 15 ~ 45%, pulse-repetition is to carry out under the constant current mode of 60 ~ 200Hz.
The said differential arc oxidation time is 5 ~ 20min.
Carry out differential arc oxidation under the said constant current mode, promptly electric current changes from small to big in the differential arc oxidation process, and is invariable during to set(ting)value.
The present invention mainly is to biomedical sector; Select the component and the rational proportion of environmental protection electrolytic solution; Control current density and frequency utilize differential arc oxidization technique to be implemented in the preparation that the fine and close bio-medical ceramic membrane of porous of Ca and P is rich in the original position generation on the magnesium alloy substrate at Mg alloy surface.Not only have toxicological harmless and higher solidity to corrosion (the especially solidity to corrosion in Hank ' s solution) and wear resistance; Can overcome simultaneously matrix phase transformation and the embrittlement adopting the preparation of conventional high-temperature paint-on technique and cause; Be implemented in the conception that forms uniform ceramic on the metal base of complex-shaped or porous surface; And rete and matrix bond are quite firm, thereby have further widened the range of application of magnesiumalloy in clinical medicine domain.Advantages such as this invention has also that processing unit is simple, working method is easy to control, the low effect of product cost is good, safe and reliable, suitable clinical medicine is promoted in the human body, development and application has a extensive future.
Description of drawings:
Fig. 1 is the XRF spectrogram of the ceramic coating formed by micro-arc oxidation that contains Ca and P for preparing at Mg alloy surface;
Fig. 2 is the electron scanning micrograph of the ceramic coating formed by micro-arc oxidation that contains Ca and P for preparing at Mg alloy surface;
Fig. 3 is the electrokinetic potential polarization curve of the ceramic coating formed by micro-arc oxidation that contains Ca and P for preparing at Mg alloy surface;
Embodiment:A kind of direct method for preparing Ca/P bio-medical ceramic membrane at Mg alloy surface of the present invention is made up of pre-treatment 1 and differential arc oxidation 2 process steps.Mg alloy surface is being carried out must carry out pre-treatment 1 before the differential arc oxidation 2, pre-treatment 1 mainly is to magnesiumalloy sanding and polishing successively, acetone ultrasonic cleaning; Purpose is to remove Mg alloy surface oxide compound and grease, makes it clean more.Differential arc oxidation 2 is key links of the present invention; It is to be solvent with the deionized water; Any one 1 ~ 5g/L, EDTA-Ca 1 ~ 10g/L form electrolytic solution in sodium metaaluminate 10 ~ 30g/L, Pottasium Hydroxide 1 ~ 5g/L, Sodium phosphate, dibasic or inferior sodium phosphate or the Sodium hexametaphosphate 99; Be anode with the magnesiumalloy after pre-treatment 1 art breading again, work nest is a negative electrode, electrical parameter is set be: the direct impulse current density is 15 ~ 45mA/cm
2, forward work ratio is 15 ~ 45%, the negative-going pulse current density is 5 ~ 15mA/cm
2, negative sense work ratio is 15 ~ 45%, pulse-repetition is 60 ~ 200Hz, differential arc oxidation 5 ~ 20min under constant current mode.The used for magnesium alloy deionized water rinsing that then differential arc oxidation 2 is obtained 3 ~ 4 times, seasoning promptly obtains at the bio-medical ceramic membrane that be rich in Ca/P of Mg alloy surface through the differential arc oxidation preparation.When adopting constant current mode to carry out differential arc oxidation, voltage changes from small to big in the differential arc oxidation process, and is constant until steadily, voltage change scope 50-400V.See following embodiment (technical scheme of the present invention is not limited to the following stated embodiment) for details:
Embodiment one: at first Mg alloy surface is used 240 successively
#, 600
#, 800
#, 1200
#, 1500
#, 2000
#Sand paper carries out sanding and polishing, uses acetone ultrasonic cleaning 20min then, and is for use with putting into acetone soln after the washed with de-ionized water again.It promptly is pre-treatment 1; With the deionized water is solvent, gets sodium metaaluminate 15g/L, Pottasium Hydroxide 2g/L, Sodium phosphate, dibasic 4g/L, EDTA-Ca 2g/L and prepares differential arc oxidation electrolytic solution (each component materials is analytical pure in this electrolytic solution, the commercially available prod); Magnesiumalloy after handling with pre-treatment 1 again is an anode, and work nest is a negative electrode, and it is 15mA/cm that forward current density is set
2, forward work ratio is 45%, negative current density is 10mA/cm
2, negative sense work ratio is 45%, and pulse-repetition is to carry out differential arc oxidation 2 under the constant current mode of 60Hz, and the time is 5min; Then with promptly obtaining after the used for magnesium alloy deionized water rinsing 3 times of differential arc oxidation, the seasoning at the bio-medical ceramic membrane that is rich in Ca/P of Mg alloy surface through the differential arc oxidation preparation.We carry out X-ray fluorescence spectra (XRF) analysis to present embodiment at the ceramic membrane of Mg alloy surface preparation, and the test spectrogram is as shown in Figure 1.By knowing among Fig. 1,, Ca and P element have been rich in the rete through direct differential arc oxidation.
Embodiment two: what it was different with embodiment one is the composition of differential arc oxidation electrolytic solution: be made up of sodium metaaluminate 20g/L, Pottasium Hydroxide 2g/L, Sodium phosphate, dibasic 2g/L, EDTA-Ca 4g/L.
Embodiment three: what it was different with embodiment one also is that differential arc oxidation electrolytic solution is made up of sodium metaaluminate 25g/L, Pottasium Hydroxide 2g/L, inferior sodium phosphate 1g/L, EDTA-Ca 4g/L.
Embodiment four: it with implement one different be that differential arc oxidation electrolytic solution is made up of sodium metaaluminate 28g/L, Pottasium Hydroxide 3g/L, inferior sodium phosphate 5g/L, EDTA-Ca 5g/L.
Embodiment five: what present embodiment and embodiment one were different is that differential arc oxidation electrolytic solution is made up of sodium metaaluminate 15g/L, Pottasium Hydroxide 2g/L, Sodium hexametaphosphate 99 5g/L, EDTA-Ca 6g/L.
Embodiment six: it with embodiment one to five in one of different be that differential arc oxidation is at forward current density 30mA/cm
2, pulse-repetition 160Hz condition under carry out.One of other step and parameter and embodiment one to five are identical.
Embodiment seven: it with embodiment one to six in one of different be that differential arc oxidation is at forward current density 45mA/cm
2, pulse-repetition 100Hz condition under carry out.Other step and parameter are identical with one of embodiment one to six.
Embodiment eight: what it was different with one of embodiment one to seven is that the differential arc oxidation time is 10min.Other step and parameter are identical with embodiment one to seven.
Embodiment nine: what it was different with one of embodiment one to eight is that the differential arc oxidation time is 15min.Other step and parameter are identical with one of embodiment one to eight.
Above embodiment is all consistent with embodiment one through the XRF spectrogram that the experiment gained contains calcium phosphorus rete, can show further that containing calcium phosphorus in the oxidation film layer is Ca and P.
The electron scanning micrograph that contains calcium phosphorus rete that obtains for the present invention shown in Figure 2 can be known that by Fig. 2 the rete that the present invention obtains is typical differential arc oxidation pattern, also can see little micropore among the figure, and it is the spark discharge passage in the differential arc oxidation process.
The electrokinetic potential polarization curve that contain calcium phosphorus rete of Fig. 3 for obtaining in the specific embodiment of the invention, and following table 1 is the fitting result of Fig. 3.
The electrokinetic potential polarization curve fitting result of the ceramic membrane of table 1 the present invention preparation
Can know that by Fig. 3 and table 1 solidity to corrosion of the rete that this experiment obtains in Hank ' s solution is superior to the not rete of calcic phosphorus, is superior to the solidity to corrosion of magnesium alloy substrate more.Thus it is clear that, compared with prior art have outstanding substantive distinguishing features and obvious improvement by the Ca/P bio-medical ceramic membrane of the present invention's preparation.
Claims (3)
1. method that directly prepares Ca/P bio-medical ceramic membrane at Mg alloy surface; Form by pre-treatment (1) and differential arc oxidation (2) process step; It is characterized in that: said differential arc oxidation (2) is to be solvent with the deionized water; A kind of 1 ~ 5g/L of sodium metaaluminate 10 ~ 30g/L, Pottasium Hydroxide 1 ~ 5g/L, Sodium phosphate, dibasic or inferior sodium phosphate or Sodium hexametaphosphate 99, EDTA-Ca 1 ~ 10g/L form electrolytic solution, and are 15 ~ 45mA/cm in the direct impulse current density
2, forward work ratio is 15 ~ 45%, the negative-going pulse current density is 5 ~ 15mA/cm
2, negative sense work ratio is 15 ~ 45%, pulse-repetition is to carry out under the constant current mode of 60 ~ 200Hz.
2. the method that directly prepares Ca/P bio-medical ceramic membrane at Mg alloy surface according to claim 1, it is characterized in that: said differential arc oxidation (2) time is 5 ~ 20min.
3. the method that directly prepares Ca/P bio-medical ceramic membrane at Mg alloy surface according to claim 1, it is characterized in that: carry out differential arc oxidation under the said constant current mode, promptly electric current changes from small to big in the differential arc oxidation process, and is invariable during to set(ting)value.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103173765A (en) * | 2013-03-26 | 2013-06-26 | 哈尔滨工业大学 | Method for preparing composite film layer through depositing hydroxylapatite on magnesium alloy micro-arc oxidation film |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103173765A (en) * | 2013-03-26 | 2013-06-26 | 哈尔滨工业大学 | Method for preparing composite film layer through depositing hydroxylapatite on magnesium alloy micro-arc oxidation film |
| CN103173765B (en) * | 2013-03-26 | 2015-04-29 | 哈尔滨工业大学 | Method for preparing composite film layer through depositing hydroxylapatite on magnesium alloy micro-arc oxidation film |
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