CN101775632B - Method for preparing hydroxyapatite film layer directly on surface of medical nickel-titanium alloy - Google Patents
Method for preparing hydroxyapatite film layer directly on surface of medical nickel-titanium alloy Download PDFInfo
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- CN101775632B CN101775632B CN2010101445080A CN201010144508A CN101775632B CN 101775632 B CN101775632 B CN 101775632B CN 2010101445080 A CN2010101445080 A CN 2010101445080A CN 201010144508 A CN201010144508 A CN 201010144508A CN 101775632 B CN101775632 B CN 101775632B
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Abstract
The invention discloses a method for preparing a hydroxyapatite film layer directly on the surface of a medical nickel-titanium alloy, in particular to a method for preparing the hydroxyapatite film layer on the surface of the nickel-titanium alloy. The method solves the problems of the existing method for preparing bioactive film layer by means of microarc oxidation on the surface of the nickel-titanium alloy: the nickel-titanium alloy is needed to be pretreated, the technology is complex, and the combination intensity of the obtained film layer and base body is low. The method comprises the following steps of: 1. treating the surface of the medical nickel-titanium alloy; 2. preparing electrolyte; 3. setting electric parameter by taking the medical nickel-titanium alloy as anode and the stainless steel as cathode to perform the microarc oxidation; and 4. performing hydro-thermal treatment in a hot-water high-pressure kettle to obtain the hydroxyapatite film layer. The method has simple technology, and directly prepares the hydroxyapatite film layer with high bioactivity and bonding force on the medical nickel-titanium alloy by means of microarc oxidation and hydro-thermal treatment, wherein the film layer is a composite film layer of hydroxyapatite and aluminium oxide.
Description
Technical field
The present invention relates to a kind of method of Ni-Ti alloy surface preparation hydroxyapatite film layer.
Background technology
NiTi (NiTi) shape memory alloy has obtained application owing to have excellent properties such as shape memory characteristic, super-elasticity, low elastic modulus and good anti-corrosion as bio-medical material in dentistry, orthopaedics, reduction face amount surgery and thoracic surgery.But because NiTi shape memory alloy built-in problem and shortcoming though obtained to use at clinical medicine, also can't satisfy clinical demand as embedded material.The NiTi shape memory alloy exists the problem aspect two in clinical application: the Ni that contains nearly 50% (at) in (1) NiTi shape memory alloy, in the long-term implantation process, owing to corrosion causes the Ni ion stripping with genotoxic potential, thereby cause the safety issue of human body; Need bear anti abrasive implant such as joint prosthesis for some,, the biocompatibility of NiTi shape memory alloy be reduced because the chip that wearing and tearing produce can injure human body.(2) the NiTi shape memory alloy is not have bioactive inert material, can not directly combine with bone.This implant must make healing time prolong, and increases patient's misery.The direct bonded stress transmission of NiTi shape memory alloy and bone is discontinuous, be hit for a long time, after the burn into wearing and tearing, implant is easy to become flexible, and causes the failure of operation.Therefore, how overcoming the NiTi shape memory alloy by surface modification and have above-mentioned shortcoming, is the active demand of clinical medicine.
Hydroxyapatite is the main component that constitutes bone and tooth, has good biocompatibility and biological activity, is typical biological active materials.But its mechanical property is relatively poor, can only be used for the not position of carry load.At NiTi shape memory alloy surface preparation hydroxyapatite film layer, can give full play to the good mechanical property of NiTi shape memory alloy and the biological activity of hydroxylapatite ceramic material by surface modifying method.At present, the application surface modification mainly contains in the method for medical NiTi alloy surface preparation activity hydroxy phosphatic rock: carry out methods such as bionical deposition, sol-gel process after plasma spraying, the chemical treatment in simulated body fluid, though using aforesaid method can be at medical NiTi alloy surface preparation uniform hydroxylapatite rete, but regrettably prepared hydroxyapatite film layer and high base strength are not high, can't satisfy the clinical medicine demand.
Differential arc oxidation is a kind of new technology at metallic surface growth in situ membrane of oxide ceramics, the modification that differential arc oxidization technique is used for medical titanium and titanium alloy surface has many advantages, as prepared ceramic membrane surface rough porous, can increase the contact area of embedded material and organism.In addition, the most outstanding advantage is that prepared ceramic film and matrix has very high bonding strength.
Therefore, at present researchist's sight drops on one after another again having on the Ni-Ti alloy of better medical value and utilizes differential arc oxidation to prepare bioactive film, and is active and by the prepared not high problem of active rete bonding strength of additive method to solve existing NiTi alloy lifeless matter.With medical pure Ti and Ti-6Al-4V alloy phase ratio, the NiTi alloy ratio is difficult to differential arc oxidation, the researchist is before carrying out differential arc oxidation to Ni-Ti alloy, all it is carried out pre-treatment, carry out titanizing etc. as thermal treatment, arc ion plating apparatus, form titanium or titanium oxide layer at the NiTi alloy surface, carry out differential arc oxidation again and handle.Though this method can prepare oxidation film layer and bioactive film at the NiTi alloy surface, but be essentially different with differential arc oxidation method, to not be metallurgical binding between rete and the matrix, be difficult to give full play to the advantage of differential arc oxidation method: rete and matrix have very high bonding strength.Simultaneously, because the existence of pretreatment technology, make process complications, production cost is higher.
Prepare TiO by thermal treatment at the NiTi alloy surface
2Rete punctures preparation activity hydroxy phosphatic rock rete by big electric current then, and this method can produce a large amount of crackles at film surface, further reduces rete and high base strength.Even activity hydroxy phosphatic rock rete and matrix have very high bonding strength, still lack permanent stability.Carry out titanizing by arc ion plating apparatus, carry out differential arc oxidation then, clearly titanium and NiTi alloy are not metallurgical binding in this way, and the bonding strength by follow-up differential arc oxidation method prepared membrane and NiTi alloy substrate can be starkly lower than directly by rete and the high base strength of differential arc oxidation in the preparation of NiTi alloy surface.
Summary of the invention
The objective of the invention is needs carry out pre-treatment to Ni-Ti alloy, complex process, cost height, and rete that obtains and the low problem of substrate combinating strength in order to solve in the method that existing Ni-Ti alloy surface by micro-arc oxidation prepares bioactive film.The invention provides a kind of direct method at Nickel-titanium alloy for medical purpose surface preparation hydroxyapatite film layer.
Direct method at Nickel-titanium alloy for medical purpose surface preparation hydroxyapatite film layer of the present invention realizes by following steps: one, Nickel-titanium alloy for medical purpose is carried out deoxidation film, oil removal treatment successively; Two, the sodium phosphate of the neurosin of the sodium aluminate of preparation electrolytic solution: 8 ~ 15g/L, 6 ~ 12g/L or calcio-disodium edetate, 4 ~ 8g/L, solvent is a deionized water; Three, be anode with the Nickel-titanium alloy for medical purpose after the step 1 processing, in the electrolytic solution with the configuration of the fixing immersion of anchor clamps step 2, the stainless steel electrolytic liquid bath is a negative electrode, adopt the bidirectional pulse power supply, electrical parameter is set is: positive pulse voltage is that 300 ~ 500V, negative pulse voltage are that 0 ~ 30 V, pulse-repetition 30 ~ 500Hz, dutycycle are 45%, carries out differential arc oxidation 3 ~ 30min; Four, the Ni-Ti alloy after step 3 is handled is put into the hydro-thermal autoclave, temperature rise rate with 2 ~ 10 ℃/min is warming up to 200 ~ 300 ℃ then, insulation 2 ~ 10h, control hydro-thermal autoclave internal pressure is 2 ~ 10MPa in the insulating process, promptly gets hydroxyapatite film layer in the Ni-Ti alloy surface preparation.
Sodium phosphate can also replace with inferior sodium phosphate in the electrolytic solution of step 2 of the present invention, and the mass concentration of inferior sodium phosphate is 6 ~ 10g/L.Sodium phosphate can also replace with sodium polyphosphate in the electrolytic solution of step 2, and the mass concentration of sodium polyphosphate is 4 ~ 10g/L.
The present invention adopts constant voltage mode to carry out differential arc oxidation, in the differential arc oxidation process current density from large to small, invariable to the minimum value.The current density change scope is that current density is 5 ~ 0.2A/cm
2
The present invention at first directly adopts the differential arc oxidation method to prepare the ceramic film that is rich in Ca and P on Nickel-titanium alloy for medical purpose, is a kind of metallurgical binding between rete and the Ni-Ti alloy substrate, the bonding force height; Utilize hydrothermal treatment consists to make that Ca and P are transformed into hydroxyapatite in the ceramic film then, prepare biologically active, hydroxyapatite film layer that bonding force is strong at Ni-Ti alloy.
The present invention has broken through the application limitations that differential arc oxidation is only realized on valve metal, simplified technology, has saved cost, has realized the preparation of Nickel-titanium alloy for medical purpose surface bioactive hydroxyapatite film layer; By choosing suitable electrolytic solution composition and respective concentration, control differential arc oxidation voltage, frequency, containing the Ca of higher concentration and the ceramic film of P in the generation of the surperficial directly differential arc oxidation of Nickel-titanium alloy for medical purpose.By the time and the pressure of control hydrothermal treatment consists, hydroxyapatite film layer is separated out on the Nickel-titanium alloy for medical purpose surface then.
The present invention is hydroxyapatite (HA) and aluminium sesquioxide (Al at the rete of Nickel-titanium alloy for medical purpose surface preparation
2O
3) composite film.The present invention has not only improved the erosion resistance and the biocompatibility of Nickel-titanium alloy for medical purpose, the more important thing is to make Nickel-titanium alloy for medical purpose possess biological activity, and promotion Nickel-titanium alloy for medical purpose embedded material combines with osseous tissue.This composite film (HA-Al
2O
3) have higher binding strength with matrix, enlarged the range of application of Nickel-titanium alloy for medical purpose.
Description of drawings
Fig. 1 is X-ray diffraction (XRD) spectrogram of the hydroxyapatite film layer that obtains in the Ni-Ti alloy surface preparation in the embodiment one; Fig. 2 is the electron scanning micrograph of the hydroxyapatite film layer that obtains in the Ni-Ti alloy surface preparation in the embodiment 23.
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 directly realizes by following steps in the method for Nickel-titanium alloy for medical purpose surface preparation hydroxyapatite film layer: one, Nickel-titanium alloy for medical purpose is carried out deoxidation film, oil removal treatment successively; Two, the sodium phosphate of the neurosin of the sodium aluminate of preparation electrolytic solution: 8 ~ 15g/L, 6 ~ 12g/L or calcio-disodium edetate, 4 ~ 8g/L, solvent is a deionized water; Three, be anode with the Nickel-titanium alloy for medical purpose after the step 1 processing, in the electrolytic solution with the configuration of the fixing immersion of anchor clamps step 2, the stainless steel electrolytic liquid bath is a negative electrode, adopt the bidirectional pulse power supply, electrical parameter is set is: positive pulse voltage is that 300 ~ 500V, negative pulse voltage are that 0 ~ 30 V, pulse-repetition 30 ~ 500Hz, dutycycle are 45%, carries out differential arc oxidation 3 ~ 30min; Four, the Ni-Ti alloy after step 3 is handled is put into the hydro-thermal autoclave, temperature rise rate with 2 ~ 10 ℃/min is warming up to 200 ~ 300 ℃ then, insulation 2 ~ 10h, control hydro-thermal autoclave internal pressure is 2 ~ 12MPa in the insulating process, promptly gets hydroxyapatite film layer in the Ni-Ti alloy surface preparation.
The electrolytic solution ingredients substance is analytical pure in the present embodiment, the commercially available prod.
Present embodiment adopts constant voltage mode to carry out differential arc oxidation, and current density is for from large to small in the differential arc oxidation process, and the current density change scope is 5 ~ 0.2A/cm
2
Present embodiment has broken through the application limitations that differential arc oxidation is only realized on valve metal, simplified technology, has saved cost; Present embodiment is the composite film (HA-Al of hydroxyapatite and aluminium sesquioxide at the hydroxyapatite film layer of Nickel-titanium alloy for medical purpose surface preparation
2O
3), make Nickel-titanium alloy for medical purpose possess biological activity.
Present embodiment is carried out the test of X-ray diffraction spectrogram to get hydroxyapatite film layer in the Ni-Ti alloy surface preparation, and the test spectrogram as shown in Figure 1.By among Fig. 1 as can be known, contain aluminium sesquioxide (" " mark among the figure) and hydroxyapatite (" ● " mark among the figure) in the hydroxyapatite film layer, be the composite film of hydroxyapatite and aluminium sesquioxide.
Embodiment two: present embodiment and embodiment one are different be in the step 1 to Nickel-titanium alloy for medical purpose carry out the deoxidation film successively, oil removal treatment is: successively with 240#, 800#, the 1000# sand paper deoxidation film of polishing, clean with acetone then and remove surface and oil contaminant, deionized water ultrasonic cleaning is again dried naturally.
Embodiment three: what present embodiment was different with embodiment one or two is the sodium aluminate of preparing electrolytic solution: 10～13g/L in the step 2, the calcio-disodium edetate of 6 ~ 8g/L, the sodium phosphate of 5 ~ 7g/L.Other step and parameter are identical with embodiment one or two.
Embodiment four: present embodiment is different with embodiment one or two is the sodium phosphate of the neurosin of the sodium aluminate of preparing electrolytic solution: 12.3g/L in the step 2,6.2g/L or calcio-disodium edetate, 5.7g/L.Other step and parameter are identical with embodiment one or two.
Embodiment five: what present embodiment was different with embodiment one or two is the sodium aluminate of preparing electrolytic solution: 10～13g/L in the step 2, the neurosin of 7 ~ 10g/L, the sodium phosphate of 4.5 ~ 6.5g/L.Other step and parameter are identical with embodiment one or two.
Embodiment six: what present embodiment was different with embodiment one or two is the sodium aluminate of preparing electrolytic solution: 12g/L in the step 2, the neurosin of 8g/L, the sodium phosphate of 6g/L.Other step and parameter are identical with embodiment one or two.
Embodiment seven: what present embodiment was different with one of embodiment one to six is electrical parameter to be set in the step 3 be: positive pulse voltage is that 350 ~ 450V, negative pulse voltage are that 0 ~ 10 V, pulse-repetition 60 ~ 300Hz, dutycycle are 45%.Other step and parameter are identical with one of embodiment one to six.
Embodiment eight: what present embodiment was different with one of embodiment one to six is electrical parameter to be set in the step 3 be: positive pulse voltage is that 400V, negative pulse voltage are that 0V, pulse-repetition 150Hz, dutycycle are 45%.Other step and parameter are identical with one of embodiment one to six.
Embodiment nine: what present embodiment was different with one of embodiment one to eight is to carry out differential arc oxidation 5 ~ 20min in the step 3.Other step and parameter are identical with one of embodiment one to eight.
Embodiment ten: what present embodiment was different with one of embodiment one to eight is to carry out differential arc oxidation 10min in the step 3.Other step and parameter are identical with one of embodiment one to eight.
Embodiment 11: what present embodiment was different with one of embodiment one to ten is that the temperature rise rate with 4 ~ 8 ℃/min is warming up to 230 ~ 280 ℃ in the step 4.Other step and parameter are identical with one of embodiment one to ten.
Embodiment 12: what present embodiment was different with one of embodiment one to ten is that the temperature rise rate with 6 ℃/min is warming up to 250 ℃ in the step 4.Other step and parameter are identical with one of embodiment one to ten.
Embodiment 13: what present embodiment was different with one of embodiment one to 12 is to be incubated 4 ~ 8h in the step 4.Other step and parameter are identical with one of embodiment one to 12.
Embodiment 14: what present embodiment was different with one of embodiment one to 12 is to be incubated 6h in the step 4.Other step and parameter are identical with one of embodiment one to 12.
Embodiment 15: present embodiment is different with one of embodiment one to 14 be in the step 4 in the insulating process control hydro-thermal autoclave internal pressure be 6 ~ 10 MPa.Other step and parameter are identical with one of embodiment one to 14.
Embodiment 16: present embodiment is different with one of embodiment one to 14 be in the step 4 in the insulating process control hydro-thermal autoclave internal pressure be 8MPa.。Other step and parameter are identical with one of embodiment one to 14.
Embodiment 17: what present embodiment was different with one of embodiment one to 16 is that the electrolytic solution that step 2 disposes is: the inferior sodium phosphate of the sodium aluminate of 8 ~ 15g/L, the neurosin of 6 ~ 12g/L or calcio-disodium edetate, 6～10g/L, solvent are deionized water.Other step and parameter are identical with one of embodiment one to 16.
Embodiment 18: present embodiment and embodiment 17 are different is that the electrolytic solution of step 2 configuration is: the inferior sodium phosphate of the sodium aluminate of 10 ~ 13g/L, the neurosin of 6 ~ 10g/L or calcio-disodium edetate, 7～9g/L, solvent are deionized water.Other step and parameter are with specifically enforcement 17 is identical.
Embodiment 19: present embodiment and embodiment 17 are different is that the electrolytic solution of step 2 configuration is: the inferior sodium phosphate of the sodium aluminate of 12g/L, the neurosin of 8g/L or calcio-disodium edetate, 8g/L, solvent are deionized water.Other step and parameter are with specifically enforcement 17 is identical.
Embodiment 20: what present embodiment was different with one of embodiment one to 16 is that the electrolytic solution that step 2 disposes is: the sodium polyphosphate of the sodium aluminate of 8 ~ 15g/L, the neurosin of 6 ~ 12g/L or calcio-disodium edetate, 4 ~ 10g/L, solvent are deionized water.Other step and parameter are identical with one of embodiment one to 16.
Embodiment 21: present embodiment and embodiment 20 are different is that the electrolytic solution of step 2 configuration is: the sodium polyphosphate of the sodium aluminate of 10 ~ 13g/L, the neurosin of 6 ~ 10g/L or calcio-disodium edetate, 5 ~ 9g/L, solvent are deionized water.Other step and parameter are identical with embodiment 20.
Embodiment 22: present embodiment with concrete implement 20 different be that the electrolytic solution of step 2 configuration is: the sodium polyphosphate of the sodium aluminate of 12g/L, the neurosin of 8g/L or calcio-disodium edetate, 7g/L, solvent are deionized water.Other step and parameter are identical with embodiment 20.
Embodiment 23: present embodiment directly realizes by following steps in the method for Nickel-titanium alloy for medical purpose surface preparation hydroxyapatite film layer: one, to Nickel-titanium alloy for medical purpose successively with 240#, 800#, the 1000# sand paper deoxidation film of polishing, clean with acetone then and remove surface and oil contaminant, deionized water ultrasonic cleaning is again dried naturally; Two, the sodium aluminate of preparation electrolytic solution: 12.3g/L, the calcio-disodium edetate of 6.2g/L, the sodium phosphate of 5.0g/L; Three, be anode with the Nickel-titanium alloy for medical purpose after the step 1 processing, immerse in the electrolytic solution with anchor clamps are fixing, the stainless steel electrolytic liquid bath is a negative electrode, adopt the bidirectional pulse power supply, electrical parameter is set is: positive pulse voltage is that 400V, negative pulse voltage are that 0V, pulse-repetition 60Hz, dutycycle are 45%, carries out differential arc oxidation 15min; Four, the Ni-Ti alloy after step 3 is handled is put into the hydro-thermal autoclave, temperature rise rate with 4 ℃/min is warming up to 250 ℃ then, insulation 4h, control autoclave internal pressure is 8MPa in the insulating process, promptly gets hydroxyapatite film layer in the Ni-Ti alloy surface preparation.
The chemical ingredients of medical Ni-Ti alloy is 50.8% Ni by mass percentage in the present embodiment, 49.2% Ti.Sodium aluminate, calcio-disodium edetate and sodium phosphate are analytical pure, the commercially available prod.
Present embodiment adopts constant voltage mode to carry out differential arc oxidation, and current density is for from large to small in the differential arc oxidation process, and the current density change scope is 3 ~ 0.2A/cm
2
The XRD graphic representation of the hydroxyapatite film layer that present embodiment obtains is consistent with embodiment one, as shown in Figure 1.As seen from Figure 1, the main component of hydroxyapatite film layer is aluminium sesquioxide and hydroxyapatite, has good biological activity.
The electron scanning micrograph of the hydroxyapatite film layer that present embodiment obtains as shown in Figure 2, as shown in Figure 2, hydroxyapatite generates at film surface, hydroxyapatite is a needle crystal; Also can see little micropore by Fig. 2, it is the spark discharge passage in the differential arc oxidation process.
Embodiment 24: what present embodiment and embodiment 23 were different is the sodium aluminate of preparing electrolytic solution: 12.3g/L in the step 2, the calcio-disodium edetate of 6.2g/L, the inferior sodium phosphate of 8g/L, and solvent is a deionized water; Electrical parameter is set in the step 3 is: positive pulse voltage is that 400V, negative pulse voltage are that 0V, pulse-repetition 100Hz, dutycycle are 45%, carries out differential arc oxidation 15min; Temperature rise rate with 6 ℃/min in the step 4 is warming up to 300 ℃, insulation 4h, and control autoclave internal pressure is 10MPa in the insulating process.Other step and parameter are identical with embodiment 23.
The chemical ingredients of medical Ni-Ti alloy is 50.8% Ni by mass percentage in the present embodiment, 49.2% Ti.Sodium aluminate, calcio-disodium edetate and inferior sodium phosphate are analytical pure, the commercially available prod.
Present embodiment adopts constant voltage mode to carry out differential arc oxidation, and current density is for from large to small in the differential arc oxidation process, and the current density change scope is 3 ~ 0.2A/cm
2
The XRD graphic representation of the hydroxyapatite film layer that present embodiment obtains as shown in Figure 1.As seen from Figure 1, the main component of hydroxyapatite film layer is aluminium sesquioxide and hydroxyapatite, has good biological activity.
Embodiment 25: present embodiment directly realizes by following steps in the method for Nickel-titanium alloy for medical purpose surface preparation hydroxyapatite film layer: one, to Nickel-titanium alloy for medical purpose successively with 240#, 800#, the 1000# sand paper deoxidation film of polishing, clean with acetone then and remove surface and oil contaminant, deionized water ultrasonic cleaning is again dried naturally; Two, the sodium aluminate of preparation electrolytic solution: 12g/L, the calcio-disodium edetate of 8g/L, the sodium polyphosphate of 7g/L, solvent is a deionized water; Three, be anode with the Nickel-titanium alloy for medical purpose after the step 1 processing, immerse in the electrolytic solution with anchor clamps are fixing, the stainless steel electrolytic liquid bath is a negative electrode, adopt the bidirectional pulse power supply, electrical parameter is set is: positive pulse voltage is that 300V, negative pulse voltage are that 10V, pulse-repetition 300Hz, dutycycle are 45%, carries out differential arc oxidation 30min; Four, the Ni-Ti alloy after step 3 is handled is put into the hydro-thermal autoclave, temperature rise rate with 5 ℃/min is warming up to 300 ℃ then, insulation 4h, control autoclave internal pressure is 10MPa in the insulating process, promptly gets hydroxyapatite film layer in the Ni-Ti alloy surface preparation.
The chemical ingredients of medical Ni-Ti alloy is 50.8% Ni by mass percentage in the present embodiment, 49.2% Ti.Sodium aluminate, calcio-disodium edetate and sodium polyphosphate are analytical pure, the commercially available prod.
Present embodiment adopts constant voltage mode to carry out differential arc oxidation, and current density is for from large to small in the differential arc oxidation process, and the current density change scope is 2.8 ~ 0.2A/cm
2
The XRD graphic representation of the hydroxyapatite film layer that present embodiment obtains is consistent with embodiment one, as shown in Figure 1.As seen from Figure 1, the main component of hydroxyapatite film layer is aluminium sesquioxide and hydroxyapatite, has good biological activity.
Embodiment 26: present embodiment directly realizes by following steps in the method for Nickel-titanium alloy for medical purpose surface preparation hydroxyapatite film layer: one, to Nickel-titanium alloy for medical purpose successively with 240#, 800#, the 1000# sand paper deoxidation film of polishing, clean with acetone then and remove surface and oil contaminant, deionized water ultrasonic cleaning is again dried naturally; Two, the sodium aluminate of preparation electrolytic solution: 12g/L, the neurosin of 8g/L, the sodium phosphate of 6g/L; Three, be anode with the Nickel-titanium alloy for medical purpose after the step 1 processing, immerse in the electrolytic solution with anchor clamps are fixing, the stainless steel electrolytic liquid bath is a negative electrode, adopt the bidirectional pulse power supply, electrical parameter is set is: positive pulse voltage is that 400V, negative pulse voltage are that 0V, pulse-repetition 100Hz, dutycycle are 45%, carries out differential arc oxidation 20min; Four, the Ni-Ti alloy after step 3 is handled is put into the hydro-thermal autoclave, temperature rise rate with 4 ℃/min is warming up to 200 ℃ then, insulation 4h, control autoclave internal pressure is 6MPa in the insulating process, promptly gets hydroxyapatite film layer in the Ni-Ti alloy surface preparation.
The chemical ingredients of medical Ni-Ti alloy is 50.8% Ni by mass percentage in the present embodiment, 49.2% Ti.Sodium aluminate, neurosin and sodium phosphate are analytical pure, the commercially available prod.
Present embodiment adopts constant voltage mode to carry out differential arc oxidation, and current density is for from large to small in the differential arc oxidation process, and the current density change scope is 3 ~ 0.2A/cm
2
The XRD graphic representation of the hydroxyapatite film layer that present embodiment obtains is consistent with embodiment one, as shown in Figure 1.As seen from Figure 1, the main component of hydroxyapatite film layer is aluminium sesquioxide and hydroxyapatite, has good biological activity.
Claims (10)
1. a direct method at Nickel-titanium alloy for medical purpose surface preparation hydroxyapatite film layer is characterized in that direct method at Nickel-titanium alloy for medical purpose surface preparation hydroxyapatite film layer realizes by following steps: one, Nickel-titanium alloy for medical purpose is carried out deoxidation film, oil removal treatment successively; Two, the sodium phosphate of the neurosin of the sodium aluminate of preparation electrolytic solution: 8～15g/L, 6～12g/L or calcio-disodium edetate, 4～8g/L, solvent is a deionized water; Three, be anode with the Nickel-titanium alloy for medical purpose after the step 1 processing, in the electrolytic solution with the configuration of the fixing immersion of anchor clamps step 2, the stainless steel electrolytic liquid bath is a negative electrode, adopt the bidirectional pulse power supply, electrical parameter is set is: positive pulse voltage is that 300～500V, negative pulse voltage are that 0～30V, current density are 0.2～5A/cm
2, pulse-repetition 30～500Hz, dutycycle be 45%, carries out differential arc oxidation 3～30min; Four, the Ni-Ti alloy after step 3 is handled is put into the hydro-thermal autoclave, temperature rise rate with 2～10 ℃/min is warming up to 200～300 ℃ then, insulation 2～10h, control hydro-thermal autoclave internal pressure is 2～12MPa in the insulating process, promptly gets hydroxyapatite film layer in the Ni-Ti alloy surface preparation.
2. according to claim 1 a kind of directly in the method for Nickel-titanium alloy for medical purpose surface preparation hydroxyapatite film layer, it is characterized in that preparing in the step 2 sodium aluminate of electrolytic solution: 10～13g/L, the calcio-disodium edetate of 6～8g/L, the sodium phosphate of 5～7g/L.
3. according to claim 1 a kind of directly in the method for Nickel-titanium alloy for medical purpose surface preparation hydroxyapatite film layer, it is characterized in that preparing in the step 2 sodium aluminate of electrolytic solution: 10～13g/L, the neurosin of 7～10g/L, the sodium phosphate of 4.5～6.5g/L.
4. according to claim 1,2 or 3 described a kind of directly in the methods of Nickel-titanium alloy for medical purpose surface preparation hydroxyapatite film layer, it is characterized in that being provided with in the step 3 electrical parameter and be: positive pulse voltage is that 350～450V, negative pulse voltage are that 0～10V, pulse-repetition 60～300Hz, dutycycle are 45%.
5. according to claim 4 a kind of directly in the method for Nickel-titanium alloy for medical purpose surface preparation hydroxyapatite film layer, it is characterized in that carrying out in the step 3 differential arc oxidation 5～20min.
6. according to claim 1,2,3 or 5 described a kind of direct methods, it is characterized in that being incubated in the step 4 4～8h at Nickel-titanium alloy for medical purpose surface preparation hydroxyapatite film layer.
7. according to claim 6 a kind of directly in the method for Nickel-titanium alloy for medical purpose surface preparation hydroxyapatite film layer, it is characterized in that controlling hydro-thermal autoclave internal pressure in the insulating process in the step 4 is 6～10MPa.
8. according to claim 1,2,3,5 or 7 described a kind of direct methods, it is characterized in that being warming up to 230～280 ℃ with the temperature rise rate of 4～8 ℃/min at Nickel-titanium alloy for medical purpose surface preparation hydroxyapatite film layer.
9. according to claim 1,2,3,5 or 7 described a kind of direct methods at Nickel-titanium alloy for medical purpose surface preparation hydroxyapatite film layer, the electrolytic solution that it is characterized in that the step 2 configuration adopts following electrolytic solution to replace: the inferior sodium phosphate of the sodium aluminate of 8～15g/L, the neurosin of 6～12g/L or calcio-disodium edetate, 6～10g/L, solvent are deionized water.
10. according to claim 1,2,3,5 or 7 described a kind of direct methods at Nickel-titanium alloy for medical purpose surface preparation hydroxyapatite film layer, the electrolytic solution that it is characterized in that the step 2 configuration adopts following electrolytic solution to replace: the sodium polyphosphate of the sodium aluminate of 8～15g/L, the neurosin of 6～12g/L or calcio-disodium edetate, 4～10g/L, solvent are deionized water.
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Cited By (2)
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|---|---|---|---|---|
| CN102560601A (en) * | 2012-02-29 | 2012-07-11 | 哈尔滨工业大学 | Preparation method for microarc oxidation/hydrothermal treatment composite film on surface of magnesium alloy |
| CN102560595A (en) * | 2012-01-05 | 2012-07-11 | 哈尔滨工业大学 | Process for preparing composite coating of hydroxyapatite and porous titanium dioxide on biomedical titanium metal surface |
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| CN102560597A (en) * | 2012-01-05 | 2012-07-11 | 哈尔滨工业大学 | Method for preparing high bioactivity titanium dioxide coating containing nano-crystalline grains |
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| CN112281199B (en) * | 2020-10-05 | 2022-02-15 | 华中科技大学 | Preparation and application of ultrasonic-assisted micro-arc oxidation composite film layer based on solution system |
| CN113368315B (en) * | 2021-06-09 | 2022-04-19 | 河北工业大学 | Medical nickel-titanium alloy material with temperature-sensitive hydrogel coating and preparation method and application thereof |
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| JP2002129387A (en) * | 2000-10-19 | 2002-05-09 | R & D Inst Of Metals & Composites For Future Industries | Surface treatment method for titanium-nickel alloy |
| CN101153409A (en) * | 2006-09-30 | 2008-04-02 | 中南大学 | Method for producing TiO*/Na*Ti*O* biological ceramic film by differential arc oxidization |
| CN1974876B (en) * | 2006-11-02 | 2010-07-07 | 华南理工大学 | Bioactive film on titanium metal surface and its sand blasting-micro arc oxidizing compounding process |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102560595A (en) * | 2012-01-05 | 2012-07-11 | 哈尔滨工业大学 | Process for preparing composite coating of hydroxyapatite and porous titanium dioxide on biomedical titanium metal surface |
| CN102560601A (en) * | 2012-02-29 | 2012-07-11 | 哈尔滨工业大学 | Preparation method for microarc oxidation/hydrothermal treatment composite film on surface of magnesium alloy |
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