CN1486751A - Medical fluorinated calcium phosphate coating material and its prepn process - Google Patents
Medical fluorinated calcium phosphate coating material and its prepn process Download PDFInfo
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- CN1486751A CN1486751A CNA031422470A CN03142247A CN1486751A CN 1486751 A CN1486751 A CN 1486751A CN A031422470 A CNA031422470 A CN A031422470A CN 03142247 A CN03142247 A CN 03142247A CN 1486751 A CN1486751 A CN 1486751A
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- Prior art keywords
- fluorine
- calcium phosphate
- coating
- containing calcium
- medical material
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- 238000000576 coating method Methods 0.000 title claims abstract description 38
- 239000011248 coating agent Substances 0.000 title claims abstract description 37
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical class [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 title claims abstract description 25
- 238000000034 method Methods 0.000 title claims abstract description 20
- 239000000463 material Substances 0.000 title description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 33
- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical class [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 22
- 229910052588 hydroxylapatite Inorganic materials 0.000 claims abstract description 21
- 238000002360 preparation method Methods 0.000 claims abstract description 17
- 239000012567 medical material Substances 0.000 claims abstract description 15
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 14
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000002243 precursor Substances 0.000 claims abstract description 10
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 9
- 239000010452 phosphate Substances 0.000 claims abstract description 9
- 239000000203 mixture Substances 0.000 claims abstract description 8
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 7
- 229910052751 metal Inorganic materials 0.000 claims abstract description 6
- 239000002184 metal Substances 0.000 claims abstract description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 4
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 41
- 229910052731 fluorine Inorganic materials 0.000 claims description 41
- 239000011737 fluorine Substances 0.000 claims description 41
- 239000001506 calcium phosphate Substances 0.000 claims description 22
- 239000011575 calcium Substances 0.000 claims description 19
- 229910000389 calcium phosphate Inorganic materials 0.000 claims description 19
- 235000011010 calcium phosphates Nutrition 0.000 claims description 19
- 239000000243 solution Substances 0.000 claims description 16
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 claims description 14
- 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 claims description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- 239000011159 matrix material Substances 0.000 claims description 11
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 claims description 10
- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 claims description 10
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 9
- 229910052791 calcium Inorganic materials 0.000 claims description 9
- 229910052586 apatite Inorganic materials 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 8
- -1 phosphate ester Chemical class 0.000 claims description 7
- 238000004528 spin coating Methods 0.000 claims description 7
- 238000003618 dip coating Methods 0.000 claims description 6
- 238000007598 dipping method Methods 0.000 claims description 6
- 239000007921 spray Substances 0.000 claims description 6
- 125000005587 carbonate group Chemical group 0.000 claims description 5
- 230000002950 deficient Effects 0.000 claims description 5
- 230000032050 esterification Effects 0.000 claims description 5
- 238000005886 esterification reaction Methods 0.000 claims description 5
- 229910052587 fluorapatite Inorganic materials 0.000 claims description 5
- 229940077441 fluorapatite Drugs 0.000 claims description 5
- 239000012688 phosphorus precursor Substances 0.000 claims description 5
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical class CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 4
- 229940043430 calcium compound Drugs 0.000 claims description 4
- 150000001674 calcium compounds Chemical class 0.000 claims description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 4
- 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 4
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 3
- 239000012298 atmosphere Substances 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
- 229910000391 tricalcium phosphate Inorganic materials 0.000 claims description 3
- 235000019731 tricalcium phosphate Nutrition 0.000 claims description 3
- 229940078499 tricalcium phosphate Drugs 0.000 claims description 3
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 claims description 3
- 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 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 2
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 2
- 229910052698 phosphorus Inorganic materials 0.000 claims description 2
- 239000011574 phosphorus Substances 0.000 claims description 2
- 239000006104 solid solution Substances 0.000 claims description 2
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical group CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 claims description 2
- 239000012535 impurity Substances 0.000 abstract description 4
- 159000000007 calcium salts Chemical class 0.000 abstract description 2
- 238000005507 spraying Methods 0.000 abstract description 2
- 238000002791 soaking Methods 0.000 abstract 2
- 238000007591 painting process Methods 0.000 abstract 1
- 239000011247 coating layer Substances 0.000 description 3
- 210000001519 tissue Anatomy 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 230000004071 biological effect Effects 0.000 description 2
- 239000008199 coating composition Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000007943 implant Substances 0.000 description 2
- 230000005923 long-lasting effect Effects 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000001476 alcoholic effect Effects 0.000 description 1
- 239000012620 biological material Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 210000000988 bone and bone Anatomy 0.000 description 1
- JUNWLZAGQLJVLR-UHFFFAOYSA-J calcium diphosphate Chemical compound [Ca+2].[Ca+2].[O-]P([O-])(=O)OP([O-])([O-])=O JUNWLZAGQLJVLR-UHFFFAOYSA-J 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 229940043256 calcium pyrophosphate Drugs 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 235000019821 dicalcium diphosphate Nutrition 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 108010025899 gelatin film Proteins 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000002156 mixing Methods 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
- 239000000758 substrate Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
Landscapes
- Materials For Medical Uses (AREA)
Abstract
The present invention relates to one kind of medical material used for hard tissue. It consists of medical base body and surface fluorinated calcium phosphate coating, which is fluorinated hydroxyapatite, fluorinated calciprivic hydroxyapatite, fluorinated tricalcium phosphate or carbonate radical substituted hydroxyapatite. During the preparation, alcohol solution of the mixture of alcohol soluble calcium salt and phosphate or partially esterified phosphoric acid is used as precursor and surface coating is formed on alumina ceramic or medical metal base body via conventional sol-gel soaking pulling process, rotary painting process, combined soaking pulling and centrifuging process or hot solution spraying process. The coating has high crystalline phase content, no impurity phase and high phase purity. The preparation process of th present invention can obtain coating with thickness adjustable from several hundred nanometers to several decade microns.
Description
Technical field
The present invention relates to a kind of biomaterial for medical purpose, especially a kind of surface can deposit the osteoid mineral, be used for sclerous tissues have medical material of fluorine-containing calcium phosphate coating 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 in the preparation process of hydroxyapatite coating layer owing to adopt plasma spraying, can occur impurity mutually and himself dissolubility excessive relatively, cause and the coating dissolving may take place in application come off the problem that implant lost efficacy.In view of this, Chinese patent 97119791.1 takes to improve method improvement coating long-lasting that the coating composition adds bio-vitric powder and titania powder, has obtained certain effect.From improving the performance that preparation method and coating composition improve bioactivity coatings, be the problem that everybody paid close attention to always.
Summary of the invention
The purpose of this invention is to provide medical material of the fluorine-containing calcium phosphate coating of having of a kind of excellent performance and preparation method thereof.
Medical material with fluorine-containing calcium phosphate coating of the present invention is formed by medical base with at the fluorine-containing calcium phosphate coating of matrix surface, wherein fluorine-containing calcium phosphate coating is fluorine-containing hydroxyapatite, fluorine-containing calcium-deficient apatite, fluorine-containing tricalcium phosphate phase and fluorine-containing carbonate substituted hydroxy apatite, the mol ratio of Ca/P is 1.5～1.7, and the mol ratio of F/Ca is 0.001～0.2.
Above-mentioned fluorine-containing hydroxyapatite, fluorine-containing calcium-deficient apatite and fluorine-containing carbonate substituted hydroxy apatite are to adopt the solid solution that do not contain less hydroxyapatite of other impurity phase, dissolubility and fluor-apatite for well.Medical base can be aluminium oxide ceramics or medical metal.
Preparation method of the present invention is to adopt the alcoholic solution of phosphate mixture of the calcium salt dissolve in alcohol and phosphate ester or partial esterification as precursor, lifts in conjunction with centrifugation method or solution hot spray process in aluminium oxide ceramics or medical metal matrix surface coating with sol-gel dip-coating method, spin-coating method, the dipping of routine.Concrete steps are as follows:
1) to be dissolved in and to form concentration in the alcohol be the calcium precursor of 0.5mol/L～3.5mol/L to the calcium compounds that will dissolve in liquid alcohol;
2) phosphate mixture of phosphate ester or partial esterification is dissolved in is made into the phosphorus precursor that concentration is 0.5mol/L～6.0mol/L in the liquid alcohol;
3) with calcium precursor, phosphorus precursor and fluorochemical by predefined Ca: P: the F mixed, be mixed with and be coated with film sol, wherein the adding of fluorochemical in the dropping mode for well;
4) lift in conjunction with centrifuging or solution hot spray process in the matrix surface coating with sol-gel dip-coating method, spin-coating method, dipping, promptly get product of the present invention.
Among the present invention, said alcohol comprises methanol, ethanol, propanol or butanols.Calcium compounds can be lime nitrate, calcium acetate.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, and in methanol, ethanol, propanol or butanols, forming phosphorus concentration is 0.5mol/L～6mol/L solution, and wherein part of O H group is PO (OH) by alcohol radical replacement, molecular formula
X(OR)
3-XPhosphoric acid, R is an alcohol radical in the formula, X equals 1 or 2, this solution is refluxed was prepared from again in 24 hours.
Said fluorochemical can be trifluoroacetic acid (CF
3COOH), hexafluorophosphoric acid (HPF
6), ammonium hexafluorophosphate (NH
4PF
6), single fluorophosphoric acid (H
2PO
3F) or ammonium fluoride (NH
4F).According to the difference that adds fluorochemical content, the apatite of gained can be fluorine-containing hydroxyapatite, fluorine-containing calcium-deficient apatite, fluorine-containing tricalcium phosphate phase and fluorine-containing carbonate substituted hydroxy apatite mutually.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.
When adopting conventional sol-gel dip-coating method, spin-coating method, dipping to lift in conjunction with centrifuging or solution hot spray process when matrix surface prepares coating; film forming for the benefit of; usually can adopt atmosphere protection; promptly in preparation process, make matrix be in nitrogen atmosphere all the time or contain alcohol vapor (methanol; ethanol; propanol or butanols) air atmosphere in, with the evaporation rate of regulating solvent in the liquid film and suppress dried glued membrane and absorb moisture content.
Lift in conjunction with centrifuging with sol-gel dip-coating method, spin-coating method or dipping 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.
Prepare coating with the solution hot spray process, can adopt gel film is formed retes through 50 ℃～200 ℃ oven dry and 500 ℃～1000 ℃ heat treatments, repeatedly repeat to film and heat treatment process can make coating reach required thickness.
The present invention introduces fluorine in calcium phosphate, have dissolubility and the close or better ability at surface deposition osteoid apatite layer much smaller than hydroxyapatite owing to introduce the fluor-apatite that forms behind the fluorine, the variation on this composition will very help taking into account the long-lasting and biological activity of coating.The present invention has generated the fluor-apatite phase with the synthetic method of original position, crystal content height in the coating of gained, and phase purity height does not have impurity phases such as calcium oxide, calcium pyrophosphate substantially.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.
Example 1
Lime nitrate is dissolved in the ethanol forms concentration at 2mol/L solution.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 2mol/L, and refluxed 24 hours, as fluorochemical, the three presses Ca with trifluoroacetic acid: P: F=5: mix at 3: 1, and in adding triethanolamine with 1: 1 ratio of trifluoroacetic acid in mixed liquor; Film as precursor with this colloidal sol and promptly to get pure fluor-apatite film.
Example 2
Lime nitrate is dissolved in forms concentration among the ethanol at 1mol/L solution.With phosphorus pentoxide be dissolved in part of O H group that ethanol forms by alcohol radical to replace, molecular formula such as PO (OH)
X(OR)
3-XConcentration be the phosphoric acid of 1mol/L, and refluxed 24 hours, as fluorochemical, the three presses Ca with hexafluorophosphoric acid: P: F=15: mix to form mixed sols at 9: 2; Film as precursor with this colloidal sol and promptly to get the fluoridated hydroxyapatite film.
Example 3
Lime nitrate is dissolved in forms concentration among the ethanol at 3mol/L solution.With phosphorus pentoxide be dissolved in part of O H group that ethanol forms by alcohol radical to replace, molecular formula such as PO (OH)
X(OR)
3-XConcentration be the phosphoric acid of 2mol/L, and refluxed 24 hours, as fluorochemical, the three presses Ca with single fluorophosphoric acid: P: F=15: mix to form mixed sols at 9: 1; Film as precursor with this colloidal sol and promptly to get the fluoridated hydroxyapatite film.
Example 4
Calcium acetate is dissolved in forms concentration among the ethanol at 1mol/L solution.Adopt triethyl phosphate as the phosphorus precursor, as fluorochemical, the three presses Ca with hexafluorophosphoric acid: P: F=15: mixing in 9: 1 forms mixed sols; Film as precursor with this colloidal sol and promptly to get the fluoridated hydroxyapatite film.
Claims (10)
1. medical material with fluorine-containing calcium phosphate coating, it is characterized in that forming by medical base with at the fluorine-containing calcium phosphate coating of matrix surface, wherein fluorine-containing calcium phosphate coating is fluorine-containing hydroxyapatite, fluorine-containing calcium-deficient apatite, fluorine-containing tricalcium phosphate phase and fluorine-containing carbonate substituted hydroxy apatite, the mol ratio of Ca/P is 1.5～1.7, and the mol ratio of F/Ca is 0.001～0.2.
2. the medical material with fluorine-containing calcium phosphate coating according to claim 1 is characterized in that said fluorine-containing hydroxyapatite, fluorine-containing calcium-deficient apatite and fluorine-containing carbonate substituted hydroxy apatite are the solid solution of hydroxyapatite and fluor-apatite.
3. the medical material with fluorine-containing calcium phosphate coating according to claim 1 is characterized in that said medical base is aluminium oxide ceramics or medical metal.
4. the preparation method with medical material of fluorine-containing calcium phosphate 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 0.5mol/L～3.5mol/L to the calcium compounds that will dissolve in liquid alcohol;
2) phosphate mixture of phosphate ester or partial esterification is dissolved in is made into the phosphorus precursor that concentration is 0.5mol/L～6.0mol/L in the liquid alcohol;
3) calcium precursor, phosphorus precursor and fluorochemical are pressed predefined Ca: P: the F mixed is mixed with and is coated with film sol;
4) lift in conjunction with centrifuging or solution hot spray process in the matrix surface coating with sol-gel dip-coating method, spin-coating method, dipping, promptly get product of the present invention.
5. the preparation method with medical material of fluorine-containing calcium phosphate coating according to claim 3 is characterized in that said liquid alcohol is methanol, ethanol, propanol or butanols.
6. the preparation method with medical material of fluorine-containing calcium phosphate coating according to claim 3 is characterized in that said calcium compounds is lime nitrate, calcium acetate, and said phosphate ester is tributyl phosphate or triethyl phosphate.
7. the preparation method with medical material of fluorine-containing calcium phosphate coating according to claim 3 is characterized in that said fluorochemical is trifluoroacetic acid, hexafluorophosphoric acid, ammonium hexafluorophosphate, single fluorophosphoric acid or ammonium fluoride.
8. the preparation method with medical material of fluorine-containing calcium phosphate coating according to claim 6 is characterized in that when fluorochemical adopts trifluoroacetic acid the ratio in 1: 1 when adding trifluoroacetic acid adds triethanolamine.
9. the preparation method with medical material of fluorine-containing calcium phosphate coating according to claim 3, 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 0.5mol/L～6mol/L solution, and this solution is refluxed was prepared from again in 24 hours.
10. the preparation method with medical material of fluorine-containing calcium phosphate coating according to claim 3, it is characterized in that adopting sol-gel dip-coating method, spin-coating method, dipping to lift in conjunction with centrifuging or solution hot spray process when matrix surface prepares coating, matrix is in nitrogen atmosphere all the time or contains in the air atmosphere of alcohol vapor.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03142247 CN1228097C (en) | 2003-08-08 | 2003-08-08 | Medical fluorinated calcium phosphate coating material and its prepn process |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03142247 CN1228097C (en) | 2003-08-08 | 2003-08-08 | Medical fluorinated calcium phosphate coating material and its prepn process |
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| CN1486751A true CN1486751A (en) | 2004-04-07 |
| CN1228097C CN1228097C (en) | 2005-11-23 |
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|---|---|---|---|
| CN 03142247 Expired - Fee Related CN1228097C (en) | 2003-08-08 | 2003-08-08 | Medical fluorinated calcium phosphate coating material and its prepn process |
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| CN102821793A (en) * | 2010-02-12 | 2012-12-12 | 斯特劳曼控股公司 | Process for preparing an osteointegrative surface on a ceramic body |
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2003
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