CN104178765A - Method for preparing controlled degradation metal composite coating on surface of medical magnesium alloy - Google Patents
Method for preparing controlled degradation metal composite coating on surface of medical magnesium alloy Download PDFInfo
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- CN104178765A CN104178765A CN201410449643.4A CN201410449643A CN104178765A CN 104178765 A CN104178765 A CN 104178765A CN 201410449643 A CN201410449643 A CN 201410449643A CN 104178765 A CN104178765 A CN 104178765A
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Abstract
The invention discloses a method for preparing a controlled degradation metal composite coating on the surface of a medical magnesium alloy. The method comprises the following steps: deoiling, grinding and polishing the surface of the magnesium alloy, and depositing a magnesium (Mg)/iron (Fe) periodic composite multilayer film on the surface of the magnesium alloy material through physical vapor deposition, chemical vapor deposition, cold spraying or plasma spraying, wherein the periodicity of magnesium and iron is 2-20, a thickness ratio (blending ratio) of magnesium to iron is 1:(0.1-10), and the total thickness of the coating is 100nm-1000mu m. According to the metal composite coating, the corrosion rate of a magnesium alloy base material can be effectively relieved, good relevance is formed between the corrosion and degradation speed of the magnesium alloy and the periodicity, blending ratio and total thickness of the coating; the composite coating has the characteristics of high biological activity and controllable degradation speed, and the problem that the magnesium alloy is extremely short in implant time in a human body is solved.
Description
Technical field
The present invention relates to bio-medical metal implant material or interventional technique field, be specifically related to a kind of method of preparing controlled degradation metal composite coating at medical magnesium alloy surface.
Background technology
Magnesium alloy is compared with the embedded material of now clinical use to be had advantages of many outstandingly, and magnesium alloy has higher specific tenacity and specific rigidity, and density and people's bone density are substantially suitable, and Young's modulus is about 45 GPa, closer to people's bone.Magnesium is the fourth-largest mineral element that is only second to calcium, sodium and potassium in human body, is also to participate in one of necessary element of human body metabolism.In recent years, magnesium and magnesium alloy are more and more subject to people's attention as metal implant material.But extracorporeal simulating experiment and results of animal show: pure magnesium and magnesium alloy its corrosion degradation speed without protection in the situation that is too fast, and the degradation rate in simulated body fluid is on average up to 0.2 ~ 1.0 mm/a.
Generally, human body is implanted into requirement on devices and at least reaches 4 months active times to half a year, during whole treatment, suitable mechanical property (higher intensity and hardness must be able to be provided, Young's modulus and the toughness of coupling), the hydrogen producing during degradation in vivo is more few better, to avoid forming subcutaneous bubbling, cause field of operation healing to delay or tissue necrosis
But be full of Cl at human body
?corrosive environment in, magnesium and magnesium alloy can't meet the requirement of clinical application to biomaterial corrosion resisting property.
Research discovery, the methods such as modern melting and solidification technology, alloying and amorphization techniques improve the solidity to corrosion of magnesium alloy to a certain extent, but still can not meet clinical service requirements.Surface modification is at present most widely used general and can realize a kind of very practical means of Biocomposite material performance, by can effectively improving its performance to the surface modification of metallic substance, the metallic character of matrix and the biological activity on top layer are combined well, thereby obtain suitable surface composition, structural form and surface property, to improve solidity to corrosion and the biocompatibility of implant.The method of the surface modification treatment of medical magnesium alloy mainly contains: chemical conversion processing, sol-gel method, differential arc oxidation, electroless plating, organic coating and ion implantation etc.
By chemical conversion, process, at Mg alloy surface, form the good insoluble compound rete of one deck sticking power, this tunic not only can protect magnesium alloy not to be subject to the impact of water and other corrosive atmospheres, and the while can also be improved the sticking power of follow-up coating.But no matter be chromate conversion method or cobaltates conversion method, all can introduce poisonous element (chromium, cobalt element all have immunosuppressive action), weakened the biocompatibility of medical magnesium alloy.
Utilizing organic coating to protect magnesium and alloy thereof is that technique is simple, the significant technological approaches of effect.The compactness of coating and the combination of coating/matrix are the principal elements that affects organic coating protection effect.But, the method of utilizing organic coating to improve magnesium alloy is subject to the restriction of coated material, as: the acid degradation product of poly(lactic acid) and multipolymer rete can make in-vivo tissue pH value around decline, can produce the anti-host response of a kind of non-inflammation to human body, and acid product likely can accelerate the corrosion of magnesium alloy conversely.
Ion implantationly under vacuum condition, inject any element toward Mg alloy surface, but it is limited to inject the degree of depth, is generally 50 ~ 500 nm.In addition, Mg alloy surface is ion implantation likely causes the degradation speed of magnesium alloy to substantially exceed not carrying out surface to be injected, and makes it to produce comparatively serious galvanic corrosion problem.In addition, the poisonous or difficult degraded of metal ion of likely injecting, produces new problem.
Sol-gel method is a kind of wet chemical method, and it is mainly suitable for preparing thin-film material, can on the base material of any shape and any area, prepare film or coating.But, at Mg alloy surface, prepare in sol-gel rete process, be acid colloidal sol and can corrode Mg alloy surface, cause rete imperfect, and then reduce the coverage of rete and the bonding strength between rete and matrix.
Electroless plating is to make by displacement or oxidation-reduction reaction the process that in plating solution, metal ion reduces and deposits on protected metal.Magnesium alloy can be protected with chemical plating technology.In recent years, chemical Ni-P plating binary alloy technology is increasingly mature and be widely used in material surface modifying field.Consider the toxic action of Ni element to human body, this rete can not be applied in biomaterial.
Differential arc oxidization technique is that the metals such as aluminium, titanium, magnesium are placed in to electrolyte solution, under thermochemistry, plasma chemical and electrochemical acting in conjunction, makes material surface produce spark discharge and generates ceramic layer.But existing achievement shows, after magnesium alloy differential arc oxidation, although can improve the corrosion resistance nature of magnesium alloy substrate in human body, also fails to reach desirable controllable degradation property.
For magnesium alloy, above-mentioned conventional process for modifying surface cannot obtain and integrate biological activity and the controlled coating of degradation speed.Therefore, guaranteeing, under the prerequisite of mechanics adaptation between material and osseous tissue, to improve wear-resisting, the corrosion resisting property of material, safe metabolism, controlled degradation and the physiology realized under internal milieu are adaptive, are that magnesium alloy is in the key that is implanted into apparatus acquisition application.
Document (CN1250820A) discloses the corrosion resisting property that the method that adopts magnesium to close plating metal on surface titanium is improved magnesium alloy materials, but titanium is a kind of inert material, cause the biological activity of material to decline and do not relate to the controlled degradation problem of magnesium alloy, because titanium is nondegradable in human body, and it is single coating; Document (CN102341527A) discloses a kind of method that forms laminated coating on substrate surface, in described coating, there are at least one ceramic material layer and at least one metallic substance, in the material that particularly used, having at least a kind of is shape memory alloy, and its main purpose is to utilize the distortion of coating to realize the recovery that matrix is out of shape.The type that this multiple film layer application target and multilayer film form is different.Preparation and blood compatibility > > (the investigation of materials journal of document < < degradable pure iron film, 2008 the 5th phases) method that a kind of filtered cathodic vacuum arc source method is prepared pure iron film on monocrystalline silicon substrate is disclosed, obviously, except body material is different, coating is single metallic coating.But document also reported, pure iron film surface activates smaller to the thrombin in blood plasma, and has good erosion resistance and blood compatibility.
Summary of the invention
The object of the invention is to: a kind of method of preparing controlled degradation metal composite coating at medical magnesium alloy surface is provided, the method provides a kind of method of preparing metal composite coating at medical magnesium alloy surface, not only can guarantee the original high reactivity of material, can also realize the controlled degradation of magnesium alloy, and coating is without physiology toxicity.
Technical solution of the present invention is that the preparation of this metal composite coating comprises the following steps:
(1) medical magnesium alloy surface is carried out to oil removing, polishing and mechanical polishing and process, after acetone and dehydrated alcohol cleaning, dry stand-by;
(2) by coating production, at medical magnesium alloy surface, deposit periodically composite multilayer membrane of magnesium (Mg)/iron (Fe).
Wherein, described medical magnesium alloy is pure Mg, Mg-Al-Zn, Mg-Zn-Ca series magnesium alloy.
Wherein, described coating production is physical vapor deposition (PVD), chemical vapor deposition (CVD), cold spraying or plasma spraying.
Wherein, the metal composite multilayer film obtaining is periodically composite multilayer membrane of magnesium (Mg)/iron (Fe), and wherein: the cycle life of Mg and Fe is 2 ~ 20, modulation ratio is 1:(0.1 ~ 10), the total thickness 100 nm ~ 1000 μ m of coating.
The inventive method is compared with other technology, and the rete of preparation is combined closely with magnesium alloy substrate, and has the advantages such as good biological activity and cellular affinity, by selecting suitable cycle and modulation ratio can realize the accurately controlled of magnesium alloy degradation speed.
Accompanying drawing explanation
Fig. 1 is the electromicroscopic photograph of embodiment 2 gained metal composite coating.
Fig. 2 is the electromicroscopic photograph of embodiment 4 gained metal composite coating
.
Embodiment
Below in conjunction with specific embodiment, further illustrate technical solution of the present invention, these embodiment can not be interpreted as it is the restriction to technical scheme.
embodiment 1:according to following steps, on pure magnesium (Mg99.95) surface, prepare Mg/Fe controlled degradation metal composite coating
The first step: pure magnesium surface is carried out to oil removing, sand papering and mechanical polishing and process, after acetone and dehydrated alcohol cleaning, dry stand-by;
Second step: carry out the plated film growth of Mg/Fe metal composite coating on Pvd equipment; The thickness of described Mg/Fe metal composite coating is 100 nm, and cycle life is 20, and modulation ratio is 1:10; Described Mg/Fe metal composite coating is Mg layer by matrix one side, is then Fe layer.
embodiment 2:according to following steps, on Mg-Al-Zn alloy (AZ31 magnesium alloy) surface, prepare Mg/Fe controlled degradation metal composite coating
The first step: AZ31 Mg alloy surface is carried out to oil removing, sand papering and mechanical polishing and process, clean through acetone and dehydrated alcohol, dry stand-by;
Second step: utilize chemical Vapor deposition process to carry out the plated film growth of Mg/Fe metal composite coating at magnesium alloy; The thickness of described Mg/Fe metal composite coating is 1000 nm, and cycle life is 10, and modulation ratio is 1:2; Described Mg/Fe metal composite coating is Mg layer by matrix one side, is then Fe layer.
embodiment 3:according to following steps, on Mg-Al-Zn alloy (AZ61 magnesium alloy) surface, prepare Mg/Fe controlled degradation metal composite coating
The first step: AZ61 Mg alloy surface is carried out to oil removing, sand papering and mechanical polishing and process, clean through acetone and dehydrated alcohol, dry stand-by;
Second step: carry out the preparation of Mg/Fe metal composite coating on cold spray apparatus; The thickness of described Mg/Fe metal composite coating is 1000 μ m, and cycle life is 2, and modulation ratio is 10:1 (1:0.1); Described Mg/Fe metal composite coating is Mg layer by matrix one side, is then Fe layer.
embodiment 4:according to following steps at Mg-Zn-Ca alloy (Mg
95.2zn
4ca
0.8magnesium alloy) surface preparation Mg/Fe controlled degradation metal composite coating
The first step: to Mg
95.2zn
4ca
0.8mg alloy surface carries out oil removing, sand papering and mechanical polishing to be processed, and after acetone and dehydrated alcohol cleaning, dries stand-by;
Second step: carry out the preparation of Mg/Fe metal composite coating on plasma spraying equipment; The thickness of described Mg/Fe metal composite coating is 300 μ m, and cycle life is 3, and modulation ratio is 5:1; Described Mg/Fe metal composite coating is Mg layer by matrix one side, is then Fe layer.
Described embodiment of the present invention is only used to clearly demonstrate example of the present invention, and is not the restriction to embodiment of the present invention.For those of ordinary skill in the field; also can make other changes in different forms on the basis of the above description; here exhaustive without also giving all embodiments, and these belong to apparent variation that spirit of the present invention amplified out or change still in protection scope of the present invention.
Claims (4)
1. at medical magnesium alloy surface, prepare the method for controlled degradation metal composite coating, it is characterized in that the preparation of this metal composite coating comprises the following steps:
(1) medical magnesium alloy surface is carried out to oil removing, polishing and mechanical polishing and process, after acetone and dehydrated alcohol cleaning, dry stand-by;
(2) by coating production, at medical magnesium alloy surface, deposit periodically composite multilayer membrane of magnesium (Mg)/iron (Fe).
2. the method for preparing controlled degradation metal composite coating at medical magnesium alloy surface according to claim 1, is characterized in that: described medical magnesium alloy is pure Mg, Mg-Al-Zn, Mg-Zn-Ca series magnesium alloy.
3. the method for preparing controlled degradation metal composite coating at medical magnesium alloy surface according to claim 1, is characterized in that: described coating production is physical vapor deposition (PVD), chemical vapour deposition CVD), cold spraying or plasma spraying.
4. the method for preparing controlled degradation metal composite coating at medical magnesium alloy surface according to claim 1, it is characterized in that: the metal composite multilayer film obtaining is periodically composite multilayer membrane of magnesium (Mg)/iron (Fe), wherein: the cycle life of Mg and Fe is 2 ~ 20, modulation ratio is 1:(0.1 ~ 10), the total thickness 100 nm ~ 1000 μ m of coating.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105251060A (en) * | 2015-10-29 | 2016-01-20 | 中国科学院宁波材料技术与工程研究所 | Method for preparing drug sustained-release coating by vacuum cold spray coating technology and product prepared by method |
| CN107557783A (en) * | 2017-08-31 | 2018-01-09 | 常州富思通管道有限公司 | A kind of preparation method of composite medical magnesium alloy |
| CN111485211A (en) * | 2020-05-18 | 2020-08-04 | 东莞立德生物医疗有限公司 | Degradable magnesium alloy biological implantation material and preparation method thereof |
| CN112111738A (en) * | 2020-07-22 | 2020-12-22 | 上海微创医疗器械（集团）有限公司 | Medical implant device, preparation method thereof and preparation method of intravascular stent |
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| CN101337090A (en) * | 2008-08-29 | 2009-01-07 | 乐普（北京）医疗器械股份有限公司 | Composite coating magnesium/magnesium alloy biology device and preparation method thereof |
| CN102758174A (en) * | 2012-07-02 | 2012-10-31 | 中国科学院宁波材料技术与工程研究所 | Protective film on surface of workpiece basal body and preparation method of protective film |
| CN102797010A (en) * | 2012-08-31 | 2012-11-28 | 淮阴工学院 | Method for preparing titanium dioxide active film on surface of medical magnesium alloy |
| CN103465542A (en) * | 2013-09-16 | 2013-12-25 | 天津大学 | Degradable iron, zinc and magnesium-based gradient composite material based on biological bone healing and preparation thereof |
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2014
- 2014-09-05 CN CN201410449643.4A patent/CN104178765A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101337090A (en) * | 2008-08-29 | 2009-01-07 | 乐普（北京）医疗器械股份有限公司 | Composite coating magnesium/magnesium alloy biology device and preparation method thereof |
| CN102758174A (en) * | 2012-07-02 | 2012-10-31 | 中国科学院宁波材料技术与工程研究所 | Protective film on surface of workpiece basal body and preparation method of protective film |
| CN102797010A (en) * | 2012-08-31 | 2012-11-28 | 淮阴工学院 | Method for preparing titanium dioxide active film on surface of medical magnesium alloy |
| CN103465542A (en) * | 2013-09-16 | 2013-12-25 | 天津大学 | Degradable iron, zinc and magnesium-based gradient composite material based on biological bone healing and preparation thereof |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105251060A (en) * | 2015-10-29 | 2016-01-20 | 中国科学院宁波材料技术与工程研究所 | Method for preparing drug sustained-release coating by vacuum cold spray coating technology and product prepared by method |
| CN107557783A (en) * | 2017-08-31 | 2018-01-09 | 常州富思通管道有限公司 | A kind of preparation method of composite medical magnesium alloy |
| CN111485211A (en) * | 2020-05-18 | 2020-08-04 | 东莞立德生物医疗有限公司 | Degradable magnesium alloy biological implantation material and preparation method thereof |
| CN112111738A (en) * | 2020-07-22 | 2020-12-22 | 上海微创医疗器械（集团）有限公司 | Medical implant device, preparation method thereof and preparation method of intravascular stent |
| WO2022017101A1 (en) * | 2020-07-22 | 2022-01-27 | 上海微创医疗器械（集团）有限公司 | Implantable medical device and method for manufacturing same, and method for manufacturing stent |
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