CN1775305A - 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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- CN1775305A CN1775305A CNA2005100609294A CN200510060929A CN1775305A CN 1775305 A CN1775305 A CN 1775305A CN A2005100609294 A CNA2005100609294 A CN A2005100609294A CN 200510060929 A CN200510060929 A CN 200510060929A CN 1775305 A CN1775305 A CN 1775305A
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- calcium
- phosphate
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- 239000012567 medical material Substances 0.000 title claims abstract description 15
- 239000011248 coating agent Substances 0.000 title claims description 43
- 238000000576 coating method Methods 0.000 title claims description 43
- 238000000034 method Methods 0.000 title claims description 12
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims abstract description 32
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 claims abstract description 28
- 239000001506 calcium phosphate Substances 0.000 claims abstract description 22
- 229910000389 calcium phosphate Inorganic materials 0.000 claims abstract description 19
- 235000011010 calcium phosphates Nutrition 0.000 claims abstract description 19
- 229910000019 calcium carbonate Inorganic materials 0.000 claims abstract description 16
- 239000011572 manganese Substances 0.000 claims abstract description 13
- 238000002360 preparation method Methods 0.000 claims abstract description 13
- 229910052712 strontium Inorganic materials 0.000 claims abstract description 11
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims abstract description 11
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 10
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 10
- 239000011777 magnesium Substances 0.000 claims abstract description 10
- 239000011701 zinc Substances 0.000 claims abstract description 10
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 10
- 239000011159 matrix material Substances 0.000 claims abstract description 8
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 7
- 239000011737 fluorine Substances 0.000 claims abstract description 6
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 6
- 150000002500 ions Chemical class 0.000 claims abstract description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 40
- 239000007788 liquid Substances 0.000 claims description 27
- 239000011575 calcium Substances 0.000 claims description 22
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- IIZPXYDJLKNOIY-JXPKJXOSSA-N 1-palmitoyl-2-arachidonoyl-sn-glycero-3-phosphocholine Chemical compound CCCCCCCCCCCCCCCC(=O)OC[C@H](COP([O-])(=O)OCC[N+](C)(C)C)OC(=O)CCC\C=C/C\C=C/C\C=C/C\C=C/CCCCC IIZPXYDJLKNOIY-JXPKJXOSSA-N 0.000 claims description 12
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 12
- 239000000787 lecithin Substances 0.000 claims description 12
- 229940067606 lecithin Drugs 0.000 claims description 12
- 235000010445 lecithin Nutrition 0.000 claims description 12
- 239000000843 powder Substances 0.000 claims description 12
- -1 phosphate ester Chemical class 0.000 claims description 10
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 8
- 229910019142 PO4 Inorganic materials 0.000 claims description 8
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 claims description 8
- 239000010452 phosphate Substances 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 7
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical group [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 6
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 6
- 238000004945 emulsification Methods 0.000 claims description 6
- 239000000839 emulsion Substances 0.000 claims description 6
- 239000012467 final product Substances 0.000 claims description 6
- 229910052588 hydroxylapatite Inorganic materials 0.000 claims description 6
- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical group [OH-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical class CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 5
- 229910052586 apatite Inorganic materials 0.000 claims description 5
- 230000015572 biosynthetic process Effects 0.000 claims description 5
- VSIIXMUUUJUKCM-UHFFFAOYSA-D pentacalcium;fluoride;triphosphate Chemical group [F-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O VSIIXMUUUJUKCM-UHFFFAOYSA-D 0.000 claims description 5
- 238000004528 spin coating Methods 0.000 claims description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 4
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 4
- 229910002651 NO3 Inorganic materials 0.000 claims description 4
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 4
- 229910052791 calcium Inorganic materials 0.000 claims description 4
- 159000000007 calcium salts Chemical class 0.000 claims description 4
- 238000003618 dip coating Methods 0.000 claims description 4
- 230000032050 esterification Effects 0.000 claims description 4
- 238000005886 esterification reaction Methods 0.000 claims description 4
- 150000002696 manganese Chemical class 0.000 claims description 4
- 239000007921 spray Substances 0.000 claims description 4
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims description 3
- 239000012298 atmosphere Substances 0.000 claims description 3
- 238000007598 dipping method Methods 0.000 claims description 3
- RHFUXPCCELGMFC-UHFFFAOYSA-N n-(6-cyano-3-hydroxy-2,2-dimethyl-3,4-dihydrochromen-4-yl)-n-phenylmethoxyacetamide Chemical compound OC1C(C)(C)OC2=CC=C(C#N)C=C2C1N(C(=O)C)OCC1=CC=CC=C1 RHFUXPCCELGMFC-UHFFFAOYSA-N 0.000 claims description 3
- PNGLEYLFMHGIQO-UHFFFAOYSA-M sodium;3-(n-ethyl-3-methoxyanilino)-2-hydroxypropane-1-sulfonate;dihydrate Chemical compound O.O.[Na+].[O-]S(=O)(=O)CC(O)CN(CC)C1=CC=CC(OC)=C1 PNGLEYLFMHGIQO-UHFFFAOYSA-M 0.000 claims description 3
- 229910000391 tricalcium phosphate Inorganic materials 0.000 claims description 3
- 229940078499 tricalcium phosphate Drugs 0.000 claims description 3
- 229910001069 Ti alloy Inorganic materials 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- 229910000771 Vitallium Inorganic materials 0.000 claims description 2
- FUFJGUQYACFECW-UHFFFAOYSA-L calcium hydrogenphosphate Chemical class [Ca+2].OP([O-])([O-])=O FUFJGUQYACFECW-UHFFFAOYSA-L 0.000 claims description 2
- XAAHAAMILDNBPS-UHFFFAOYSA-L calcium hydrogenphosphate dihydrate Chemical compound O.O.[Ca+2].OP([O-])([O-])=O XAAHAAMILDNBPS-UHFFFAOYSA-L 0.000 claims description 2
- 125000005587 carbonate group Chemical group 0.000 claims description 2
- 239000000919 ceramic Substances 0.000 claims description 2
- 230000002950 deficient Effects 0.000 claims description 2
- 235000019700 dicalcium phosphate Nutrition 0.000 claims description 2
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 2
- 239000010935 stainless steel Substances 0.000 claims description 2
- 229910001220 stainless steel Inorganic materials 0.000 claims description 2
- 239000010936 titanium Substances 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical group CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 claims description 2
- XTTGYFREQJCEML-UHFFFAOYSA-N tributyl phosphite Chemical compound CCCCOP(OCCCC)OCCCC XTTGYFREQJCEML-UHFFFAOYSA-N 0.000 claims description 2
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 claims description 2
- BDZBKCUKTQZUTL-UHFFFAOYSA-N triethyl phosphite Chemical compound CCOP(OCC)OCC BDZBKCUKTQZUTL-UHFFFAOYSA-N 0.000 claims description 2
- 239000000602 vitallium Substances 0.000 claims description 2
- 239000011247 coating layer Substances 0.000 abstract description 7
- 230000033558 biomineral tissue development Effects 0.000 abstract description 2
- 230000001737 promoting effect Effects 0.000 abstract description 2
- 102000004169 proteins and genes Human genes 0.000 abstract description 2
- 108090000623 proteins and genes Proteins 0.000 abstract description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 abstract 2
- 238000001179 sorption measurement Methods 0.000 abstract 2
- 230000009286 beneficial effect Effects 0.000 abstract 1
- 230000002559 cytogenic effect Effects 0.000 abstract 1
- 230000002349 favourable effect Effects 0.000 abstract 1
- 230000028327 secretion Effects 0.000 abstract 1
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 210000004027 cell Anatomy 0.000 description 6
- 210000001519 tissue Anatomy 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 230000006870 function Effects 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 4
- 230000003993 interaction Effects 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 2
- 210000000988 bone and bone Anatomy 0.000 description 2
- 239000007943 implant Substances 0.000 description 2
- 230000005923 long-lasting effect Effects 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000004071 biological effect Effects 0.000 description 1
- 239000012620 biological material Substances 0.000 description 1
- 230000003915 cell function Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 230000011164 ossification Effects 0.000 description 1
- 210000000963 osteoblast Anatomy 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 238000007750 plasma spraying Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000017423 tissue regeneration Effects 0.000 description 1
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Abstract
The present invention discloses a medical material with heterogeneous coating layer and its preparation method. It is composed of medical matrix and heterogeneous coating layer coated on the surface of said medical matrix, the described heterogeneous coating layer is formed by distributing zinc, magnesium or strontium contained calcium phosphate or calcium carbonate coacervate whose gain size is 200nm-20 microns into the calcium phosphate coating layer containing manganese and containing fluorine, in which the surface of calcium phosphate coating layer containing manganese or containing fluorine has high surface potential adsorption function, it is favorable for promoting adsorption of cell on its surface, the zinc, magnesium or strontium contained calcium phosphate or calcium carbonate coacervate has ion-releasing function, it can utilize the mode of releasing beneficial ions to promote cytogenic protein secretion and promote mineralization, etc.
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 sol-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 (11)
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)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100609294A CN100372575C (en) | 2005-09-28 | 2005-09-28 | Medical material with heterogeneous coating and its preparing method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100609294A CN100372575C (en) | 2005-09-28 | 2005-09-28 | Medical material with heterogeneous coating and its preparing method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1775305A true CN1775305A (en) | 2006-05-24 |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| US8784105B2 (en) | 2007-07-19 | 2014-07-22 | Osteoph I Co., Ltd. | Method of fabricating implant with improved surface properties and implant fabricated by the same method |
| CN114432499A (en) * | 2021-12-20 | 2022-05-06 | 脉通医疗科技(嘉兴)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 |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20020064926A (en) * | 1999-12-09 | 2002-08-10 | 닥터.에이치.씨. 로버트 마티즈 스티프텅 | Brushite hydraulic cement stabilized with a magnesium salt |
| CN1228097C (en) * | 2003-08-08 | 2005-11-23 | 浙江大学 | Medical fluorinated calcium phosphate coating material and its prepn process |
-
2005
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8784105B2 (en) | 2007-07-19 | 2014-07-22 | Osteoph I Co., Ltd. | Method of fabricating implant with improved surface properties and implant fabricated by the same method |
| CN101820829B (en) * | 2007-07-19 | 2014-08-13 | 奥斯蒂欧菲尔有限公司 | Method of fabricating implant with improved surface properties and implant fabricated 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 |
| CN114432499A (en) * | 2021-12-20 | 2022-05-06 | 脉通医疗科技(嘉兴)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 |
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