CN102614545A - Metal-based implant ternary compound coating material and preparation method thereof - Google Patents
Metal-based implant ternary compound coating material and preparation method thereof Download PDFInfo
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- CN102614545A CN102614545A CN2012100681085A CN201210068108A CN102614545A CN 102614545 A CN102614545 A CN 102614545A CN 2012100681085 A CN2012100681085 A CN 2012100681085A CN 201210068108 A CN201210068108 A CN 201210068108A CN 102614545 A CN102614545 A CN 102614545A
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Abstract
The invention discloses a metal-based implant ternary compound coating material and a preparation method thereof. The metal-based implant ternary compound coating material is characterized in that three-layer films are applied on the surface of metal substrate, a bottom layer is a porous oxide corrosion protection layer pretreated by an anodic oxidation method, a middle layer is a hydroxyapatite/ biomacromolecule hybridization material active layer foremd by an electrophoretic deposition method, and an outer layer is a honeycomb-shaped film packaging layer coated with polylactic acid polymer solution. The metal-based implant ternary compound coating material has low requirements for equipment and technology, and is convenient to use.
Description
Technical field:
The present invention relates to the biomaterial preparing technical field, be specially adapted to Metal Substrate implant ternary composite coating material of implanted metallic biomaterial surface modification and preparation method thereof.
Background technology:
Hydroxyapatite is a kind of bioactive materials; For cell provides the microenvironment similar with nature bone, helping bone is adhesion, the propagation of cell, mainly is used in the reparation of biological hard tissue and substitutes; But the fragility of pure ha is big, intensity is low, and the application of material is restricted.
Polylactic acid is one type of eco-friendly degradable biomaterial, has good toughness and plasticity, dissolves in the big organic solvent of various polarity, can be used for the biomaterial coatings art.People are often with polylactic acid and the compound intensity that improves polylactic acid of hydroxyapatite, and in degraded produces during with the polylactic acid implant into body acidity.
The bio-medical metal, for example magnesium metal, aluminum, zinc, titanium and alloy thereof have stronger plasticity and higher modulus of elasticity, are suitable for hard tissue repair.But be prone to be corroded in the naked metal implant or biological activity poor, therefore people attempt on metallic substrates, to apply layer of active oxide, hydroxyapatite or polylactic acid macromolecular material in recent years, so that prevent the biological activity of corrosion of metal, reinforcing material.The method of deposited hydroxyl apatite is a lot of on the metal current base; Mostly adopt methods such as electrodeposition process, bionical solution-deposition method, sol-gal process, magnetron sputtering or plasma spraying; But these methods or damage substrate, coating combine insecure, easy be full of cracks with substrate, or are to the substrate requirement is harsh, equipment requirements is high, cost is excessive.For preparation polylactic acid coating, adopt mostly and directly soak or spraying process, even being prepared into the composite refabrication with hydroxyapatite and polylactic acid, elder generation becomes film coating also can't solve to combine the fastness problem with substrate.Therefore, explore a kind of room temperature, normal pressure, the simple method of technology, on metallic substrates, prepare a kind of composite biological coatings, significant to bone reparation, life entity with bio-medical materials such as electrodes.
Summary of the invention:
The purpose of this invention is to provide a kind of can under room temperature, atmospheric pressure environment, the manufacturing, the simple Metal Substrate implant of technology ternary composite coating material and preparation method thereof.
Technical scheme of the present invention is; A kind of Metal Substrate implant ternary composite coating material, it is characterized in that: metallic substrate surface is coated with three-layer thin-film, and bottom is the porous oxide anticorrosive coat; Middle level hydroxyapatite/biomacromolecule hybrid material active layer, skin is the honeycomb thin-film encapsulation layer.Used metal base comprises: magnesium and magnesium alloy, aluminum and aluminium alloy, zinc and kirsite, titanium or titanium alloy.Hybrid material is hydroxyapatite/collagen albumen, hydroxyapatite/chitosan, hydroxyapatite/sodium alginate, the hydroxyapatite of preparing with biomimetic synthesis method/hyaluronic acid hybrid material, and containing the biomacromolecule mass fraction is 1%-20%.Polylactic acid base polymer comprises poly (l-lactic acid), gathers D, L-lactic acid or poly (l-lactic acid)-co-glycolic acid.A kind of method for preparing of Metal Substrate implant ternary composite coating material; It is characterized in that: metallic substrate surface is coated with three-layer thin-film; Bottom is to obtain the porous oxide anticorrosive coat with the anode oxidation method pretreatment; The middle level is to obtain hydroxyapatite/biomacromolecule hybrid material active layer with electrophoretic deposition method, and skin is to be coated with last layer honeycomb thin-film encapsulation layer with polylactic acid base polymer solution.The anodic oxidation voltage scope is 1V-600V, and current range is 0.01A-1A, and oxidization time is 1min-200min.Honeycomb thin-film encapsulation layer method of application comprises dip-coating and spraying, dip-coating and 10 ℃-50 ℃ of spraying ambient temperatures, dip-coating and spraying envionmental humidity 30%-90%.
The invention has the beneficial effects as follows:
1, reaction condition is room temperature, normal pressure, in aqueous solution and alcoholic solution, carries out, and equipment and specification requirement are not high;
2, deposition condition is gentle, can not destroy biomacromolecule, can make full use of its biological activity and cohesive;
3, the porous oxide coating has increased the mechanical chimeric point with substrate, improves coating adhesion;
4, utilize polylactic acid film that grain coating is carried out the sealing of hole consolidation process, make the grain coating difficult drop-off;
5, the honey comb structure polylactic acid not only helps the growth of cell, and makes part of hydroxyl apatite expose, and forms calcium ion and basic group stripping passage, accelerated cell growth, reduction polylactic acid acidity.
Description of drawings:
Fig. 1: the scanning electron microscope diagram sheet of the bottom porous magnesia anticorrosive coat of preparation;
Fig. 2: the scanning electron microscope diagram sheet of the bottom Woelm Alumina anticorrosive coat of preparation;
Fig. 3: the scanning electron microscope diagram sheet of the bottom porous zinc bloom anticorrosive coat of preparation;
Fig. 4: the scanning electron microscope diagram sheet of the bottom porous titanium oxide anticorrosive coat of preparation;
Fig. 5: the scanning electron microscope diagram sheet of the intermediate layer hydroxyapatite of preparation/biomacromolecule hybrid material active layer;
Fig. 6: the XRD figure of the hydroxyapatite of preparation/biomacromolecule hybrid material;
Fig. 7: the scanning electron microscope diagram sheet of the outside bees nido polylactic acid encapsulated layer of preparation.
The specific embodiment:
Describe embodiment in detail in conjunction with accompanying drawing,
Embodiment 1:
1, the magnesium alloy base material after will polishing is dipped in the sodium hydroxide solution as anode, and anodic oxidation 200min under 1V voltage obtains one deck porous magnesia coating;
The hydroxyapatite/collagen albumen hybrid material that 2, will contain 1% collagen protein is dissolved in that ultra-sonic dispersion becomes suspension in the ethanol, electro-deposition 1000s under 1V voltage;
3, poly (l-lactic acid) is dissolved in the chloroform, obtains one deck porous polymer coating in 10 ℃ of temperature, 30% time dip-coating of relative humidity.
Embodiment 2:
1, the aluminum alloy base material after will polishing is dipped in the oxalic acid solution as anode, and anodic oxidation 100min under 50V voltage obtains one deck Woelm Alumina coating;
The hydroxyapatite/chitosan hybrid material that 2, will contain 10% chitosan is dissolved in that ultra-sonic dispersion becomes suspension in the isopropyl alcohol, electro-deposition 100s under 100V voltage;
3, will gather D, L-lactic acid is dissolved in the dichloromethane, obtains one deck porous polymer coating in 30 ℃ of temperature, 60% time spraying of relative humidity.
Embodiment 3:
1, the kirsite base material after will polishing is dipped in the potassium hydroxide solution as anode, and anodic oxidation 10min under 100V voltage obtains one deck porous zinc bloom coating;
Hydroxyapatite/sodium alginate the hybrid material that 2, will contain 20% sodium alginate is dissolved in that ultra-sonic dispersion becomes suspension in the acetone, electro-deposition 1s under 800V voltage;
3, poly (l-lactic acid)-co-glycolic acid is dissolved in the dichloromethane, obtains one deck porous polymer coating in 50 ℃ of temperature, 90% time spraying of relative humidity.
Embodiment 4:
1, the titanium alloy base material after will polishing is dipped in the ammonium fluoride solution as anode, and anodic oxidation 100min under 100V voltage obtains one deck porous titanium oxide coating;
2, will contain 20% hyaluronic hydroxyapatite/hyaluronic acid hybrid material and be dissolved in that ultra-sonic dispersion becomes suspension in the ethanol, electro-deposition 10s under 100V voltage;
3, poly (l-lactic acid) is dissolved in the chloroform, obtains one deck porous polymer coating in 30 ℃ of temperature, 80% time dip-coating of relative humidity.
Embodiment 5:
1, the magnesium alloy base material after will polishing is dipped in the sodium hydroxide solution as anode, and anodic oxidation 100min under the 0.01A electric current obtains one deck porous magnesia coating;
The hydroxyapatite/collagen albumen hybrid material that 2, will contain 10% collagen protein is dissolved in that ultra-sonic dispersion becomes suspension in the ethanol, electro-deposition 1000s under the 0.1mA electric current;
3, poly (l-lactic acid) is dissolved in the chloroform, obtains one deck porous polymer coating in 30 ℃ of temperature, 60% time dip-coating of relative humidity.
Embodiment 6:
1, the magnesium substrates after will polishing is dipped in the sodium hydroxide solution as anode, and anodic oxidation 10min under the 0.5A electric current obtains one deck porous magnesia coating;
The hydroxyapatite/collagen albumen hybrid material that 2, will contain 5% collagen protein is dissolved in that ultra-sonic dispersion becomes suspension in the n-butyl alcohol, electro-deposition 10s under the 10mA electric current;
3, poly (l-lactic acid) is dissolved in the chloroform, obtains one deck porous polymer coating in 40 ℃ of temperature, 80% time dip-coating of relative humidity.
Embodiment 7:
1, the titanio material after will polishing is dipped in the Fluorinse as anode, and anodic oxidation 5min under the 1A electric current obtains one deck porous titanium oxide coating;
The hydroxyapatite/collagen albumen hybrid material that 2, will contain 10% collagen protein is dissolved in that ultra-sonic dispersion becomes suspension in the isopropyl alcohol, electro-deposition 1s under the 100mA electric current;
3, poly (l-lactic acid) is dissolved in the dichloromethane, obtains one deck porous polymer coating in 30 ℃ of temperature, 80% time dip-coating of relative humidity.
Claims (7)
1. Metal Substrate implant ternary composite coating material; It is characterized in that: metallic substrate surface is coated with three-layer thin-film; Bottom is the porous oxide anticorrosive coat, middle level hydroxyapatite/biomacromolecule hybrid material active layer, and skin is the honeycomb thin-film encapsulation layer.
2. a kind of Metal Substrate implant ternary composite coating material as claimed in claim 1, it is characterized in that: used metal base comprises: magnesium and magnesium alloy, aluminum and aluminium alloy, zinc and kirsite, titanium or titanium alloy.
3. a kind of Metal Substrate implant ternary composite coating material as claimed in claim 1; It is characterized in that: hybrid material is hydroxyapatite/collagen albumen, hydroxyapatite/chitosan, hydroxyapatite/sodium alginate, the hydroxyapatite of preparing with biomimetic synthesis method/hyaluronic acid hybrid material, and containing the biomacromolecule mass fraction is 1%-20%.
4. a kind of Metal Substrate implant ternary composite coating material as claimed in claim 1, it is characterized in that: polylactic acid base polymer comprises poly (l-lactic acid), gathers D, L-lactic acid or poly (l-lactic acid)-co-glycolic acid.
5. the method for preparing of a Metal Substrate implant ternary composite coating material; It is characterized in that: metallic substrate surface is coated with three-layer thin-film; Bottom is to obtain the porous oxide anticorrosive coat with the anode oxidation method pretreatment; The middle level is to obtain hydroxyapatite/biomacromolecule hybrid material active layer with electrophoretic deposition method, and skin is to be coated with last layer honeycomb thin-film encapsulation layer with polylactic acid base polymer solution.
6. the method for preparing of a kind of Metal Substrate implant ternary composite coating material as claimed in claim 5, it is characterized in that: the anodic oxidation voltage scope is 1V-600V, and current range is 0.01A-1A, and oxidization time is 1min-200min.
7. the method for preparing of a kind of Metal Substrate implant ternary composite coating material as claimed in claim 5; It is characterized in that: honeycomb thin-film encapsulation layer method of application comprises dip-coating and spraying; Dip-coating and 10 ℃-50 ℃ of spraying ambient temperatures, dip-coating and spraying envionmental humidity 30%-90%.
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103191465A (en) * | 2013-04-10 | 2013-07-10 | 浙江大学 | Aluminous artificial bone covered with biological ceramics in situ and preparation method of artificial bone |
| CN103785067A (en) * | 2012-11-01 | 2014-05-14 | 中国科学院上海硅酸盐研究所 | Porous titanium coating modified by hyaluronic acid and preparation method thereof |
| CN104212998A (en) * | 2014-08-21 | 2014-12-17 | 北京大学 | Zn-Mg zinc alloy and preparation method and application thereof |
| CN104404480A (en) * | 2014-11-19 | 2015-03-11 | 无锡光旭新材料科技有限公司 | Method for preparing hydroxyapatite and bone collagen composite coating on surface of magnesium alloy |
| CN104862757A (en) * | 2015-05-06 | 2015-08-26 | 厦门大学 | Metal surface treatment method based on chitosan and mussel adhesion protein composite membrane |
| CN105442022A (en) * | 2015-11-24 | 2016-03-30 | 哈尔滨医科大学 | Method for preparing gentamicin-loaded magnesium-based calcium phosphate/chitosan/nanotube medicine carrying film layer through electrophoresis method |
| CN105908237A (en) * | 2016-04-20 | 2016-08-31 | 深圳市龙岗区骨科医院 | Medical implant and preparation method of same |
| CN106283160A (en) * | 2016-08-05 | 2017-01-04 | 宁波江东仑斯福环保科技有限公司 | A kind of preparation method of medical metal-based biological coating |
| CN109079124A (en) * | 2018-08-01 | 2018-12-25 | 郑州大学第附属医院 | A kind of medical embedded bimetallic material and preparation method thereof |
| CN114752982A (en) * | 2022-04-15 | 2022-07-15 | 攀枝花学院 | Biomedical magnesium alloy with time sequence degradation function and preparation method thereof |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1486752A (en) * | 2003-08-06 | 2004-04-07 | 浙江大学 | Composite metal-based porous metal oxide/hydroxyapatite artificial bone and its prepn process |
| CN1869109A (en) * | 2005-05-27 | 2006-11-29 | 富士胶片株式会社 | Honeycomb composite film, and method for producing the same |
| CN101244291A (en) * | 2008-03-17 | 2008-08-20 | 哈尔滨工业大学 | Magnesium or magnesium alloy material with complex gradient layer and preparation thereof |
| CN101381881A (en) * | 2007-09-05 | 2009-03-11 | 西南交通大学 | Method for preparing hydroxylapatite/chitosan composite coating by pulse electrochemical deposition |
| CN101411892A (en) * | 2007-10-19 | 2009-04-22 | 中国科学院金属研究所 | Method for preparing hydroxylapatite/polylactic acid composite biological coating on surface of magnesium alloy |
| JP2009254581A (en) * | 2008-04-16 | 2009-11-05 | Toyo Advanced Technologies Co Ltd | Implant for living body and its production method |
| WO2011119762A1 (en) * | 2010-03-26 | 2011-09-29 | Battelle Memorial Institute | System and method for enhanced electrostatic deposition and surface coatings |
-
2012
- 2012-03-15 CN CN2012100681085A patent/CN102614545A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1486752A (en) * | 2003-08-06 | 2004-04-07 | 浙江大学 | Composite metal-based porous metal oxide/hydroxyapatite artificial bone and its prepn process |
| CN1869109A (en) * | 2005-05-27 | 2006-11-29 | 富士胶片株式会社 | Honeycomb composite film, and method for producing the same |
| CN101381881A (en) * | 2007-09-05 | 2009-03-11 | 西南交通大学 | Method for preparing hydroxylapatite/chitosan composite coating by pulse electrochemical deposition |
| CN101411892A (en) * | 2007-10-19 | 2009-04-22 | 中国科学院金属研究所 | Method for preparing hydroxylapatite/polylactic acid composite biological coating on surface of magnesium alloy |
| CN101244291A (en) * | 2008-03-17 | 2008-08-20 | 哈尔滨工业大学 | Magnesium or magnesium alloy material with complex gradient layer and preparation thereof |
| JP2009254581A (en) * | 2008-04-16 | 2009-11-05 | Toyo Advanced Technologies Co Ltd | Implant for living body and its production method |
| WO2011119762A1 (en) * | 2010-03-26 | 2011-09-29 | Battelle Memorial Institute | System and method for enhanced electrostatic deposition and surface coatings |
Non-Patent Citations (1)
| Title |
|---|
| 王周成等: "金属基生物活性羟基磷灰石涂层材料的研究进展", 《硅酸盐通报》 * |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103785067B (en) * | 2012-11-01 | 2016-03-23 | 中国科学院上海硅酸盐研究所 | Hyaluronic acid modified porous titanium coating and preparation method thereof |
| CN103785067A (en) * | 2012-11-01 | 2014-05-14 | 中国科学院上海硅酸盐研究所 | Porous titanium coating modified by hyaluronic acid and preparation method thereof |
| CN103191465B (en) * | 2013-04-10 | 2014-10-15 | 浙江大学 | Aluminous artificial bone covered with biological ceramics in situ and preparation method of artificial bone |
| CN103191465A (en) * | 2013-04-10 | 2013-07-10 | 浙江大学 | Aluminous artificial bone covered with biological ceramics in situ and preparation method of artificial bone |
| CN104212998A (en) * | 2014-08-21 | 2014-12-17 | 北京大学 | Zn-Mg zinc alloy and preparation method and application thereof |
| CN104404480A (en) * | 2014-11-19 | 2015-03-11 | 无锡光旭新材料科技有限公司 | Method for preparing hydroxyapatite and bone collagen composite coating on surface of magnesium alloy |
| CN104862757A (en) * | 2015-05-06 | 2015-08-26 | 厦门大学 | Metal surface treatment method based on chitosan and mussel adhesion protein composite membrane |
| CN105442022A (en) * | 2015-11-24 | 2016-03-30 | 哈尔滨医科大学 | Method for preparing gentamicin-loaded magnesium-based calcium phosphate/chitosan/nanotube medicine carrying film layer through electrophoresis method |
| CN105908237A (en) * | 2016-04-20 | 2016-08-31 | 深圳市龙岗区骨科医院 | Medical implant and preparation method of same |
| CN106283160A (en) * | 2016-08-05 | 2017-01-04 | 宁波江东仑斯福环保科技有限公司 | A kind of preparation method of medical metal-based biological coating |
| CN109079124A (en) * | 2018-08-01 | 2018-12-25 | 郑州大学第附属医院 | A kind of medical embedded bimetallic material and preparation method thereof |
| CN114752982A (en) * | 2022-04-15 | 2022-07-15 | 攀枝花学院 | Biomedical magnesium alloy with time sequence degradation function and preparation method thereof |
| CN114752982B (en) * | 2022-04-15 | 2023-09-29 | 攀枝花学院 | Biomedical magnesium alloy with time sequence degradation function and preparation method thereof |
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Application publication date: 20120801 |