CN1228097C - 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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- CN1228097C CN1228097C CN 03142247 CN03142247A CN1228097C CN 1228097 C CN1228097 C CN 1228097C CN 03142247 CN03142247 CN 03142247 CN 03142247 A CN03142247 A CN 03142247A CN 1228097 C CN1228097 C CN 1228097C
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- fluorine
- coating
- calcium phosphate
- containing calcium
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Abstract
The present invention relates to medical material with a fluorine containing calcium phosphate coating, which is used for hard tissues. Osteoid minerals can be deposited on the surface of the material, and the material is composed of a medical matrix and a fluorine containing calcium phosphate coating on the surface of the matrix, wherein the fluorine containing calcium phosphate coating is formed by that hydroxyapatite is replaced by fluorine containing hydroxyapatite, fluorine containing hydroxyapatite with calcium deficiency, fluorine containing tricalcium phosphate and fluorine containing carbonate radicals. A method for preparing the material of the present invention comprises: alcohol soluble calcium salt and alcoholic solution of phosphate ester or phosphoric acid mixture partially esterified are used as precursors, and a conventional sol-gel immersion crystal pulling method, a spin coating method, a method by combining immersion crystal pulling and centrifugation or a solution hot spray method is adopted to form a coating on the surface of alumina ceramic or the medical metallic matrix. The obtained coating has the advantages of high crystal phase content, no impurity phase and high phase purity. The method for preparing the material has the advantages of simplicity, low equipment requirement and simple operation, and the thickness of the coating can be regulated between hundreds of nanometers and scores of nanometers.
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 (9)
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, the mol ratio of F/Ca is 0.001～0.2, 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.
2. 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.
3. 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, be mixed with and be coated with film sol, wherein the mol ratio of Ca/P is 1.5～1.7, the mol ratio of F/Ca is 0.001～0.2;
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.
4. 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.
5. 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.
6. 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.
7. the preparation method with medical material of fluorine-containing calcium phosphate coating according to claim 6 is characterized in that when fluorochemical adopted trifluoroacetic acid, 1: 1 in molar ratio ratio added triethanolamine when adding trifluoroacetic acid.
8. 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.
9. 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.
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| CN 03142247 CN1228097C (en) | 2003-08-08 | 2003-08-08 | Medical fluorinated calcium phosphate coating material and its prepn process |
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| CN 03142247 CN1228097C (en) | 2003-08-08 | 2003-08-08 | Medical fluorinated calcium phosphate coating material and its prepn process |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100352517C (en) * | 2006-03-10 | 2007-12-05 | 浙江大学 | Double-phase medical coating with double-layer structure and production thereof |
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| CN1299778C (en) * | 2004-11-30 | 2007-02-14 | 华南理工大学 | Medical surface bioactive ceramic material and its prepn |
| CN100356991C (en) * | 2005-09-28 | 2007-12-26 | 浙江大学 | Biological medical material with biological responding coating and preparing method |
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| JP5248848B2 (en) * | 2007-12-11 | 2013-07-31 | 山八歯材工業株式会社 | Implant manufacturing method and artificial tooth root manufacturing method |
| CN101554491B (en) * | 2009-05-27 | 2012-10-03 | 四川大学 | Method for preparing bioactive glass coating by liquid-phase thermal spray |
| CN101703797B (en) * | 2009-12-07 | 2015-03-04 | 常熟致圆微管技术有限公司 | Fluorine-substituted apatite coating on surface of biologic medical magnesium or alloy thereof and preparation method |
| EP2359873A1 (en) * | 2010-02-12 | 2011-08-24 | Straumann Holding AG | Process for preparing a body having an osteointegrative surface |
| CN101879331B (en) * | 2010-06-26 | 2013-03-20 | 上海交通大学 | Preparation method of amino-terminated hyperbranched polybenzimidazole composite film |
| CN102000361B (en) * | 2010-11-02 | 2013-07-24 | 陕西科技大学 | Preparation method of HA (Hydroxyapatite)-beta-tricalcium phosphate-alumina three-phase composite bioceramic |
| US20120239068A1 (en) * | 2010-12-10 | 2012-09-20 | Morris James R | Surgical instrument |
| CN102961259A (en) * | 2012-12-12 | 2013-03-13 | 郑荣荣 | Hard coating material used for dental restoration and preparation method thereof |
| CN103723699B (en) * | 2013-12-29 | 2015-10-14 | 北京工业大学 | A kind of preparation method of the hydroxyapatite powder controlled for the scantlings of the structure of plasma thermal sprayed |
| WO2016178210A1 (en) * | 2015-05-07 | 2016-11-10 | Phosfan Ltd | Method for applying ultrafine phosphate conversion crystal coatings |
| CN105748300B (en) * | 2016-02-04 | 2019-12-03 | 重庆医科大学附属口腔医院 | Strontium nanometer hydroxyapatite procyanidine complex and preparation method thereof |
| CN105748510B (en) * | 2016-03-08 | 2018-10-30 | 景德镇陶瓷大学 | A kind of controllable fluorine sustained release calcium phosphate bioactive material and preparation method thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100352517C (en) * | 2006-03-10 | 2007-12-05 | 浙江大学 | Double-phase medical coating with double-layer structure and production thereof |
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