CN102286767B - 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
- Publication number
- CN102286767B CN102286767B CN2011101738669A CN201110173866A CN102286767B CN 102286767 B CN102286767 B CN 102286767B CN 2011101738669 A CN2011101738669 A CN 2011101738669A CN 201110173866 A CN201110173866 A CN 201110173866A CN 102286767 B CN102286767 B CN 102286767B
- Authority
- CN
- China
- Prior art keywords
- magnesium alloy
- layer
- dlc
- film
- differential arc
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
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, with magnesium alloy substrate, have good film-substrate cohesion, 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 met the requirement as orthopedic implanting material preferably, can effectively avoid the problem because causing osteoporosis to need second operation to take out; In addition, magnesium alloy degraded product and biocompatible, can not produce obvious negative interaction to human body, and the magnesium ion that trace discharges is useful to tissue growth, therefore, carried out and usingd magnesium alloy as biological implantation material at present, 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 for example evaluation of its biocompatibility in long-term body, comprise blood compatibility, cell compatibility etc., and wherein solidity to corrosion is poor is the one of the main reasons of restriction magnesium alloy clinical application.Research shows: pure magnesium and alloy thereof pH be 7.4～7.6 and be rich in the complex physiologic environment of system of chlorion in erosion rate too fast, in case implantable bioartificial body inside, not fully before healing, implant has been lost its mechanical integrity at tissue.Therefore, the corrodibility essence of research magnesium and magnesium alloy, thus by process for modifying surface, improve its performance, be that magnesium alloy is widely used in the key in organism as biological implantation material.
Quasi-diamond (DLC) film has the excellent specific properties such as high rigidity, low-friction coefficient and extensive chemical inertia, can effectively isolate matrix and Working environment, is the comparatively desirable 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, on the surface of magnesium alloy substrate, prepare the DLC film, not only can guarantee the biocompatibility of magnesium alloy biological implantation material, and can strengthen the corrosion resistance of this embedded material, for the magnesium alloy biological implantation material is widely used in organism, provide feasibility in theory and experiment basis.
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 seriously to restrict at present the key factor of DLC film as the corrosion-resisting wear-proof coating, especially high in chemically reactive, that hardness is low " soft matrix " material surface, for example magnesium and magnesium alloy matrix surface, the difficulty of preparation physiologically acceptable DLC film also will be larger.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 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 the alloy products such as magnesium, aluminium, titanium are done to anode, stainless steel is done negative electrode, be placed in the electrolytic solution of pulsed electrical field environment, make product surface produce micro-arc discharge and generate the oxide ceramic layer that one deck and matrix are combined in metallurgical mode.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, by matching suitable electrolyte system, make other harmful element can not be introduced into this modified coating, thereby avoid this modified coating incompatible with the organism environment, this method is applied in titanium alloy biological implantation material field at present to some extent.But there is micropore in the oxide ceramic layer surface that differential arc oxidation produces, is difficult to, in the complex physiologic environment, the magnesium alloy biological implantation material is played to effective protective effect.
Therefore, how by surface modification, making the magnesium alloy biological implantation material have good biocompatibility and erosion resistance, is the important topic that promotes that the magnesium alloy biological implantation material is applied in organism.
Summary of the invention
Technical purpose of the present invention is the deficiency that exists as biological implantation material for 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 adulterates, the N that for example adulterates, Ti constituent element in the DLC film.
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 is significantly 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, select the chemical reagent of introducing without harmful element, make the silicate differential arc oxidation electrolytic solution that is suitable for medical magnesium alloy surface modification requirement;
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 processed carries out ultrasonic cleaning, removes the remaining electrolytic solution post-drying that contains in the micropore of magnesium alloy matrix surface differential arc oxidation porous-film;
Step 4: the magnesium alloy substrate after step 3 is processed is placed in ionic fluid combined magnetic-controlled sputter depositing system, vacuumize, then by ion source, in the plated film cavity, pass into acetylene gas, on magnesium alloy substrate, apply-100～-pulsed bias of 300V, open ion source, electric current is 0.1～0.5A, at differential arc oxidation porous film surface deposit thickness, is the DLC thin film layer of 300～1000nm.
As preferably, in 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 described step 4, by ion source, in the plated film cavity, pass into simultaneously nitrogen, thereby obtain the DLC thin film layer of nitrogen doping, detailed process is:
Magnesium alloy substrate after step 3 is processed is placed in ionic fluid combined magnetic-controlled sputter depositing system, vacuumize, then by ion source to the mixed gas that passes into acetylene and nitrogen in the plated film cavity, on the bitter earth alloy matrix, apply-100～-pulsed bias of 300V, open ion source, electric current is 0.1～0.5A, at differential arc oxidation porous film surface deposit thickness, is the DLC thin film layer of the nitrogen doping of 300～1000nm.
As preferably, in described step 4, open simultaneously sputtering source, take titanium as sputtering target material, the thin film layer detailed process of adulterating at differential arc oxidation porous film surface titanium deposition is:
Magnesium alloy substrate after step 3 is processed is placed in ionic fluid combined magnetic-controlled sputter depositing system, vacuumize, then by ion source, in the plated film cavity, pass into acetylene gas, on the bitter earth alloy matrix, apply-100～-pulsed bias of 300V, open ion source, electric current is 0.1～0.5A, take titanium as sputtering target material, open sputtering source, electric current, at 1～3A, is the titanium doped DLC thin film layer of 300～1000nm at differential arc oxidation porous film surface deposit thickness.
Compared with prior art, the present invention is take the magnesium alloy biological implantation material as matrix, on its surface, at first utilizing differential arc oxidization technique to introduce thickness is that 3～15 μ m, surface apertures are usingd interior arc differential oxide ceramic layer as transition layer at 1000nm, then on this transition layer surface, prepare the DLC thin film layer that thickness is 300～1000nm, 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 technique 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 adulterates, 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) due to the existence of transition layer in the MAO/DLC compound coating, the combination of DLC thin film layer and magnesium alloy substrate is changed into to the combination of the porous ceramic layer of DLC thin film layer and high rigidity, be conducive to 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 is conducive to slow down the interfacial electrochemistry corrosion, improves the film matrix and ties up to the 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 have of DLC thin film layer, be conducive to improve 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 the useful modification to magnesium alloy matrix surface, meet 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.
The accompanying drawing explanation
Fig. 1 is MAO/DLC compound coating in the embodiment of the present invention 1 and existing coating is the polarization curve in 3.5% NaCl solution in concentration.
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 DLC thin film layer, transition layer is 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, through mechanical polishing, is selected the chemical reagent of introducing without harmful element, makes the silicate differential arc oxidation electrolytic solution that is suitable for medical magnesium alloy surface modification requirement;
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 at magnesium alloy matrix surface, preparing thickness 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 processed, through the acetone ultrasonic cleaning, is removed the remaining electrolytic solution post-drying that contains in magnesium alloy matrix surface arc differential oxide ceramic layer micropore;
Step 4: the magnesium alloy substrate after step 3 is processed is placed in ionic fluid combined magnetic-controlled sputter depositing system, forvacuum to 2 * 10
-5Torr; By ion source, in the plated film cavity, pass into the acetylene that gas flow is 40sccm, on the differential arc oxidation magnesium alloy substrate, apply-pulsed bias of 100V, open ion source, electric current is 0.2A, remaining this process 60min, is the DLC thin film layer of 600nm at ceramic layer surface deposition thickness.
The nano-indentation hardness value of MAO/DLC compound coating obtained above is 12GPa, with steel ball to the mill frictional coefficient below 0.2, corrosion electric current density is significantly 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 DLC thin film layer (referred to as the N-DLC thin film layer) of magnesium alloy matrix surface and nitrogen doping, transition layer is 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, through mechanical polishing, is selected the chemical reagent of introducing without harmful element, makes the silicate differential arc oxidation electrolytic solution that is suitable for medical magnesium alloy surface modification requirement;
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 at magnesium alloy matrix surface, preparing thickness 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 processed, through the acetone ultrasonic cleaning, is removed the remaining electrolytic solution post-drying that contains in magnesium alloy matrix surface arc differential oxide ceramic layer micropore;
Step 4: the magnesium alloy substrate after step 3 is processed is placed in the ionic fluid combined magnetic-controlled sputter depositing system of independent development, forvacuum to 2 * 10
-5Torr; By the mixed gas of ion source to the nitrogen of the acetylene that passes into 30sccm in the plated film cavity and 10sccm, on the differential arc oxidation magnesium alloy substrate, apply-pulsed bias of 100V, open ion source, electric current is 0.2A, remaining this process 60min, is the N-DLC thin film layer of 500nm at ceramic layer surface deposition thickness.
The nano-indentation hardness value of MAO/N-DLC compound coating obtained above is 6GPa, with steel ball to the mill frictional coefficient below 0.2, corrosion electric current density is significantly 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 titanium doped DLC thin film layer (referred to as the Ti-DLC thin film layer), transition layer is 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, 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, through mechanical polishing, is selected the chemical reagent of introducing without harmful element, makes the silicate differential arc oxidation electrolytic solution that is suitable for medical magnesium alloy surface modification requirement;
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 at magnesium alloy matrix surface, preparing thickness 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 processed, through the acetone ultrasonic cleaning, is removed the remaining electrolytic solution post-drying that contains in magnesium alloy matrix surface arc differential oxide ceramic layer micropore;
Step 4: the magnesium alloy substrate after step 3 is processed is placed in the ionic fluid combined magnetic-controlled sputter depositing system of independent development, forvacuum to 2 * 10
-5Torr; By ion source, in the plated film cavity, pass into acetylene gas, on the differential arc oxidation magnesium alloy substrate, apply-pulsed bias of 100V, open ion source, electric current is 0.2A, take Ti as sputtering target material, open sputtering source, electric current is at 2A, remaining this process 70min, is the Ti-DLC thin film layer of 800nm at ceramic layer surface deposition thickness.
The nano-indentation hardness value of MAO/Ti-DLC compound coating obtained above is 10GPa, with steel ball to the mill frictional coefficient below 0.2, corrosion electric current density is significantly lower than the Ti/DLC compound coating, and this compound coating has good biocompatibility.
Claims (7)
1. a magnesium alloy materials is as the application of biological implantation material, described magnesium alloy materials is comprised of the magnesium alloy substrate compound coating surperficial with it, described compound coating is 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; 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; 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.
2. magnesium alloy materials according to claim 1, as the application of biological implantation material, is characterized in that: active component adulterates in described DLC film.
3. magnesium alloy materials according to claim 2, as the application of biological implantation material, is characterized in that: described active component is nitrogen or titanium.
4. magnesium alloy materials according to claim 1, as the application of biological implantation material, is characterized in that: the preparation method of described compound coating comprises the steps:
Step 1: according to the matching principle of magnesium alloy differential arc oxidation electrolytic solution, select the chemical reagent of introducing without harmful element, make the silicate differential arc oxidation electrolytic solution that is suitable for medical magnesium alloy surface modification requirement;
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 processed carries out ultrasonic cleaning, removes the remaining electrolytic solution post-drying that contains in the micropore of magnesium alloy matrix surface differential arc oxidation porous-film;
Step 4: the magnesium alloy substrate after step 3 is processed is placed in ionic fluid combined magnetic-controlled sputter depositing system, vacuumize, then by ion source, in the plated film cavity, pass into acetylene gas, on magnesium alloy substrate, apply-100～-pulsed bias of 300V, open ion source, electric current is 0.1～0.5A, at differential arc oxidation porous film surface deposit thickness, is the DLC thin film layer of 300～1000nm.
5. magnesium alloy materials according to claim 4 is as the application of biological implantation material, it is characterized in that: in described step 2, the monopulse output voltage of DC pulse mao power source is 280～350V, and frequency is 400～800Hz, dutycycle is 5～10%, and oxidization time is 3～10min.
6. magnesium alloy materials according to claim 4, as the application of biological implantation material, is characterized in that: in described step 4, by ion source, in the plated film cavity, pass into simultaneously nitrogen, thereby obtain the DLC thin film layer of nitrogen doping, detailed process is:
Magnesium alloy substrate after step 3 is processed is placed in ionic fluid combined magnetic-controlled sputter depositing system, vacuumize, then by ion source to the mixed gas that passes into acetylene and nitrogen in the plated film cavity, on the bitter earth alloy matrix, apply-100～-pulsed bias of 300V, open ion source, electric current is 0.1～0.5A, at differential arc oxidation porous film surface deposit thickness, is the DLC thin film layer of the nitrogen doping of 300～1000nm.
7. magnesium alloy materials according to claim 4, as the application of biological implantation material, is characterized in that: in described step 4, open simultaneously sputtering source, take titanium as sputtering target material, the thin film layer detailed process of adulterating at differential arc oxidation porous film surface titanium deposition is:
Magnesium alloy substrate after step 3 is processed is placed in ionic fluid combined magnetic-controlled sputter depositing system, vacuumize, then by ion source, in the plated film cavity, pass into acetylene gas, on the bitter earth alloy matrix, apply-100～-pulsed bias of 300V, open ion source, electric current is 0.1～0.5A, take titanium as sputtering target material, open sputtering source, electric current, at 1～3A, is the titanium doped DLC thin film layer of 300～1000nm at differential arc oxidation porous film surface deposit thickness.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011101738669A CN102286767B (en) | 2011-06-24 | 2011-06-24 | Composite coating on surface of magnesium alloy biological implant material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011101738669A CN102286767B (en) | 2011-06-24 | 2011-06-24 | Composite coating on surface of magnesium alloy biological implant material and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102286767A CN102286767A (en) | 2011-12-21 |
| CN102286767B true CN102286767B (en) | 2013-11-20 |
Family
ID=45333509
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2011101738669A Active CN102286767B (en) | 2011-06-24 | 2011-06-24 | Composite coating on surface of magnesium alloy biological implant material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102286767B (en) |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102758201B (en) * | 2012-06-26 | 2015-07-15 | 中国科学院宁波材料技术与工程研究所 | Composite coating with anti-corrosion lubricating property of surface of magnesium alloy, preparation method thereof |
| CN104138616B (en) * | 2014-07-23 | 2016-06-08 | 深圳清华大学研究院 | A kind of medical titanium and titanium alloy surface aoxidize-plate carbon-diamond like carbon composite membrane and preparation method thereof |
| CN105112981A (en) * | 2015-08-18 | 2015-12-02 | 江苏科技大学 | Method for preparing magnesium alloy micro-arc oxidation ceramics coating by staged pressurizing |
| JP2017094016A (en) * | 2015-11-18 | 2017-06-01 | 学校法人加計学園 | Bioabsorbable medical instrument and method for adjusting decomposition rate of the same |
| CN109622973A (en) * | 2018-11-22 | 2019-04-16 | 淮北市菲美得环保科技有限公司 | A kind of preparation process of wearability stainless steel alloy coating |
| 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 |
| JP7041902B2 (en) * | 2020-06-09 | 2022-03-25 | 学校法人加計学園 | Surface treatment method for bioabsorbable medical equipment |
| CN112656993B (en) * | 2021-03-16 | 2021-05-28 | 中南大学湘雅医院 | Composite film of blood vessel stent and preparation method 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 |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5273788A (en) * | 1992-07-20 | 1993-12-28 | The University Of Utah | Preparation of diamond and diamond-like thin films |
| EP1338576B1 (en) * | 1999-05-03 | 2005-07-27 | Guardian Industries Corp. | Highly tetrahedral amorphous carbon coating on glass |
| CN101665941A (en) * | 2008-09-04 | 2010-03-10 | 中国科学院兰州化学物理研究所 | Method for preparing diamond-like composite coating on surface of magnesium alloy |
| CN101792898A (en) * | 2010-04-09 | 2010-08-04 | 中国科学院宁波材料技术与工程研究所 | Carbon film for improving abrasion resistance of magnesium alloy and preparation method thereof |
| CN101871119A (en) * | 2010-07-28 | 2010-10-27 | 哈尔滨工业大学 | Preparation method of magnesium alloy surface micro-arc oxidation/spray coating compound film |
| CN102021513A (en) * | 2010-12-02 | 2011-04-20 | 中国科学院宁波材料技术与工程研究所 | High-tenacity oxidation-resistant anti-friction coating on substrate surface and preparation method thereof |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2617209B2 (en) * | 1988-08-30 | 1997-06-04 | 浜松ホトニクス株式会社 | Optical arithmetic unit |
| JPH0963027A (en) * | 1995-08-28 | 1997-03-07 | Yamaha Corp | Magnetic head |
-
2011
- 2011-06-24 CN CN2011101738669A patent/CN102286767B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5273788A (en) * | 1992-07-20 | 1993-12-28 | The University Of Utah | Preparation of diamond and diamond-like thin films |
| EP1338576B1 (en) * | 1999-05-03 | 2005-07-27 | Guardian Industries Corp. | Highly tetrahedral amorphous carbon coating on glass |
| CN101665941A (en) * | 2008-09-04 | 2010-03-10 | 中国科学院兰州化学物理研究所 | Method for preparing diamond-like composite coating on surface of magnesium alloy |
| CN101792898A (en) * | 2010-04-09 | 2010-08-04 | 中国科学院宁波材料技术与工程研究所 | Carbon film for improving abrasion resistance of magnesium alloy and preparation method thereof |
| CN101871119A (en) * | 2010-07-28 | 2010-10-27 | 哈尔滨工业大学 | Preparation method of magnesium alloy surface micro-arc oxidation/spray coating compound film |
| CN102021513A (en) * | 2010-12-02 | 2011-04-20 | 中国科学院宁波材料技术与工程研究所 | High-tenacity oxidation-resistant anti-friction coating on substrate surface and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102286767A (en) | 2011-12-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102286767B (en) | Composite coating on surface of magnesium alloy biological implant material and preparation method thereof | |
| CN1974876B (en) | Bioactive film on titanium metal surface and its sand blasting-micro arc oxidizing compounding process | |
| CN101461964B (en) | Bioactivity surface modification method of biological medical degradable magnesium alloy | |
| CN102677126B (en) | Process for preparing compact magnesium oxide/hydroxyapatite nano fiber double-layer coating on surface of magnesium base | |
| Zhao et al. | Preparation and properties of composite MAO/ECD coatings on magnesium alloy | |
| CN103372232B (en) | Micro-arc oxidation self-sealing hole active coating of magnesium-based implant material and preparation method of micro-arc oxidation self-sealing hole active coating | |
| CN100496622C (en) | Strontium containing hydroxyapatite biologically active film and preparation method thereof | |
| CN102268711B (en) | Method for preparing biological composite coating on surface of magnesium-based material | |
| CN101775632B (en) | Method for preparing hydroxyapatite film layer directly on surface of medical nickel-titanium alloy | |
| CN101244291B (en) | Magnesium or magnesium alloy material with complex gradient layer and preparation thereof | |
| CN101537208A (en) | Biological active coating on surface of titanium or titanium alloy and preparation method thereof | |
| CN101575726B (en) | Method for preparing bioactive gradient film of fluor-hydroxyapatite | |
| CN105420789A (en) | Hydrophobic composite biological activity coating on surface of pure-magnesium or magnesium alloy and preparation method of hydrophobic composite biological activity coating | |
| CN102181842A (en) | Method for modifying titanium surface | |
| CN102304745B (en) | Method for preparing bio-ceramic film on surface of magnesium/magnesium alloy through micro-arc oxidation | |
| Zhu et al. | Characterization of hydrothermally treated anodic oxides containing Ca and P on titanium | |
| CN105420680A (en) | Preparation method of pure titanium surface Ag/Sr co-doped TiO2 porous film | |
| Mardali et al. | Microstructure and corrosion characterization of a MgO/Hydroxyapatite bilayer coating by plasma electrolytic oxidation coupled with flame spraying on a Mg alloy | |
| CN102304746A (en) | Polypyrrole calcium phosphate/magnesium oxide bioceramic coating and preparation method thereof | |
| CN104694994A (en) | Method for carrying out electrochemical treatment on surface of biomedical magnesium or magnesium alloy with high biological activity and low degradation rate | |
| CN103290455A (en) | Titanium micro/nanometer double-structured dioxide thin film with high biological activity and preparation method thereof | |
| CN102425000A (en) | Method for preparing biologically active titanium dioxide film on NiTi alloy surface | |
| CN104032272B (en) | In the method that medical magnesium alloy surface prepares amorphous titanium oxide active membrane layer | |
| CN100488574C (en) | Rare earth-hydroxyapatite composite biologically active film layer and preparation method thereof | |
| CN104178765A (en) | Method for preparing controlled degradation metal composite coating on surface of medical magnesium alloy |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |