CN100372575C - Medical material with heterogeneous coating and its preparing method - Google Patents
Medical material with heterogeneous coating and its preparing method Download PDFInfo
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- CN100372575C CN100372575C CNB2005100609294A CN200510060929A CN100372575C CN 100372575 C CN100372575 C CN 100372575C CN B2005100609294 A CNB2005100609294 A CN B2005100609294A CN 200510060929 A CN200510060929 A CN 200510060929A CN 100372575 C CN100372575 C CN 100372575C
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Abstract
The present invention discloses a medical material with a heterogeneous coating and a preparation method of the medical material with a heterogeneous coating. The medical material with a heterogeneous coating is composed of a medical basal body and a heterogeneous coating which is coated on the surface of the basal body, wherein the heterogeneous coating is formed by that calcium phosphate or calcium carbonate coacervates which contain zinc, magnesium, or calcium are distributed in a calcium phosphate coating which comprises manganese and fluorine, the sizes of the calcium phosphate or the calcium carbonate coacervates are from 200 nm to 20 mu m, the surface of the calcium phosphate coating which comprises manganese and fluorine has a high surface potential adsorption function which is beneficial to promote the adsorption of cells on the surface of the calcium phosphate coating, the calcium phosphate or the calcium carbonate coacervates which contain zinc, magnesium, or calcium have an ion release function, the protein secretion of cells, the mineralization, etc. are promoted by the method of releasing beneficial ions. The medical material of the present invention can promote the adhesion and the proliferation of cells on the surface of the medical material, and has fortified bioactivity performance. The binding strength of the coating and a metal basal plate is high, and the stability is high.
Description
Technical field
The present invention relates to a kind of biomaterial for medical purpose, especially a kind of surface has medical material heterogeneous coating, that be used for hard tissue repair that the different micron order blocks of two kinds of functions constitute and preparation method thereof.
Background technology
Because sclerous tissues's multidigits such as bone and tooth are in the carrying position, correspondingly, when considering that can its implant produce good bonding with biological tissue, its mechanical property is very important.But being difficult to satisfy, single material takes into account mechanical property and biological activity performance demands.The at present employing at the medical metal matrix surface applies the mode that one deck can deposit the active coating of osteoid apatite more.Adopt plasma spray coating process to prepare one deck hydroxyapatite coating layer in tooth section metal surface as Chinese patent CN1064610, Chinese patent CN1270841 adopts hydro-thermal method synthesis of nano hydroxyl apatite biological painting or the like.But hydroxyapatite coating layer exists several significant weak points: at first, its dissolubility is relatively large, and this will cause the long-lasting decline of coating.Secondly, its activity is still strong inadequately, is difficult to promote the interaction of implant and tissue, reaches to quicken the purpose that new osteanagenesis and material and osseous tissue are integrated fast.Simultaneously, preparation method plays important effect to the performance of coating, because the high temperature in its preparation process causes the decomposition of hydroxyapatite, makes the long-lasting of coating more descend as the coating of plasma spraying.
Although the coating of material surface has only several to arrive the dozens of micron thickness, because material and tissue interaction start from the outermost surface of material, therefore, the structure of coating surface has conclusive effect to the performance of itself and tissue interaction.Tissue at first is embodied in using of cell and material with the effect of material, usually, can be divided into cell attachment and two processes of performance function.Be generally several micron and do not wait because osteoblast is neglected greatly whether to sprawl to tens microns, and need each other to have certain space so that performance osteogenesis function and biomineralization, this explanation ideal material surface should be heterogeneous body on micro-meter scale, uneven: part micron zone should help adhering to of cell, other micron order zone then should be unfavorable for cell attachment, and helps the performance of cell function thereafter.In view of this, prepare heterogeneously, the coating with difference in functionality micron zone can play the effect of getting twice the result with half the effort.
Summary of the invention
What the purpose of this invention is to provide a kind of excellent performance has medical material of heterogeneous coating and preparation method thereof.
Medical material with heterogeneous coating of the present invention is made up of medical base and the heterogeneous coating that is coated in matrix surface, and said heterogeneous coating is that the size that distributes in containing manganese and fluorine-containing calcium phosphate coating is the calcium phosphate that contains zinc, magnesium or strontium of 200nm～20 μ m or the formation of calcium carbonate aggregate.
Above-mentioned medical base can adopt aluminium oxide ceramics, Titanium, titanium alloy, vitallium or medical stainless steel.
Have the preparation method of the medical material of heterogeneous coating, may further comprise the steps:
1) one or more the nanoscale calcium phosphate or the calcium carbonate powder that will contain in zinc, magnesium, three kinds of ions of strontium is scattered in liquid alcohol or the chloroform, and adding the lecithin vigorous stirring simultaneously and imposing ultrasonic emulsification becomes emulsion A; With respect to liquid alcohol or chloroform, the consumption of calcium phosphate or calcium carbonate powder volume by weight counts 0.5%～50%, and the consumption of lecithin volume by weight counts 0.1%～10%;
2) phosphoric acid of phosphate ester or partial esterification, the calcium salt, manganese salt and the fluorochemical that dissolve in alcohol are dissolved in form sol solutions B in the liquid alcohol, the Ca/P mol ratio is 1～2, and Mn/Ca mol ratio 0.0001～0.05, F/Ca mol ratio are 0.001～0.2;
3) A liquid and B liquid were mixed in 1: 50 by volume～2: 1 form coating liquid, lift in conjunction with centrifuging or solution hot spray process at the medical base face coat,, get final product at 500～700 ℃ of heat treatments with so-gel dip-coating method, spin-coating method, dipping.
Among the present invention, described calcium phosphate or the calcium carbonate powder that contains zinc, magnesium, strontium is selected from type alpha tricalcium phosphate, bata-tricalcium phosphate, calcium carbonate, calcium-deficient apatite, hydroxyapatite, carbonate substituted apatite, calcium hydrogen phosphate, one or more in calcium phosphate dibasic dihydrate or the amorphous state calcium phosphate hydroxyapatite powder.Said liquid alcohol is methanol, ethanol, propanol or butanols.Said phosphate ester can be tributyl phosphate, triethyl phosphate, tributyl phosphite or NSC 5284; The phosphoric acid of the said partial esterification phosphoric acid that to be part of O H replaced by ethanol based or butanols base, its molecular formula is PO (OH)
X(OR)
3-X, R is an alcohol radical in the formula, X equals 1 or 2.The said calcium salt that dissolves in alcohol is the nitrate or the acetate of calcium; The manganese salt that dissolves in alcohol is the nitrate or the acetate of manganese.Fluorochemical can be hexafluorophosphoric acid (HPF
6), ammonium hexafluorophosphate (NH
4PF
6), trifluoroacetic acid (CF
3COOH), single fluorophosphoric acid (H
2PO
3F) or ammonium fluoride (NH
4F).As use trifluoroacetic acid, and should in mixed liquor, add triethanolamine in 1: 1 ratio to reduce the acidity of solution, suppress the volatilization of fluorine.
Lift in conjunction with centrifuging with sol-gel dip-coating method, spin-coating method or the dipping of known routine and to prepare coating, can reach required thickness by repeatedly repeating to make the coating on the matrix.Generally lift substrate speed and be controlled between 1cm/min～20cm/min, spin-coating method control rotating speed is between 1000rpm～4000rpm.
Film forming for the benefit of; usually can adopt at nitrogen atmosphere or contain alcohol vapor (methanol; ethanol; propanol or butanols) air atmosphere protection under heat-treat; matrix is under the atmosphere protection all the time, with the evaporation rate of regulating solvent in the liquid film and suppress dried glued membrane and absorb moisture content.
Heterogeneous coating among the present invention has two kinds of heterogeneous mac function surfaces: wherein containing manganese or fluorine-containing calcium phosphate coating surface is " the absorption block " with high surface potential, help promoting the absorption of cell on its surface, calcium phosphate or calcium carbonate aggregate that another kind contains zinc, magnesium or strontium are " the slow release blocks " with ion release function, promote cell performance protein branch to ooze, promote functions such as mineralising by discharging useful ionic mode.In addition, the coating matrix dissolubility is lower, and the bond strength height of coating and metal basal board, has guaranteed the long-time stability of coating.
Description of drawings
Fig. 1 is a heterogeneous body coating sketch map, and the granule that distributes among the figure is calcium phosphate or the calcium carbonate aggregate that contains zinc, magnesium or strontium.
The specific embodiment
Further specify the present invention below in conjunction with example.
Embodiment 1
Zinciferous nanometer alpha-tricalcium phosphate powder is scattered in the methanol, and adding the lecithin vigorous stirring simultaneously and imposing ultrasonic emulsification becomes emulsion A; With respect to methanol, the consumption of type alpha tricalcium phosphate powder volume by weight counts 0.5%, and the consumption of lecithin volume by weight counts 0.1%; With phosphate ester, lime nitrate, manganese nitrate and hexafluorophosphoric acid are dissolved in and form sol solutions B in the methanol, and the Ca/P mol ratio is 1, and Mn/Ca mol ratio 0.0001, F/Ca mol ratio are 0.001.A liquid and B liquid were mixed the formation coating liquid in 1: 50 by volume, and at the medical base face coat, heat treatment under 500 ℃ of nitrogen atmospheres gets final product with the sol-gel dip-coating method.The structure of the heterogeneous coating on medical base surface as shown in Figure 1.
Embodiment 2
Magniferous nano beta-tricalcium phosphate powder is scattered in the ethanol, and adding the lecithin vigorous stirring simultaneously and imposing ultrasonic emulsification becomes emulsion A; With respect to ethanol, the consumption of bata-tricalcium phosphate powder volume by weight counts 1%, and the consumption of lecithin volume by weight counts 5%; With phosphate ester, lime nitrate, manganese nitrate and ammonium fluoride are dissolved in and form sol solutions B in the ethanol, and the Ca/P mol ratio is 2, and Mn/Ca mol ratio 0.05, F/Ca mol ratio are 0.2.A liquid and B liquid were mixed the formation coating liquid in 1: 1 by volume, and at the medical base face coat, heat treatment under 600 ℃ of nitrogen atmospheres gets final product with spin-coating method.
Embodiment 3
The nanometer grade calcium carbonate powder that will contain strontium is scattered in the ethanol, and adding the lecithin vigorous stirring simultaneously and imposing ultrasonic emulsification becomes emulsion A; With respect to ethanol, the consumption of calcium carbonate powder volume by weight counts 25%, and the consumption of lecithin volume by weight counts 6%; With phosphate ester, lime nitrate, manganese nitrate and single fluorophosphoric acid are dissolved in and form sol solutions B in the ethanol, and the Ca/P mol ratio is 1.67, and Mn/Ca mol ratio 0.005, F/Ca mol ratio are 0.05.A liquid and B liquid mixed forming coating liquid in 1: 25 by volume, at the medical base face coat, heat treatment under 700 ℃ of air atmospheres that contain the ethanol steam gets final product with the solution hot spray process.
Embodiment 4
Zinciferous nano-grade hydroxy apatite powder is scattered in the propanol, and adding the lecithin vigorous stirring simultaneously and imposing ultrasonic emulsification becomes emulsion A; With respect to propanol, the consumption of level hydroxyapatite powder volume by weight counts 50%, and the consumption of lecithin volume by weight counts 10%; With phosphate ester, lime nitrate, manganese nitrate and trifluoroacetic acid are dissolved in and form sol solutions B in the propanol, and the Ca/P mol ratio is 1.5, and Mn/Ca mol ratio 0.01, F/Ca mol ratio are 0.15.A liquid and B liquid mixed forming coating liquid in 2: 1 by volume, at the medical base face coat, heat treatment under 600 ℃ of air atmospheres that contain the propanol steam gets final product with the solution hot spray process.
Claims (8)
1. medical material with heterogeneous coating, it is characterized in that being made up of medical base and the heterogeneous coating that is coated in matrix surface, said heterogeneous coating is that the size that distributes in containing manganese and fluorine-containing calcium phosphate coating is the calcium phosphate that contains zinc, magnesium or strontium of 200nm～20 μ m or the formation of calcium carbonate aggregate.
2. the medical material with heterogeneous coating according to claim 1 is characterized in that said medical base is aluminium oxide ceramics, Titanium, titanium alloy, vitallium or medical stainless steel.
3. the preparation method with medical material of heterogeneous coating according to claim 1 is characterized in that may further comprise the steps:
1) one or more the nanoscale calcium phosphate or the calcium carbonate powder that will contain in zinc, magnesium, three kinds of ions of strontium is scattered in liquid alcohol or the chloroform, and adding the lecithin vigorous stirring simultaneously and imposing ultrasonic emulsification becomes emulsion A; With respect to liquid alcohol or chloroform, the consumption of calcium phosphate or calcium carbonate powder volume by weight counts 0.5%～50%, and the consumption of lecithin volume by weight counts 0.1%～10%;
2) phosphoric acid of phosphate ester or partial esterification, the calcium salt, manganese salt and the fluorochemical that dissolve in alcohol are dissolved in form sol solutions B in the liquid alcohol, the Ca/P mol ratio is 1～2, and Mn/Ca mol ratio 0.0001～0.05, F/Ca mol ratio are 0.001～0.2;
3) A liquid and B liquid were mixed in 1: 50 by volume～2: 1 form coating liquid, lift in conjunction with centrifuging or solution hot spray process at the medical base face coat,, get final product at 500～700 ℃ of heat treatments with sol-gel dip-coating method, spin-coating method, dipping.
4. the preparation method with medical material of heterogeneous coating according to claim 3, it is characterized in that described calcium phosphate or the calcium carbonate powder that contains zinc, magnesium, strontium is selected from type alpha tricalcium phosphate, bata-tricalcium phosphate, calcium carbonate, calcium-deficient apatite, hydroxyapatite, carbonate substituted apatite, calcium hydrogen phosphate, one or more in calcium phosphate dibasic dihydrate or the amorphous state calcium phosphate hydroxyapatite powder.
5. the preparation method with medical material of heterogeneous coating according to claim 3 is characterized in that described liquid alcohol is methanol, ethanol, propanol or butanols;
6. the preparation method with medical material of heterogeneous coating according to claim 3 is characterized in that described phosphate ester is tributyl phosphate, triethyl phosphate, tributyl phosphite or NSC 5284; The phosphoric acid of the described partial esterification phosphoric acid that to be part of O H replaced by ethanol based or butanols base, its molecular formula is PO (OH)
X(OR)
3-X, R is an alcohol radical in the formula, X equals 1 or 2.
7. the preparation method with medical material of heterogeneous coating according to claim 3 is characterized in that the described calcium salt that dissolves in alcohol is the nitrate or the acetate of calcium; The manganese salt that dissolves in alcohol is the nitrate or the acetate of manganese; Fluorochemical is hexafluorophosphoric acid, ammonium hexafluorophosphate, trifluoroacetic acid, single fluorophosphoric acid or ammonium fluoride.
8. the preparation method with medical material of heterogeneous coating according to claim 3 is characterized in that heat treatment is at nitrogen atmosphere or contain under the air atmosphere protection of alcohol vapor and carry out.
Priority Applications (1)
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|---|---|---|---|
| CNB2005100609294A CN100372575C (en) | 2005-09-28 | 2005-09-28 | Medical material with heterogeneous coating and its preparing method |
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|---|---|---|---|
| CNB2005100609294A CN100372575C (en) | 2005-09-28 | 2005-09-28 | Medical material with heterogeneous coating and its preparing method |
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|---|---|
| CN1775305A CN1775305A (en) | 2006-05-24 |
| CN100372575C true CN100372575C (en) | 2008-03-05 |
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Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100775537B1 (en) * | 2007-07-19 | 2007-11-28 | (주)오스테오필 | Method of fabricating implant with improved surface properties and implant fabiricated by the same method |
| CN102886073A (en) * | 2012-10-09 | 2013-01-23 | 天津大学 | Biological glass coat for medical magnesium alloy surface and preparation method of biological glass coat |
| CN114432499B (en) * | 2021-12-20 | 2023-02-17 | 浙江脉通智造科技(集团)有限公司 | Artificial blood vessel and preparation method thereof |
| CN115844737A (en) * | 2022-12-31 | 2023-03-28 | 广西信业生物技术有限公司 | Preparation method of bioactive mineral material for repairing enamel calcium |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1378464A (en) * | 1999-12-09 | 2002-11-06 | H·C·罗伯特·马泰斯·斯蒂夫腾 | Brushite hydraulic cement stabilized with magnesium salt |
| CN1486751A (en) * | 2003-08-08 | 2004-04-07 | 浙江大学 | Medical fluorinated calcium phosphate coating material and its prepn process |
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2005
- 2005-09-28 CN CNB2005100609294A patent/CN100372575C/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1378464A (en) * | 1999-12-09 | 2002-11-06 | H·C·罗伯特·马泰斯·斯蒂夫腾 | Brushite hydraulic cement stabilized with magnesium salt |
| CN1486751A (en) * | 2003-08-08 | 2004-04-07 | 浙江大学 | Medical fluorinated calcium phosphate coating material and its prepn process |
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Granted publication date: 20080305 Termination date: 20120928 |