CN104189962B - A kind of surface has Fe-TiO 2angiocarpy bracket of coating and preparation method thereof - Google Patents
A kind of surface has Fe-TiO 2angiocarpy bracket of coating and preparation method thereof Download PDFInfo
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- CN104189962B CN104189962B CN201410437929.0A CN201410437929A CN104189962B CN 104189962 B CN104189962 B CN 104189962B CN 201410437929 A CN201410437929 A CN 201410437929A CN 104189962 B CN104189962 B CN 104189962B
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- angiocarpy bracket
- colloid
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Abstract
The invention provides a kind of surface and there is Fe-TiO
2the angiocarpy bracket of coating, the basic unit of angiocarpy bracket is coated with Fe-TiO
2coating; Described angiocarpy bracket basic unit is magnesium titanium alloy, magnesium titanium-aluminium alloy, magnesium titanium chrome alloy, magnesium titanium chrome-nickel, magnesium titanium cochrome; Described Fe-TiO
2coating comprises oxide membranous layer, containing Nanoscale Iron and/or ferric oxide particles in this oxide membranous layer.Described Fe-TiO
2coating makes angiocarpy bracket have good biocompatibility, extends the useful life of described angiocarpy bracket in human body, has very high use value.
Description
Technical field
The present invention relates to angiocarpy bracket technical field, particularly, relate to a kind of surface and there is Fe-TiO
2angiocarpy bracket of coating and preparation method thereof.
Background technology
In recent years, magnesium alloy obtains the wide application sent out clinically as angiocarpy bracket material.Magnesium alloy utilizes magnesium can progressively degrade human internal environment and finally disappear, and can realize metal implant repair function in vivo.And magnesium is the biological element of organism, have good biocompatibility, unique degradability, excellent comprehensive mechanical property, thus its medical application prospect is very tempting and wide.
But the decay resistance of Magnesium and magnesium alloys is poor, the normal potential of pure magnesium is-2.37V, is especially containing Cl
-in the human physiological environment of ion more very; Conventional Magnesium and magnesium alloys is in simulated body fluid, and corrosion degradation speed can reach 0.05-6mm/year.In addition, magnesium alloy bracket implants cardiovascular, by the impact of blood flow, is easy to fracture or subsides; Thus before blood vessel is moulding, losing the effect of support, even causing death, this limits the further application of magnesium alloy bracket in angiocarpy bracket to a great extent.
Summary of the invention
In order to overcome the deficiencies in the prior art, the invention provides a kind of surface and there is Fe-TiO
2the angiocarpy bracket of coating, described Fe-TiO
2coating makes angiocarpy bracket have good biocompatibility, antibiotic property, and extends the useful life of described angiocarpy bracket in human body, has very high use value.
Technical scheme of the present invention is as follows: a kind of surface has Fe-TiO
2the angiocarpy bracket of coating, the basic unit of angiocarpy bracket is coated with Fe coating; Described angiocarpy bracket basic unit is magnesium titanium alloy, magnesium titanium-aluminium alloy, magnesium titanium chrome alloy, magnesium titanium chrome-nickel, magnesium titanium cochrome; The content of titanium elements described in alloy is not less than 30%, and described Fe coating comprises oxide membranous layer, containing Nanoscale Iron and/or ferric oxide particles in this oxide membranous layer.
Described oxide membranous layer covers described angiocarpy bracket basic unit equably, and its thickness is 1-100um, preferred 10-100um, most preferably 20-40um.
The main component of described oxide membranous layer is TiO
2.
Described oxide membranous layer is rough rete.
Described Nanoscale Iron and/or ferric oxide particles nonuniform deposition or embed in described oxide membranous layer, its concentration reduces along with the increase of described oxidation film layer depth.
The preparation method of above-mentioned angiocarpy bracket, comprises the steps:
1) prepare dispersion system of colloid, described dispersion system of colloid comprises the pure water or ion exchange water with zero or low conductivity, discrete particles, electrolyte and additive; Wherein, described discrete particles concentration is 1-100mg/L, and be Nanoscale Iron and/or ferric oxide particles, particle diameter is 10-100nm; Described additive concentration is 1-10mg/L, is selected from magnesium oxide, calcium phosphate, waterglass sodium, the compositions of one or several in waterglass potassium or waterglass silicon; Described electrolytical formula is Na
2siO
310-15g/L, NaOH15-20g/L, organic amine 10-20g/L, peroxidase 12-5g/L;
2) described dispersion system of colloid is put into electrolysis bath, angiocarpy bracket is impregnated in described dispersion system of colloid, then, described angiocarpy bracket is connected positive source, in described electrolysis bath, power cathode is set, this power cathode is cup and surrounds described positive source, AC voltage difference is produced between positive source and power cathode, be oxidation film by plasma electrolytic oxidation by the surface conversion of the angiocarpy bracket be immersed in described dispersion system of colloid, discrete particles Nanoscale Iron in dispersion system of colloid and/or ferric oxide particles deposit in this oxidation film, wherein, the time of plasma electrolytic oxidation is 10-30 minute.
The maximum of described AC voltage difference is 0.1V-4800V, and has the frequency of 0.01Hz-1200Hz.
The temperature of described dispersion system of colloid is-20-150 DEG C, and circulates with the cycle rate of 0-5000L/min.
Described AC voltage is symmetrical or asymmetric AC voltage.
In above-mentioned preparation method, described angiocarpy bracket base material is as the positive pole of electrolytic cell, pass through plasma electrolysis oxidation process, described angiocarpy bracket substrate surface under an applied electric field, form plasma discharge and produce at substrate surface and spark, thus metal surface is converted into corresponding metal-oxide, form oxidation film, this oxidation film be in fact base material chemical conversion and from original metal surface simultaneously inwardly with to outgrowth, be made up of crystalline phase, there is highly porous surface.This oxidation film has rough surface, and thickness is 1-100um, preferred 10-100um, most preferably 20-40um.In the application, because base material contains titanium, thus form the oxidation film containing titanium dioxide.
Described discrete particles to be dispersed in described dispersion system of colloid and to provide electric conductivity for it, and discrete particles nonuniform deposition is on described oxidation film surface.Discrete particles of the present invention is nano iron particles/or ferrum oxide.Nano iron particles/or ferrum oxide have good biocompatibility, thus extend the useful life of angiocarpy bracket.
Beneficial effect of the present invention is: a kind of surface has Fe-TiO
2angiocarpy bracket of coating and preparation method thereof, by arranging Fe-TiO on angiocarpy bracket surface
2coating makes angiocarpy bracket have good biocompatibility, extends the useful life of described angiocarpy bracket in human body, has very high use value.
Accompanying drawing explanation
Fig. 1 is that surface of the present invention has Fe-TiO
2the structural representation of the angiocarpy bracket of coating.
Detailed description of the invention
Embodiment 1:
A kind of surface has Fe-TiO
2the angiocarpy bracket of coating, is included in the basic unit 1 of angiocarpy bracket and the Fe-TiO of upper covering thereof
2coating 2, described Fe-TiO
2coating 2 comprises oxide membranous layer 21, containing Nanoscale Iron and/or ferric oxide particles 22 in this oxide membranous layer 21.
Described angiocarpy bracket basic unit 1 is magnesium titanium alloy, magnesium titanium-aluminium alloy, magnesium titanium chrome alloy, magnesium titanium chrome-nickel, the one in magnesium titanium cochrome.
The main component of described oxide membranous layer 21 is TiO
2, be rough rete.Cover in described angiocarpy bracket basic unit 1 equably, its thickness is 1-100um, preferred 10-100um, most preferably 20-40um.
Described Nanoscale Iron and/or ferric oxide particles 22 nonuniform deposition or embed in described oxide membranous layer 21, its concentration reduces along with the increase of described oxide membranous layer 21 degree of depth.
Embodiment 2
The preparation method of above-mentioned angiocarpy bracket, comprises the steps:
1) prepare dispersion system of colloid, described dispersion system of colloid comprises the pure water with zero conductivity, discrete particles, electrolyte and additive; Wherein, described discrete particles concentration is 50mg/L, is nano iron particles, and particle diameter is 10-30nm; Described additive concentration is 10mg/L, is magnesium oxide; Described additive concentration is 10mg/L, is magnesium oxide; Described electrolytical formula is Na
2siO
3115g/L, NaOH20g/L, organic amine 15g/L, peroxide 5g/L;
2) described dispersion system of colloid is put into an electrolysis bath, angiocarpy bracket is impregnated in described dispersion system of colloid, then, described angiocarpy bracket is connected positive source, in described electrolysis bath, arrange power cathode, described power cathode is cup-shaped and surrounds described positive source, and produces asymmetric AC voltage difference between a positive electrode and a negative electrode, the maximum of voltage difference is 1200V, and has the frequency of 300Hz.The temperature of described dispersion system of colloid is 20 DEG C, and circulates with the cycle rate of 2000L/min.Be oxidation film by plasma electrolytic oxidation by the surface conversion of the angiocarpy bracket be immersed in described dispersion system of colloid, containing Nanoscale Iron and/or ferric oxide particles in this oxidation film.
Embodiment 3
The preparation method of above-mentioned angiocarpy bracket, comprises the steps:
1) prepare dispersion system of colloid, described dispersion system of colloid comprises the ion exchange water with low conductivity, discrete particles, electrolyte and additive; Wherein, described discrete particles concentration is 100mg/L, and be ferric oxide particles and/or nano iron particles, particle diameter is 10nm; Described electrolytical formula is Na
2siO
310g/L, NaOH20g/L, organic amine 20g/L, peroxidase 12 g/L;
2) described dispersion system of colloid is put into electrolysis bath, angiocarpy bracket is impregnated in described dispersion system of colloid, then, described angiocarpy bracket is connected positive source, in described electrolysis bath, power cathode is set, described power cathode is cup-shaped and surrounds described positive source, and produce AC voltage difference between a positive electrode and a negative electrode, be oxidation film by plasma electrolytic oxidation by the surface conversion of the angiocarpy bracket be immersed in described dispersion system of colloid, containing Nanoscale Iron and/or ferric oxide particles in this oxidation film.
The maximum of described AC voltage difference is 4800V, and has the frequency of 1200Hz.
The temperature of described dispersion system of colloid is 150 DEG C, and circulates with the cycle rate of 5000L/min.
Described AC voltage is asymmetric AC voltage.
Embodiment 4
The preparation method of above-mentioned angiocarpy bracket, comprises the steps:
1) prepare dispersion system of colloid, described dispersion system of colloid comprises the pure water or ion exchange water with zero or low conductivity, discrete particles, additive; Wherein, described discrete particles concentration is 1mg/L, and be ferric oxide particles and/or nano iron particles, particle diameter is 10nm; Described additive concentration is 1mg/L, is selected from magnesium oxide, calcium phosphate, waterglass sodium, the compositions of one or several in waterglass potassium or waterglass silicon; Described electrolytical formula is Na
2siO
315g/L, NaOH20g/L, organic amine 10g/L, peroxidase 12 g/L;
2) described dispersion system of colloid is put into electrolysis bath, angiocarpy bracket is impregnated in described dispersion system of colloid, then, described angiocarpy bracket is connected positive source, in described electrolysis bath, power cathode is set, described power cathode is cup-shaped and surrounds described positive source, and produce AC voltage difference between a positive electrode and a negative electrode, be oxidation film by plasma electrolytic oxidation by the surface conversion of the angiocarpy bracket be immersed in described dispersion system of colloid, containing Nanoscale Iron and/or ferric oxide particles in this oxidation film.
The maximum of described AC voltage difference is 0.1V, and has the frequency of 0.01Hz.
The temperature of described dispersion system of colloid is-20 DEG C, and circulates with the cycle rate of 100L/min.
Described AC voltage is symmetrical voltage.
Above content is in conjunction with concrete preferred implementation further description made for the present invention, can not assert that specific embodiment of the invention is confined to these explanations.For general technical staff of the technical field of the invention, without departing from the inventive concept of the premise, its framework form can be flexible and changeable, can subseries product.Just make some simple deduction or replace, all should be considered as belonging to the scope of patent protection that the present invention is determined by submitted to claims.
Claims (7)
1. a surface has Fe-TiO
2the angiocarpy bracket of coating, is characterized in that, the basic unit of angiocarpy bracket is coated with Fe coating; Described angiocarpy bracket basic unit is magnesium titanium alloy, magnesium titanium-aluminium alloy, magnesium titanium chrome alloy, magnesium titanium chrome-nickel, magnesium titanium cochrome; Described Fe coating comprises oxide membranous layer, containing Nanoscale Iron and/or ferric oxide particles in this oxide membranous layer; The main component of described oxide membranous layer is TiO
2.
2. surface as claimed in claim 1 has Fe-TiO
2the angiocarpy bracket of coating, is characterized in that, described oxide membranous layer covers described angiocarpy bracket basic unit equably, and its thickness is 1-100um.
3. surface as claimed in claim 1 has Fe-TiO
2the angiocarpy bracket of coating, is characterized in that, described Nanoscale Iron and/or ferric oxide particles nonuniform deposition or embed in described oxide membranous layer, and its concentration reduces along with the increase of described oxidation film layer depth.
4. the preparation method of angiocarpy bracket as described in any one of claim 1-3, is characterized in that, comprise the steps:
1) prepare dispersion system of colloid, described dispersion system of colloid comprises the pure water or ion exchange water with zero or low conductivity, discrete particles, electrolyte and additive; Wherein, described discrete particles concentration is 1-100mg/L, and be Nanoscale Iron and/or ferric oxide particles, particle diameter is 10-100nm; Described additive concentration is 1-10mg/L, is selected from magnesium oxide, calcium phosphate, waterglass sodium, the compositions of one or several in waterglass potassium or waterglass silicon; Described electrolytical formula is Na
2siO
310-15g/L, NaOH15-20g/L, organic amine 10-20g/L, peroxidase 12-5g/L;
2) described dispersion system of colloid is put into electrolysis bath, angiocarpy bracket is impregnated in described dispersion system of colloid, then, described angiocarpy bracket is connected positive source, in described electrolysis bath, power cathode is set, this power cathode is cup and surrounds described positive source, AC voltage difference is produced between positive source and power cathode, be oxidation film by plasma electrolytic oxidation by the surface conversion of the angiocarpy bracket be immersed in described dispersion system of colloid, discrete particles Nanoscale Iron in dispersion system of colloid and/or ferric oxide particles deposit in this oxidation film, wherein, the time of plasma electrolytic oxidation is 10-30 minute.
5. the preparation method of angiocarpy bracket as claimed in claim 4, it is characterized in that, the maximum of described AC voltage difference is 0.1V-4800V, and has the frequency of 0.01Hz-1200Hz.
6. the preparation method of angiocarpy bracket as claimed in claim 4, it is characterized in that, the temperature of described dispersion system of colloid is-20-150 DEG C, and circulates with the cycle rate of 0-5000L/min.
7. the preparation method of angiocarpy bracket as claimed in claim 4, is characterized in that, described AC voltage is symmetrical or asymmetric AC voltage.
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| CN1791437A (en) * | 2003-05-16 | 2006-06-21 | 布卢薄膜有限责任公司 | Medical implants comprising biocompatible coatings |
| WO2008098922A2 (en) * | 2007-02-13 | 2008-08-21 | Cinvention Ag | Biodegradable porous stent |
| CN101257860A (en) * | 2005-04-05 | 2008-09-03 | 万能医药公司 | Degradable implantable medical devices |
| 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 |
| CN103028148A (en) * | 2012-12-28 | 2013-04-10 | 上海交通大学 | Medical degradable Fe-Mg-X alloy material and preparation method thereof |
| CN103614601A (en) * | 2013-12-16 | 2014-03-05 | 苏州奥芮济医疗科技有限公司 | In-vivo controlled degradable bacteriostatic Mg-Ag-Zn-Mn magnesium alloy implant material and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2009158333A2 (en) * | 2008-06-25 | 2009-12-30 | Boston Scientific Scimed, Inc. | Medical devices for delivery of therapeutic agent in conjunction with galvanic corrosion |
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Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1791437A (en) * | 2003-05-16 | 2006-06-21 | 布卢薄膜有限责任公司 | Medical implants comprising biocompatible coatings |
| CN101257860A (en) * | 2005-04-05 | 2008-09-03 | 万能医药公司 | Degradable implantable medical devices |
| WO2008098922A2 (en) * | 2007-02-13 | 2008-08-21 | Cinvention Ag | Biodegradable porous stent |
| 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 |
| CN103028148A (en) * | 2012-12-28 | 2013-04-10 | 上海交通大学 | Medical degradable Fe-Mg-X alloy material and preparation method thereof |
| CN103614601A (en) * | 2013-12-16 | 2014-03-05 | 苏州奥芮济医疗科技有限公司 | In-vivo controlled degradable bacteriostatic Mg-Ag-Zn-Mn magnesium alloy implant material and preparation method thereof |
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