CN1743014A - Biological medical material with biological responding coating and preparing method - Google Patents
Biological medical material with biological responding coating and preparing method Download PDFInfo
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- CN1743014A CN1743014A CN 200510060928 CN200510060928A CN1743014A CN 1743014 A CN1743014 A CN 1743014A CN 200510060928 CN200510060928 CN 200510060928 CN 200510060928 A CN200510060928 A CN 200510060928A CN 1743014 A CN1743014 A CN 1743014A
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- 238000000576 coating method Methods 0.000 title claims description 31
- 239000011248 coating agent Substances 0.000 title claims description 30
- 238000000034 method Methods 0.000 title claims description 12
- 239000012567 medical material Substances 0.000 title abstract description 4
- 229910052588 hydroxylapatite Inorganic materials 0.000 claims abstract description 15
- 238000002360 preparation method Methods 0.000 claims abstract description 15
- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical compound [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 abstract description 14
- 239000011247 coating layer Substances 0.000 claims abstract description 6
- 239000002103 nanocoating Substances 0.000 claims abstract description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 43
- 239000011575 calcium Substances 0.000 claims description 20
- 229910021645 metal ion Inorganic materials 0.000 claims description 20
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 14
- 239000003519 biomedical and dental material Substances 0.000 claims description 14
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 8
- 229910052791 calcium Inorganic materials 0.000 claims description 8
- 239000002243 precursor Substances 0.000 claims description 8
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 7
- 239000011701 zinc Substances 0.000 claims description 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 6
- 239000012688 phosphorus precursor Substances 0.000 claims description 6
- 229910052691 Erbium Inorganic materials 0.000 claims description 5
- 229910052693 Europium Inorganic materials 0.000 claims description 5
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 5
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 5
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 5
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 5
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 5
- YWEUIGNSBFLMFL-UHFFFAOYSA-N diphosphonate Chemical compound O=P(=O)OP(=O)=O YWEUIGNSBFLMFL-UHFFFAOYSA-N 0.000 claims description 5
- UYAHIZSMUZPPFV-UHFFFAOYSA-N erbium Chemical compound [Er] UYAHIZSMUZPPFV-UHFFFAOYSA-N 0.000 claims description 5
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 claims description 5
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 5
- 239000010931 gold Substances 0.000 claims description 5
- 229910052737 gold Inorganic materials 0.000 claims description 5
- 229910052746 lanthanum Inorganic materials 0.000 claims description 5
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 5
- 239000011777 magnesium Substances 0.000 claims description 5
- 229910052749 magnesium Inorganic materials 0.000 claims description 5
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 5
- DLYUQMMRRRQYAE-UHFFFAOYSA-N phosphorus pentoxide Inorganic materials O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 claims description 5
- 229910052710 silicon Inorganic materials 0.000 claims description 5
- 239000010703 silicon Substances 0.000 claims description 5
- 229910052708 sodium Inorganic materials 0.000 claims description 5
- 239000011734 sodium Substances 0.000 claims description 5
- 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 5
- 238000004528 spin coating Methods 0.000 claims description 5
- 229910052712 strontium Inorganic materials 0.000 claims description 5
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims description 5
- 229910052725 zinc Inorganic materials 0.000 claims description 5
- 229910052726 zirconium Inorganic materials 0.000 claims description 5
- 229910019142 PO4 Inorganic materials 0.000 claims description 4
- 229940043430 calcium compound Drugs 0.000 claims description 4
- 150000001674 calcium compounds Chemical class 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- 239000013078 crystal Substances 0.000 claims description 4
- 238000003618 dip coating Methods 0.000 claims description 4
- 238000007598 dipping method Methods 0.000 claims description 4
- 230000032050 esterification Effects 0.000 claims description 4
- 238000005886 esterification reaction Methods 0.000 claims description 4
- 239000011159 matrix material Substances 0.000 claims description 4
- 239000010452 phosphate Substances 0.000 claims description 4
- -1 phosphate ester Chemical class 0.000 claims description 4
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 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
- VSGNNIFQASZAOI-UHFFFAOYSA-L calcium acetate Chemical compound [Ca+2].CC([O-])=O.CC([O-])=O VSGNNIFQASZAOI-UHFFFAOYSA-L 0.000 claims description 3
- 239000001639 calcium acetate Substances 0.000 claims description 3
- 229960005147 calcium acetate Drugs 0.000 claims description 3
- 235000011092 calcium acetate Nutrition 0.000 claims description 3
- 239000000919 ceramic Substances 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
- 239000011591 potassium Substances 0.000 claims description 3
- 229910052700 potassium Inorganic materials 0.000 claims description 3
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 2
- 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
- 239000012467 final product Substances 0.000 claims description 2
- 239000011574 phosphorus Substances 0.000 claims description 2
- 229910052698 phosphorus Inorganic materials 0.000 claims description 2
- 239000007921 spray 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
- 238000003756 stirring Methods 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
- 239000000602 vitallium Substances 0.000 claims description 2
- 210000000988 bone and bone Anatomy 0.000 abstract description 4
- 230000004072 osteoblast differentiation Effects 0.000 abstract description 4
- 238000013036 cure process Methods 0.000 abstract 1
- 239000010410 layer Substances 0.000 abstract 1
- 230000035755 proliferation Effects 0.000 abstract 1
- 230000001476 alcoholic effect Effects 0.000 description 10
- 230000015572 biosynthetic process Effects 0.000 description 7
- 238000002156 mixing Methods 0.000 description 4
- 230000011164 ossification Effects 0.000 description 4
- 230000004936 stimulating effect Effects 0.000 description 4
- 210000001519 tissue Anatomy 0.000 description 4
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 4
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 3
- 230000004071 biological effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- 239000011737 fluorine Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 210000002997 osteoclast Anatomy 0.000 description 3
- VSIIXMUUUJUKCM-UHFFFAOYSA-D pentacalcium;fluoride;triphosphate Chemical compound [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 description 3
- 229910052586 apatite Inorganic materials 0.000 description 2
- 230000000975 bioactive effect Effects 0.000 description 2
- 239000007943 implant Substances 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000007750 plasma spraying Methods 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- DHEQXMRUPNDRPG-UHFFFAOYSA-N strontium nitrate Chemical compound [Sr+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O DHEQXMRUPNDRPG-UHFFFAOYSA-N 0.000 description 2
- 208000035404 Autolysis Diseases 0.000 description 1
- 208000006386 Bone Resorption Diseases 0.000 description 1
- 206010057248 Cell death Diseases 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 206010061218 Inflammation Diseases 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 230000008468 bone growth Effects 0.000 description 1
- 230000024279 bone resorption Effects 0.000 description 1
- 239000001506 calcium phosphate Substances 0.000 description 1
- 238000010523 cascade reaction Methods 0.000 description 1
- 239000008199 coating composition Substances 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 229910052587 fluorapatite Inorganic materials 0.000 description 1
- 229940077441 fluorapatite Drugs 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 230000035876 healing Effects 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000004054 inflammatory process Effects 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 230000005923 long-lasting effect Effects 0.000 description 1
- 210000000963 osteoblast Anatomy 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 230000028043 self proteolysis Effects 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 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 description 1
- 229940078499 tricalcium phosphate Drugs 0.000 description 1
- 229910000391 tricalcium phosphate Inorganic materials 0.000 description 1
- 235000019731 tricalcium phosphate Nutrition 0.000 description 1
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- Materials For Medical Uses (AREA)
Abstract
The present invention discloses a biological medical material with biological resposibility coating layer and its preparation method. It is formed from medical basal body and metal-iron-doped fluorine-contained hydroxy apatite nano coating layer coated on the surface of medical basal body. Said biological medical material can stimulate osteoblast differentiation and proliferation in early stage of implatation, can promote growth of bone and can accelerate cure process. Said invention also provides the concrete steps of its preparation method.
Description
Technical field
The present invention relates to a kind of medical bio coating material with high biological responding surface, especially a kind of surface has stimulating osteoblast differentiation, propagation, promote osteogenesis, the gold doping that is used for hard tissue substituting belongs to medical material of ionic fluoridated hydroxyapatite nano coating and preparation method thereof.
Background technology
Bioactive ceramics obtains to pay close attention to widely because of having good bone conductibility and biocompatibility, but as sclerous tissues's loading material, monophasic pottery or metal are difficult to satisfy takes into account mechanical property and biological activity performance demands.The at present employing at the medical metal matrix surface applies the mode that can form synosteotic active coating with human body hard tissue more.Adopt plasma spray coating process to prepare hydroxyapatite coating layer in tooth section metal surface as Chinese patent CN1064610, Chinese patent CN1634609 adopts duplex skill plasma spraying method to prepare nano-hydroxyapatite biological coating or the like.But adopt the hydroxyapatite coating layer of plasma spraying method preparation, can occur impurity mutually and coating autolysis degree excessive relatively, may take place in application that the coating dissolving comes off and particulate formation etc., cause inflammation in the part, activate osteoclast.Bring out a series of dissolved cascade reactions of bone that cause, the problem that finally causes implant to lose efficacy.And, no matter be bioactive ceramicses such as hydroxyapatite or tricalcium phosphate, all can not promote osteogenesis or suppress bone resorption, thus limit its further application.By improving the performance that preparation method and coating composition improve bioactivity coatings, be the approach that present most researcher adopts.
Summary of the invention
The purpose of this invention is to provide a kind of surface and have stimulating osteoblast differentiation, propagation, bio-medical material of the biological responding coating of promote osteogenesis and preparation method thereof.
Bio-medical material with biological responding coating provided by the invention belongs to ionic fluoridated hydroxyapatite nano coating by medical base with the gold doping that is coated in matrix surface and forms, coating layer thickness is between 200nm～50 μ m, the mol ratio of F/Ca is 0.001～0.2 in the coating, the mol ratio of Ca/P is 1.67, and the mol ratio of metal ion and calcium is 0.0001～0.05.
Above-mentioned medical base can be titanium alloy, Titanium, vitallium, aluminium oxide ceramics or medical stainless steel.Said metal ion can be selected from zinc, strontium, magnesium, lanthanum, europium, erbium, manganese, silicon, zirconium, one or more in sodium and the potassium.Gold doping belongs in the ionic fluoridated hydroxyapatite nano coating crystal grain size between 10～20nm.
Preparation method with bio-medical material of biological responding coating of the present invention may further comprise the steps:
1) to be dissolved in and to form concentration in the alcohol be the calcium precursor of 1～4mol/L to the calcium compounds that will dissolve in liquid alcohol;
2) to be dissolved in and to form concentration in the alcohol be the metal ion precursor of 0.005mol/L～0.1mol/L to the metal ion compound that will dissolve in liquid alcohol;
3) phosphoric acid of phosphate ester or partial esterification is dissolved in is made into the phosphorus precursor that concentration is 1.0～4.0mol/L in the liquid alcohol;
4) with calcium precursor, metal ion precursor, phosphorus precursor and fluorochemical ratio and the Ca in predefined metal ion and calcium: P: the F mixed, and stir this mixed liquor;
5) above-mentioned mixed-liquor return is formed the sol solutions of filming after 12～24 hours;
6) lift in conjunction with centrifuging or solution hot spray process at the medical base face coat with sol-gel dip-coating method, spin-coating method, dipping, get final product.
Among the present invention, said liquid alcohol comprises methanol, ethanol or propanol.Calcium compounds can be lime nitrate or calcium acetate.Metal ion compound can be a zinc, strontium, magnesium, lanthanum, europium, erbium, manganese, silicon, zirconium, the nitrate or the acetate of sodium or potassium metal ion.Phosphate ester can adopt tributyl phosphate or triethyl phosphate etc.The phosphoric acid of said partial esterification can adopt and earlier phosphorus pentoxide is dissolved in liquid alcohol, in methanol, ethanol or propanol, forming phosphorus concentration is 1.0～4.0mol/L solution, and this solution is refluxed was prepared from again in 24 hours, and wherein part of O H group is PO (OH) by alcohol radical replacement, molecular formula
X(OR)
3-X, R is an alcohol radical in the formula, X equals 1 or 2.Said fluorochemical is hexafluorophosphoric acid (HPF
6), single fluorophosphoric acid or ammonium fluoride.According to the difference that adds fluorochemical content, the apatite of gained can be hydroxyapatite, fluoridated hydroxyapatite, fluor-apatite mutually.
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～10cm/min, spin-coating method control rotating speed is between 1500rpm～4000rpm.
The present invention introduces metal ion and comprises zinc, strontium, magnesium, lanthanum, europium, erbium, manganese, silicon, zirconium, sodium, potassium in hydroxyapatite.Studies show that these metal ions are relevant with enzyme with the intravital multiple protein of people, have the stimulating osteoblast differentiation, propagation, the effect that promote osteogenesis and inhibition osteoclast form.But the introducing stimulating osteoblast activity of metal ion promotes implant new bone growth on every side, thereby reaches the shortening healing time, improves the effect of implanting efficient.And the introducing of metal ion can suppress the formation of osteoclast, and then suppresses the bone dissolving, thereby the generation that prevents granule disease common in the hard tissue substituting is played a positive role.
The present invention introduces fluorine in hydroxyapatite, the fluoro-containing apatite of formation has better antilysis and close or better biological activity than hydroxyapatite, and the variation on this composition will very help taking into account the long-lasting and biological activity of coating.
Crystal content height in the coating of gained of the present invention, crystal grain is of a size of 10～20nm, phase purity height, compact structure.Adopt fluorochemical to introduce fluorine, not only the utilization rate height and the environmental pollution of fluorine are little.Preparation method of the present invention is simple, and equipment requirements is low, and is simple to operate, and coating layer thickness can more accurately be controlled from the number of times of filming, and thickness is adjustable between hundreds of nanometer to tens micron.
The specific embodiment
Further specify the present invention below in conjunction with example.
Embodiment 1
Lime nitrate is dissolved in the ethanol to form concentration be the alcoholic solution of 1mol/L.It is the alcoholic solution of 0.005mol/L that zinc nitrate is dissolved in ethanol formation concentration.Phosphorus pentoxide is dissolved in that part of O H group that ethanol forms is replaced by alcohol radical, molecular formula such as PO (OH)
X(OR)
3-XConcentration be the phosphoric acid of 1.0mol/L, and refluxed 24 hours, as fluorochemical, be 0.0001 with hexafluorophosphoric acid with the mol ratio of Zn/Ca, Ca: P: F=1000: mix at 600: 1,12 hours gained colloidal sol of mixed-liquor return adopts dip-coating method at the medical base surface coating.
Embodiment 2
Calcium acetate is dissolved in the ethanol to form concentration be the alcoholic solution of 4mol/L.It is the alcoholic solution of 0.1mol/L that strontium nitrate is dissolved in ethanol formation concentration.Phosphorus pentoxide is dissolved in that part of O H group that ethanol forms is replaced by alcohol radical, molecular formula such as PO (OH)
X(OR)
3-XConcentration be the phosphoric acid of 4.0mol/L, and refluxed 24 hours, as fluorochemical, be 0.05 with single fluorophosphoric acid with the mol ratio of Sr/Ca, Ca: P: the F mol ratio is mixing in 5: 3: 1, and 12 hours gained colloidal sol of mixed-liquor return adopts spin-coating method at the medical base surface coating.
Embodiment 3
Lime nitrate is dissolved in the ethanol to form concentration be the alcoholic solution of 2mol/L.It is the alcoholic solution of 0.1mol/L that manganese nitrate is dissolved in ethanol formation concentration.Phosphorus pentoxide is dissolved in that part of O H group that ethanol forms is replaced by alcohol radical, molecular formula such as PO (OH)
X(OR)
3-XConcentration be the phosphoric acid of 2.0mol/L, and refluxed 24 hours, as fluorochemical, be 0.006 with ammonium fluoride with the mol ratio of Mn/Ca, the mol ratio of Ca: P: F is mixing in 15: 9: 1, and 24 hours gained colloidal sol of mixed-liquor return adopts the solution spraying method at the medical base surface coating.
Embodiment 4
Lime nitrate is dissolved in the ethanol to form concentration be the alcoholic solution of 2mol/L.Zinc nitrate and manganese nitrate are dissolved in ethanol, and to form concentration be the alcoholic solution of 0.1mol/L.Adopt triethyl phosphate as the phosphorus precursor, with hexafluorophosphoric acid as fluorochemical, mol ratio with (Zn+Mn)/Ca is 0.009, and the mol ratio of Ca: P: F is mixing in 5: 3: 1, and 24 hours gained colloidal sol of mixed-liquor return adopts dipping to lift in conjunction with centrifuging at the medical base surface coating.
Embodiment 5
Lime nitrate is dissolved in the ethanol to form concentration be the alcoholic solution of 2mol/L.Is the alcoholic solution of 0.01mol/L with Lanthanum (III) nitrate with being dissolved in ethanol formation concentration.Adopt triethyl phosphate as the phosphorus precursor, with hexafluorophosphoric acid as fluorochemical, mol ratio with La/Ca is 0.0002, and the mol ratio of Ca: P: F is mixing in 5: 3: 1, and 24 hours gained sol impregnations of mixed-liquor return czochralski method is at the medical base surface coating.
Claims (10)
1. bio-medical material with biological responding coating, it is characterized in that belonging to ionic fluoridated hydroxyapatite nano coating by medical base with the gold doping that is coated in matrix surface forms, coating layer thickness is between 200nm～50 μ m, the mol ratio of F/Ca is 0.001～0.2 in the coating, the mol ratio of Ca/P is 1.67, and the mol ratio of metal ion and calcium is 0.0001～0.05.
2. the bio-medical material with biological responding coating according to claim 1 is characterized in that said medical base is titanium alloy, Titanium, vitallium, aluminium oxide ceramics or medical stainless steel.
3. the bio-medical material with biological responding surface according to claim 1 is characterized in that said metal ion is selected from zinc, strontium, magnesium, lanthanum, europium, erbium, manganese, silicon, zirconium, one or more in sodium and the potassium.
4. the bio-medical material with biological responding coating according to claim 1 is characterized in that gold doping belongs in the ionic fluoridated hydroxyapatite nano coating crystal grain size between 10～20nm.
5. the preparation method with bio-medical material of biological responding coating according to claim 1 is characterized in that may further comprise the steps:
1) to be dissolved in and to form concentration in the alcohol be the calcium precursor of 1～4mol/L to the calcium compounds that will dissolve in liquid alcohol;
2) to be dissolved in and to form concentration in the alcohol be the metal ion precursor of 0.005mol/L～0.1mol/L to the metal ion compound that will dissolve in liquid alcohol;
3) phosphoric acid of phosphate ester or partial esterification is dissolved in is made into the phosphorus precursor that concentration is 1.0～4.0mol/L in the liquid alcohol;
4) with calcium precursor, metal ion precursor, phosphorus precursor and fluorochemical ratio and the Ca in predefined metal ion and calcium: P: the F mixed, and stir this mixed liquor;
5) above-mentioned mixed-liquor return is formed the sol solutions of filming after 12～24 hours;
6) lift in conjunction with centrifuging or solution hot spray process at the medical base face coat with sol-gel dip-coating method, spin-coating method, dipping, get final product.
6. the preparation method with bio-medical material of biological responding coating according to claim 5 is characterized in that said liquid alcohol is methanol, ethanol or propanol.
7. the preparation method with bio-medical material of biological responding coating according to claim 5 is characterized in that said calcium compounds is lime nitrate or calcium acetate; Said metal ion compound is a zinc, strontium, magnesium, lanthanum, europium, erbium, manganese, silicon, zirconium, the nitrate or the acetate of sodium or potassium metal ion.
8. the preparation method with bio-medical material of biological responding coating according to claim 5 is characterized in that said fluorochemical is hexafluorophosphoric acid, single fluorophosphoric acid or ammonium fluoride.
9. the preparation method with bio-medical material of biological responding coating according to claim 5 is characterized in that said phosphate ester is tributyl phosphate or triethyl phosphate.
10. the preparation method with bio-medical material of biological responding coating according to claim 5, the phosphoric acid that it is characterized in that said partial esterification is phosphorus pentoxide to be dissolved in the liquid alcohol to form phosphorus concentration be 1.0～4.0mol/L solution, this solution is refluxed again and made in 24 hours, its molecular formula is PO (OH)
X(OR)
3-X, R is an alcohol radical in the formula, X equals 1 or 2.
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