CN102286767A - Composite coating on surface of magnesium alloy biological implant material and preparation method thereof - Google Patents
Composite coating on surface of magnesium alloy biological implant material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a composite coating on the surface of a magnesium alloy biological implant material. The composite coating consists of a transition layer and a diamond-like carbon (DLC) film layer, wherein the transition layer is positioned on the surface of a magnesium alloy matrix; the DLC film layer is positioned on the surface of the transition layer; the transition layer is an oxide porous film formed by magnesium atoms of the surface layer of the magnesium alloy in situ by a microarc oxidation technology; the surface aperture of the oxide porous film is less than or equal to 1,000 nm; the thickness of the transition layer is 3 to 15 mu m; and the thickness of the DLC film layer is 300 to 1,000 nm. Compared with the conventional magnesium alloy biological implant material, the composite coating has biocompatibility, corrosion resistance more excellent than that of the Ti/DLC composite coating, wear resistance and excellent film-based bonding force with the magnesium alloy matrix, can beneficially modify the surface of the magnesium alloy matrix, and promotes application of the magnesium alloy biological implant material to the organism.
Description
Technical field
The present invention relates to bio-medical metal implant material technical field, be specifically related to a kind of biocompatibility that has, have good film-substrate cohesion with magnesium alloy substrate, can improve the surface composite coating and preparation method thereof of the corrosion-resisting wear-proof performance of magnesium alloy biological implantation material.
Background technology
Bone and articular system are the tissues that human body mainly bears load, and reparation and replacement material after its wearing and tearing should have higher mechanical strength.Magnesium alloy is as hard tissue implanting material, and its mechanical property has satisfied the requirement as orthopedic implanting material preferably, can effectively avoid the problem because of causing osteoporosis to need second operation to take out; In addition, magnesium alloy degraded product and biocompatible, can not produce tangible negative interaction to human body, and the magnesium ion that trace discharges is useful to tissue growth, therefore, carried out at present with magnesium alloy as biological implantation material, for example the Study on biocompatibility and the clinical application research of materials such as bone immobilizing material, porous bone repair material and angiocarpy bracket.
Current, the reason of restriction magnesium alloy clinical application is numerous, and evaluation of its biocompatibility in for example long-term body comprises blood compatibility, cell compatibility etc., and wherein the solidity to corrosion difference is the one of the main reasons of restriction magnesium alloy clinical application.Studies show that: pure magnesium and alloy thereof pH be 7.4～7.6 and the erosion rate that is rich in the complex physiologic environment of system of chlorion too fast, in case implantable bioartificial body inside, not fully before the healing, implant has been lost its mechanical integrity at tissue.Therefore, the corrodibility essence of research magnesium and magnesium alloy, thus improve its performance by process for modifying surface, being magnesium alloy is widely used in key in the organism as biological implantation material.
Quasi-diamond (DLC) film has excellent specific properties such as high rigidity, low-friction coefficient and extensive chemical inertia, can effectively isolate matrix and Working environment, is comparatively ideal corrosion-resisting wear-proof coating of a kind of matrix; And, as biomaterial, the biocompatibility of DLC film is also reported by the lot of domestic and foreign researcher, therefore, at the surface preparation DLC of magnesium alloy substrate film, not only can guarantee the biocompatibility of magnesium alloy biological implantation material, and can strengthen the corrosion resistance of this embedded material, provide feasibility in theory and experiment basis in the organism for the magnesium alloy biological implantation material is widely used in.
But, because the DLC film has high residual stress, easily cause the film cracking, peel off and lost efficacy, thereby restriction coating growth, cause film-substrate cohesion to descend, this is the key factor of serious at present restriction DLC film as the corrosion-resisting wear-proof coating, especially at chemically reactive height, " soft matrix " material surface that hardness is low, for example magnesium and magnesium alloy matrix surface, the difficulty of preparation physiologically acceptable DLC film will be bigger also.Therefore, strengthening the film-substrate cohesion of magnesium alloy substrate and DLC film, is that the magnesium alloy biological implantation material is widely used in one of effective way in the organism.
Differential arc oxidation (MAO) technology be a kind of can be in simple and easy technology of constructing the ceramic oxides porous membrane structure of alloy surface such as magnesium, aluminium, titaniums, its principle of work is that alloy products such as magnesium, aluminium, titanium are done anode, stainless steel is done negative electrode, place the electrolytic solution of pulsed electrical field environment, make product surface produce micro-arc discharge and generate one deck and matrix with metallurgical mode bonded oxide ceramic layer.Utilize differential arc oxidization technique at magnesium alloy biological implantation material surface construction oxide ceramic layer as modified coating, to improve the solidity to corrosion of magnesium alloy substrate, make other harmful element can not be introduced into this modified coating by matching suitable electrolyte system, thereby avoid this modified coating incompatible with the organism environment, this method is used in titanium alloy biological implantation material field at present to some extent.But there is micropore in the oxide ceramics laminar surface that differential arc oxidation produces, is difficult in the complex physiologic environment magnesium alloy biological implantation material be played effective protective effect.
Therefore, how making the magnesium alloy biological implantation material have good biocompatibility and erosion resistance by surface modification, is the important topic that promotes that the magnesium alloy biological implantation material is used in organism.
Summary of the invention
Technical purpose of the present invention is the deficiency that exists as biological implantation material at magnesium alloy, the compound coating on a kind of magnesium alloy biological implantation material surface and preparation method thereof is provided, this compound coating has biocompatibility, can improve the corrosion-resisting wear-proof performance of magnesium alloy biological implantation material, promote its application in organism.
The present invention realizes that the technical scheme that above-mentioned technical purpose adopts is: the compound coating on a kind of magnesium alloy biological implantation material surface, and by the transition layer that is positioned at magnesium alloy matrix surface, and the DLC thin film layer composition that is positioned at this transition layer surface; This transition layer is to utilize differential arc oxidization technique, make the oxide porous film of the magnesium atom original position formation on magnesium alloy substrate top layer, and the surface apertures of this oxide porous film is less than or equal to 1000nm; The thickness of this transition layer is 3～15 μ m, and the thickness of DLC thin film layer is 300～1000nm.
In order further to reduce the internal stress of DLC film, improve its biocompatibility, the active component that in the DLC film, mixes, the N that for example mixes, Ti constituent element.
The compound coating on above-mentioned magnesium alloy biological implantation material surface and the film matrix of magnesium alloy substrate are that the nano-indentation hardness value is 5～20GPa, with steel ball to the mill frictional coefficient below 0.2, corrosion electric current density significantly is lower than the Ti/DLC compound coating of titanium as transition layer.
The preparation method of the compound coating on magnesium alloy biological implantation material of the present invention surface comprises the steps:
Step 1: according to the matching principle of magnesium alloy differential arc oxidation electrolytic solution, the chemical reagent of selecting for use no harmful element to introduce, making the silicate that is fit to the requirement of medical magnesium alloy surface modification is differential arc oxidation electrolytic solution;
Step 2: adopt the DC pulse mao power source, by adjusting monopulse output energy and oxidization time, making the magnesium atom original position formation thickness on magnesium alloy substrate top layer is 3～15 μ m, and surface apertures is less than or equal to the differential arc oxidation thing porous-film of 1000nm;
Step 3: the magnesium alloy substrate after step 2 is handled carries out ultrasonic cleaning, dries behind the remaining electrolytic solution that contains in the micropore of removing magnesium alloy matrix surface differential arc oxidation porous-film;
Step 4: the magnesium alloy substrate after step 3 is handled places ionic fluid combined magnetic-controlled sputter depositing system, vacuumize, in the plated film cavity, feed acetylene gas by ion source then, on magnesium alloy substrate, apply-100～-pulsed bias of 300V, open ion source, electric current is 0.1～0.5A, is the DLC thin film layer of 300～1000nm at differential arc oxidation porous film surface deposit thickness.
As preferably, in the described step 2, the monopulse output voltage of DC pulse mao power source is 280～350V, and frequency is 400～800Hz, and dutycycle is 5～10%, and oxidization time is 3～10min.
As preferably, in the described step 4, in the plated film cavity, feed nitrogen simultaneously, thereby obtain the adulterated DLC thin film layer of nitrogen by ion source, detailed process is:
Magnesium alloy substrate after step 3 is handled places ionic fluid combined magnetic-controlled sputter depositing system, vacuumize, in the plated film cavity, feed the mixed gas of acetylene and nitrogen then by ion source, on the bitter earth alloy matrix, apply-100～-pulsed bias of 300V, open ion source, electric current is 0.1～0.5A, is the adulterated DLC thin film layer of nitrogen of 300～1000nm at differential arc oxidation porous film surface deposit thickness.
As preferably, in the described step 4, open sputtering source simultaneously, with the titanium sputtering target material, in the adulterated thin film layer detailed process of differential arc oxidation porous film surface titanium deposition be:
Magnesium alloy substrate after step 3 is handled places ionic fluid combined magnetic-controlled sputter depositing system, vacuumize, in the plated film cavity, feed acetylene gas by ion source then, on the bitter earth alloy matrix, apply-100～-pulsed bias of 300V, open ion source, electric current is 0.1～0.5A, with the titanium is sputtering target material, open sputtering source, electric current is the titanium doped DLC thin film layer of 300～1000nm at 1～3A at differential arc oxidation porous film surface deposit thickness.
Compared with prior art, the present invention is a matrix with the magnesium alloy biological implantation material, at first utilize on its surface differential arc oxidization technique introduce thickness be 3～15 μ m, surface apertures at 1000nm with interior arc differential oxide ceramic layer as transition layer, the DLC thin film layer that is 300～1000nm at this transition layer surface preparation thickness then, formation has the MAO/DLC compound coating of excellent properties, and the useful performance performance of this compound coating is as follows:
(1) arc differential oxide ceramic layer is as transition layer, and its technology is simple, environmental protection, coating structure are controlled, do not introduce harmful element, has biocompatibility; The DLC film has biocompatibility, and the DLC film of the N that especially mixes, Ti isoreactivity constituent element will further reduce the internal stress of DLC film, improves its biocompatibility; Therefore, this compound coating has excellent biocompatibility, as cell compatibility, blood compatibility etc.;
(2) because the existence of transition layer in the MAO/DLC compound coating, DLC thin film layer and combining of magnesium alloy substrate are changed into the combining of porous ceramic layer of DLC thin film layer and high rigidity, help the DLC film and discharge unrelieved stress and improve mechanical snap power, realize increasing considerably of film-substrate cohesion;
(3) metallurgical binding of the unreactiveness of DLC thin film layer self and porous ceramic layer and magnesium alloy substrate helps slowing down interfacial electrochemistry corrosion, improves the film matrix and ties up to solidity to corrosion in the organism environment, and its solidity to corrosion significantly is better than the Ti/DLC compound coating;
(4) high rigidity, low-friction coefficient, the strong film base interface bonding state of MAO/DLC compound coating and the constructional feature that the coatingsurface vesicular structure can hold biological fluid that are had of DLC thin film layer, help improving the tribological property of film matrix system, reach with steel ball the frictional coefficient of mill below 0.2.
Therefore, the MAO/DLC compound coating on magnesium alloy biological implantation material of the present invention surface is a kind of compound coating with biocompatibility, corrosion-resisting wear-proof performance, and has good film-substrate cohesion with magnesium alloy substrate, can realize useful modification to magnesium alloy matrix surface, satisfy the requirement of magnesium alloy materials in the biological and medicinal implant material field, promote the application of magnesium alloy biological implantation material in organism.
Description of drawings
Fig. 1 is MAO/DLC compound coating in the embodiment of the invention 1 and existing coating in concentration is polarization curve in 3.5% the NaCl solution.
Embodiment
Below in conjunction with specific embodiment the present invention is described in further detail.
Embodiment 1:
In the present embodiment, the compound coating on magnesium alloy biological implantation material surface is the MAO/DLC compound coating, be between magnesium alloy matrix surface and the DLC thin film layer transition layer to be arranged, this transition layer is to utilize differential arc oxidization technique, make the oxide porous film of the magnesium atom original position formation on magnesium alloy substrate top layer, and the surface apertures maximum value of this oxide porous film is 500nm, and the thickness of this transition layer is 5 μ m, and the thickness of DLC thin film layer is 600nm.
The preparation method of the compound coating on above-mentioned magnesium alloy biological implantation material surface comprises the steps:
Step 1: magnesium alloy substrate is selected the chemical reagent of no harmful element introducing for use through mechanical polishing, and making the silicate that is fit to the requirement of medical magnesium alloy surface modification is differential arc oxidation electrolytic solution;
Step 2: adopt the DC pulse mao power source, adjusting the monopulse output voltage is 300V, and frequency is 500Hz, dutycycle is 5%, oxidization time is 5min, and preparing thickness at magnesium alloy matrix surface is 5 μ m, and the surface apertures maximum value is the arc differential oxide ceramic layer of 500nm;
Step 3: the magnesium alloy substrate after step 2 is handled is dried behind the remaining electrolytic solution that contains in the removing magnesium alloy matrix surface arc differential oxide ceramic layer micropore through the acetone ultrasonic cleaning;
Step 4: the magnesium alloy substrate after step 3 is handled places ionic fluid combined magnetic-controlled sputter depositing system, forvacuum to 2 * 10
-5Torr; Feeding gas flow by ion source in the plated film cavity is the acetylene of 40sccm, apply on the differential arc oxidation magnesium alloy substrate-pulsed bias of 100V, open ion source, electric current is 0.2A, keeping this process 60min, is the DLC thin film layer of 600nm at ceramic layer surface deposition thickness.
The nano-indentation hardness value of the above-mentioned MAO/DLC compound coating that obtains is 12GPa, with steel ball to the mill frictional coefficient below 0.2, corrosion electric current density significantly is lower than Ti/DLC compound coating (as shown in Figure 1), and this compound coating has good biocompatibility.
Embodiment 2:
In the present embodiment, the compound coating on magnesium alloy biological implantation material surface is the MAO/N-DLC compound coating, be between the adulterated DLC thin film layer of magnesium alloy matrix surface and nitrogen (abbreviating the N-DLC thin film layer as) transition layer to be arranged, this transition layer is to utilize differential arc oxidization technique, make the oxide porous film of the magnesium atom original position formation on magnesium alloy substrate top layer, and the surface apertures maximum value of this oxide porous film is 400nm, and the thickness of this transition layer is 3 μ m, and the thickness of N-DLC thin film layer is 500nm.
The preparation method of the compound coating on above-mentioned magnesium alloy biological implantation material surface comprises the steps:
Step 1: magnesium alloy substrate is selected the chemical reagent of no harmful element introducing for use through mechanical polishing, and making the silicate that is fit to the requirement of medical magnesium alloy surface modification is differential arc oxidation electrolytic solution;
Step 2: adopt the DC pulse mao power source, adjusting the monopulse output voltage is 280V, and frequency is 800Hz, dutycycle is 5%, oxidization time is 3min, and preparing thickness at magnesium alloy matrix surface is 3 μ m, and the surface apertures maximum value is the arc differential oxide ceramic layer of 400nm;
Step 3: the magnesium alloy substrate after step 2 is handled is dried behind the remaining electrolytic solution that contains in the removing magnesium alloy matrix surface arc differential oxide ceramic layer micropore through the acetone ultrasonic cleaning;
Step 4: the magnesium alloy substrate after step 3 is handled places the ionic fluid combined magnetic-controlled sputter depositing system of independent development, forvacuum to 2 * 10
-5Torr; In the plated film cavity, feed the mixed gas of the nitrogen of the acetylene of 30sccm and 10sccm by ion source, on the differential arc oxidation magnesium alloy substrate, apply-pulsed bias of 100V, open ion source, electric current is 0.2A, keeping this process 60min, is the N-DLC thin film layer of 500nm at ceramic layer surface deposition thickness.
The nano-indentation hardness value of the above-mentioned MAO/N-DLC compound coating that obtains is 6GPa, with steel ball to the mill frictional coefficient below 0.2, corrosion electric current density significantly is lower than the Ti/DLC compound coating, and this compound coating has good biocompatibility.
Embodiment 3:
In the present embodiment, the compound coating on magnesium alloy biological implantation material surface is the MAO/Ti-DLC compound coating, be between magnesium alloy matrix surface and the titanium doped DLC thin film layer (abbreviating the Ti-DLC thin film layer as) transition layer to be arranged, this transition layer is to utilize differential arc oxidization technique, make the oxide porous film of the magnesium atom original position formation on magnesium alloy substrate top layer, and the surface apertures maximum value of this oxide porous film is 800nm, and the thickness of this transition layer is 12 μ m, and the thickness of Ti-DLC thin film layer is 800nm.
The preparation method of the compound coating on above-mentioned magnesium alloy biological implantation material surface comprises the steps:
Step 1: magnesium alloy substrate is selected the chemical reagent of no harmful element introducing for use through mechanical polishing, and making the silicate that is fit to the requirement of medical magnesium alloy surface modification is differential arc oxidation electrolytic solution;
Step 2: adopt the DC pulse mao power source, adjusting the monopulse output voltage is 350V, and frequency is 450Hz, dutycycle is 8%, oxidization time is 8min, and preparing thickness at magnesium alloy matrix surface is 12 μ m, and the surface apertures maximum value is the arc differential oxide ceramic layer of 800nm;
Step 3: the magnesium alloy substrate after step 2 is handled is dried behind the remaining electrolytic solution that contains in the removing magnesium alloy matrix surface arc differential oxide ceramic layer micropore through the acetone ultrasonic cleaning;
Step 4: the magnesium alloy substrate after step 3 is handled places the ionic fluid combined magnetic-controlled sputter depositing system of independent development, forvacuum to 2 * 10
-5Torr; In the plated film cavity, feed acetylene gas by ion source, on the differential arc oxidation magnesium alloy substrate, apply-pulsed bias of 100V, open ion source, electric current is 0.2A, with Ti is sputtering target material, opens sputtering source, and electric current is at 2A, keeping this process 70min, is the Ti-DLC thin film layer of 800nm at ceramic layer surface deposition thickness.
The nano-indentation hardness value of the above-mentioned MAO/Ti-DLC compound coating that obtains is 10GPa, with steel ball to the mill frictional coefficient below 0.2, corrosion electric current density significantly is lower than the Ti/DLC compound coating, and this compound coating has good biocompatibility.
Claims (8)
1. the compound coating on a magnesium alloy biological implantation material surface is characterized in that: by the transition layer that is positioned at magnesium alloy matrix surface, and the DLC thin film layer that is positioned at this transition layer surface is formed; Described transition layer is to utilize differential arc oxidization technique, make the oxide porous film of the magnesium atom original position formation on magnesium alloy substrate top layer, and the surface apertures of this oxide porous film is less than or equal to 1000nm; The thickness of described transition layer is 3～15 μ m, and the thickness of DLC thin film layer is 300～1000nm.
2. the compound coating on magnesium alloy biological implantation material according to claim 1 surface is characterized in that: active component mixes in the described DLC film.
3. the compound coating on magnesium alloy biological implantation material according to claim 1 surface is characterized in that: described active component is nitrogen or titanium.
4. the compound coating on magnesium alloy biological implantation material according to claim 1 surface is characterized in that: the film matrix of described compound coating and magnesium alloy substrate is that the nano-indentation hardness value is 5～20GPa, with steel ball to the mill frictional coefficient below 0.2.
5. the preparation method of the compound coating on magnesium alloy biological implantation material according to claim 1 surface is characterized in that: comprise the steps:
Step 1: according to the matching principle of magnesium alloy differential arc oxidation electrolytic solution, the chemical reagent of selecting for use no harmful element to introduce, making the silicate that is fit to the requirement of medical magnesium alloy surface modification is differential arc oxidation electrolytic solution;
Step 2: adopt the DC pulse mao power source, by adjusting monopulse output energy and oxidization time, making the magnesium atom original position formation thickness on magnesium alloy substrate top layer is 3～15 μ m, and surface apertures is less than or equal to the differential arc oxidation thing porous-film of 1000nm;
Step 3: the magnesium alloy substrate after step 2 is handled carries out ultrasonic cleaning, dries behind the remaining electrolytic solution that contains in the micropore of removing magnesium alloy matrix surface differential arc oxidation porous-film;
Step 4: the magnesium alloy substrate after step 3 is handled places ionic fluid combined magnetic-controlled sputter depositing system, vacuumize, in the plated film cavity, feed acetylene gas by ion source then, on magnesium alloy substrate, apply-100～-pulsed bias of 300V, open ion source, electric current is 0.1～0.5A, is the DLC thin film layer of 300～1000nm at differential arc oxidation porous film surface deposit thickness.
6. the preparation method of the compound coating on magnesium alloy biological implantation material according to claim 5 surface, it is characterized in that: in the described step 2, the monopulse output voltage of DC pulse mao power source is 280～350V, frequency is 400～800Hz, dutycycle is 5～10%, and oxidization time is 3～10min.
7. the preparation method of the compound coating on magnesium alloy biological implantation material according to claim 5 surface, it is characterized in that: in the described step 4, feed nitrogen simultaneously by ion source in the plated film cavity, thereby obtain the adulterated DLC thin film layer of nitrogen, detailed process is:
Magnesium alloy substrate after step 3 is handled places ionic fluid combined magnetic-controlled sputter depositing system, vacuumize, in the plated film cavity, feed the mixed gas of acetylene and nitrogen then by ion source, on the bitter earth alloy matrix, apply-100～-pulsed bias of 300V, open ion source, electric current is 0.1～0.5A, is the adulterated DLC thin film layer of nitrogen of 300～1000nm at differential arc oxidation porous film surface deposit thickness.
8. the preparation method of the compound coating on magnesium alloy biological implantation material according to claim 5 surface, it is characterized in that: in the described step 4, opening sputtering source simultaneously, is sputtering target material with the titanium, in the adulterated thin film layer detailed process of differential arc oxidation porous film surface titanium deposition is:
Magnesium alloy substrate after step 3 is handled places ionic fluid combined magnetic-controlled sputter depositing system, vacuumize, in the plated film cavity, feed acetylene gas by ion source then, on the bitter earth alloy matrix, apply-100～-pulsed bias of 300V, open ion source, electric current is 0.1～0.5A, with the titanium is sputtering target material, open sputtering source, electric current is the titanium doped DLC thin film layer of 300～1000nm at 1～3A at differential arc oxidation porous film surface deposit thickness.
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| CN109706503B (en) * | 2019-01-20 | 2021-03-09 | 中国科学院宁波材料技术与工程研究所 | Antibacterial wear-resistant coating on surface of titanium substrate and preparation method |
| JP2020138068A (en) * | 2020-06-09 | 2020-09-03 | 学校法人加計学園 | Surface treatment method of living body absorbing medical equipment |
| JP7041902B2 (en) | 2020-06-09 | 2022-03-25 | 学校法人加計学園 | Surface treatment method for bioabsorbable medical equipment |
| CN112656993A (en) * | 2021-03-16 | 2021-04-16 | 中南大学湘雅医院 | Composite film of blood vessel stent and preparation method thereof |
| CN114481074A (en) * | 2022-04-06 | 2022-05-13 | 中南大学湘雅医院 | Magnesium alloy surface coating material and application thereof |
| CN114481074B (en) * | 2022-04-06 | 2022-06-17 | 中南大学湘雅医院 | Magnesium alloy surface coating material and application thereof |
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