CN101293113B - Method for preparing fluorapatite/hydroxyapatite sosoloid nano-powder - Google Patents
Method for preparing fluorapatite/hydroxyapatite sosoloid nano-powder Download PDFInfo
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- CN101293113B CN101293113B CN2008100624870A CN200810062487A CN101293113B CN 101293113 B CN101293113 B CN 101293113B CN 2008100624870 A CN2008100624870 A CN 2008100624870A CN 200810062487 A CN200810062487 A CN 200810062487A CN 101293113 B CN101293113 B CN 101293113B
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- hydroxyapatite
- sosoloid
- fluor
- nanometer powder
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- 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 title claims abstract description 30
- 229910052588 hydroxylapatite Inorganic materials 0.000 title claims abstract description 25
- 229910052587 fluorapatite Inorganic materials 0.000 title claims abstract description 21
- 229940077441 fluorapatite Drugs 0.000 title claims abstract description 21
- 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 title claims abstract description 21
- 238000000034 method Methods 0.000 title claims abstract description 8
- 239000011858 nanopowder Substances 0.000 title 1
- 239000000843 powder Substances 0.000 claims abstract description 35
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000002360 preparation method Methods 0.000 claims abstract description 12
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 7
- 239000010452 phosphate Substances 0.000 claims abstract description 7
- 150000001412 amines Chemical class 0.000 claims abstract description 6
- 230000032050 esterification Effects 0.000 claims abstract description 6
- 238000005886 esterification reaction Methods 0.000 claims abstract description 6
- 229940043430 calcium compound Drugs 0.000 claims abstract description 5
- 150000001674 calcium compounds Chemical class 0.000 claims abstract description 5
- 238000002485 combustion reaction Methods 0.000 claims abstract description 4
- 239000011575 calcium Substances 0.000 claims description 29
- 239000007788 liquid Substances 0.000 claims description 24
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 20
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 13
- 229910052791 calcium Inorganic materials 0.000 claims description 13
- 239000003292 glue Substances 0.000 claims description 13
- 239000002243 precursor Substances 0.000 claims description 13
- 239000012688 phosphorus precursor Substances 0.000 claims description 12
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 10
- 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
- 238000010438 heat treatment Methods 0.000 claims description 10
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 claims description 8
- -1 phosphate ester Chemical class 0.000 claims description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 4
- 210000000988 bone and bone Anatomy 0.000 claims description 4
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 4
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims description 4
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 3
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-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
- 235000011092 calcium acetate Nutrition 0.000 claims description 3
- 229960005147 calcium acetate Drugs 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
- 230000002269 spontaneous effect Effects 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
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical class CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 2
- 235000010299 hexamethylene tetramine Nutrition 0.000 claims description 2
- 239000004312 hexamethylene tetramine Substances 0.000 claims description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 2
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical group CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 claims description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 abstract description 6
- 229910052731 fluorine Inorganic materials 0.000 abstract description 6
- 239000011737 fluorine Substances 0.000 abstract description 6
- 239000006104 solid solution Substances 0.000 abstract 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 abstract 2
- 150000002222 fluorine compounds Chemical class 0.000 abstract 1
- 239000000243 solution Substances 0.000 abstract 1
- 239000001506 calcium phosphate Substances 0.000 description 7
- 229910000389 calcium phosphate Inorganic materials 0.000 description 7
- 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 7
- 235000011010 calcium phosphates Nutrition 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 239000013078 crystal Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 4
- 230000004071 biological effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 238000007750 plasma spraying Methods 0.000 description 2
- 229910014497 Ca10(PO4)6(OH)2 Inorganic materials 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 230000000975 bioactive effect Effects 0.000 description 1
- 239000012620 biological material Substances 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
- 229940043256 calcium pyrophosphate Drugs 0.000 description 1
- 159000000007 calcium salts Chemical class 0.000 description 1
- 238000000975 co-precipitation Methods 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
- 239000007943 implant Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000005923 long-lasting effect Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 210000001519 tissue Anatomy 0.000 description 1
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- Materials For Medical Uses (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The present invention discloses a preparation method of fluorapatite/hydroxylapatite solid solution nanometer powder. The method takes calcium compound and part esterification phosphate or organic phosphate alcohol solution as the base and then adds fluoride compounds and organic amine so as to synthesize the fluorapatite/hydroxylapatite solid solution nanometer powder by the method of sol combustion self-spreading. The present invention solves the problems that the fluorapatite/hydroxylapatite solid solution nanometer powder is hard to prepare, and the fluorine content and the existence state of the fluorine are difficult to control, etc. The preparation method provided by the present invention has the advantages of simple operation, low cost and being easy for industrialization.
Description
Technical field
The present invention relates to the preparation method of fluor-apatite/hydroxyapatite sosoloid nanometer powder, belong to biomaterial for medical purpose.
Background technology
Calcium phosphate material is the pottery that hard tissue substituting material is made in a kind of extensive use.It has multiple crystal formation, wherein hydroxyapatite (Ca
10(PO
4)
6(OH)
2, HA) the most frequently used a kind of.Have been found that hydroxyapatite has superior bioactive, can form chemical bonding with osseous tissue.And hydroxyapatite is generally acknowledged to have bone conductibility.Yet, because the difference of applied environment, in the application of ask for something calcium phosphate long-time stability, as when being applied to metal base surface coating under the carrying condition or ceramic artificial eye etc., its dissolubility is excessive, causes the calcium phosphate dissolving easily, makes implant that the possibility of inefficacy be arranged.Therefore, it is very necessary in these are used its dissolubility being controlled.In hydroxyapatite structure, introduce all or part of replacement of F OH formation fluor-apatite/hydroxyapatite sosoloid and can reduce its dissolubility effectively, and it is suitable with hydroxyapatite with the interactional performance of organism.Therefore be a kind of very promising substitution material.
In a lot of practical applications, prepare coating as plasma spraying, porous or compact massive pottery etc. all need be with calcium phosphate powder as raw materials, and the particle diameter of calcium phosphate powder has played important effect in these preparation process, may influence the reactivity, sinterability, gained coating of powder or mechanical property of pottery or the like.Adopt nano-calcium phosphate powder can improve the performance of plasma spraying coating or agglomerating pottery effectively from these aspects.Chinese patent 00127421.X and 200310105951.7 discloses the nanometer hydroxyapatite powder preparation method based on coprecipitation respectively.And for fluor-apatite, CN1475436 discloses a kind of high temperature solid phase synthesis, but this method is difficult to prepare the fluoridated hydroxyapatite of nanoscale.
Summary of the invention
The preparation method that the purpose of this invention is to provide a kind of fluor-apatite/hydroxyapatite sosoloid nanometer powder of excellent performance.
The method for preparing fluor-apatite/hydroxyapatite sosoloid nanometer powder that the present invention proposes, be to adopt the alcoholic solution of phosphoric acid of the calcium salt dissolve in liquid alcohol and phosphate ester or partial esterification as precursor, add organic amine therein, form flammable colloidal sol, make it burning and obtain the dry glue powder end from spreading mode, obtain fluor-apatite/hydroxyapatite sosoloid nanometer powder by heat treatment again with colloidal sol.Concrete steps are as follows:
1) to be dissolved in and to form concentration in the liquid alcohol be the calcium precursor of 0.5mol/L～3.5mol/L to the calcium compounds that will dissolve in liquid alcohol;
2) phosphoric acid 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), form mixed liquor A with calcium precursor, phosphorus precursor Ca/P=1.55～1.67 mixed in molar ratio;
4) fluorochemical is added in the mixed liquor A F/Ca=0.01～0.20 in molar ratio, and refluxed 12 hours～48 hours, form mixed liquid B;
5) in mixed liquid B in molar ratio N/F=1～2 add organic amines;
6) heating makes the mixed liquid B spontaneous combustion or directly lights mixed liquid B, becomes the dry glue powder end to the solution bone dry;
7) with 500 ℃～700 ℃ heat treatment dry glue powders end 20 minutes～5 hours, obtain fluor-apatite/hydroxyapatite sosoloid nanometer powder.
Among the present invention, said liquid alcohol can be methanol, ethanol, propanol or butanols.Said calcium compounds can be lime nitrate or calcium acetate.
Among the present invention, said phosphate ester can adopt tributyl phosphate or triethyl phosphate.The phosphoric acid of said partial esterification is that molecular formula is PO (OH)
X(OR)
3-XPhosphoric acid, R is an alcohol radical in the formula, X equals 1 or 2.
Among the present invention, 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).
Among the present invention, said organic amine can be ethanolamine, diethanolamine, triethanolamine, diethylenetriamine or hexamethylenetetramine.
The present invention introduces fluorine in calcium phosphate, according to the difference that adds fluorochemical content, can obtain fluorine and replace the different fluor-apatite/hydroxyapatite sosoloid nanometer powder of degree, because the existence of fluorine has reduced dissolubility effectively, and its biological activity and biocompatibility are uninfluenced, when its during as coating or block ceramic applications, the variation on this composition will very help taking into account the long-lasting and biological activity of material.The present invention has generated fluor-apatite/hydroxyapatite sosoloid with colloidal sol from the method that spreads, the nanometer powder phase purity height of gained, and impurity phases such as oxygen-free calcium, calcium pyrophosphate, and fluorine content controllability is good, and crystallite dimension is controlled in 20nm～100nm scope.Preparation method of the present invention is simple, and is simple to operate, and cost is low, is easy to industrialization.
The specific embodiment
Further specify the present invention below in conjunction with example.
Example 1
Lime nitrate is dissolved in the ethanol forms concentration in 2mol/L calcium precursor; With molecular formula is PO (OH)
1(OR)
2Phosphoric acid be dissolved in the ethanol that to form concentration be the phosphorus precursor of 2mol/L; With calcium precursor, phosphorus precursor Ca/P=1.67 mixed in molar ratio, form mixed liquor A;
In trifluoroacetic acid F/Ca=0.20 adding in molar ratio mixed liquor A, and refluxed 12 hours, form mixed liquid B; N: F=1 in molar ratio in mixed liquid B: 1 adds triethanolamine, and the heating mixed liquid B makes it spontaneous combustion until forming the dry glue powder end on hot platform, and the 700 ℃ of heat treatments in dry glue powder end promptly became the fluoridated hydroxyapatite nano powder in 20 minutes, and nominal molecular formula is Ca
10(PO
4)
6(OH)
0.01F
1.99, the crystal grain mean size is 92nm.
Example 2
Lime nitrate is dissolved in the ethanol forms concentration in 0.5mol/L calcium precursor; With molecular formula such as PO (OH)
2(OR)
1Phosphoric acid be dissolved in the ethanol that to form concentration be the phosphorus precursor of 6.0mol/L; With calcium precursor, phosphorus precursor Ca/P=1.67 mixed in molar ratio, form mixed liquor A;
In trifluoroacetic acid F/Ca=0.133 adding in molar ratio mixed liquor A, and refluxed 12 hours, form mixed liquid B; N: F=1.5 in molar ratio in mixed liquid B: 1 adds diethanolamine, lights colloidal sol until forming the dry glue powder end, and the 650 ℃ of heat treatments in dry glue powder end promptly became the fluoridated hydroxyapatite nano powder in 4 hours, and nominal molecular formula is Ca
10(PO
4)
6(OH)
0.69F
1.31, the crystal grain mean size is 78nm.
Example 3
Lime nitrate is dissolved in the ethanol forms concentration in 3.5mol/L calcium precursor; With molecular formula such as PO (OH)
2(OR)
1Phosphoric acid be dissolved in the ethanol that to form concentration be the phosphorus precursor of 2.0mol/L; With calcium precursor, phosphorus precursor Ca/P=1.55 mixed in molar ratio, form mixed liquor A;
In single fluorophosphoric acid F/Ca=0.01 adding in molar ratio mixed liquor A, and refluxed 48 hours, form mixed liquid B; N: F=2 in molar ratio in mixed liquid B: 1 adds diethanolamine, lights colloidal sol until forming the dry glue powder end, and the 500 ℃ of heat treatments in dry glue powder end promptly became the fluoridated hydroxyapatite nano powder in 5 hours, and nominal molecular formula is Ca
9.3(PO
4)
6(OH)
1.907F
0.093, the crystal grain mean size is 45nm.
Example 4
Calcium acetate is dissolved in the ethanol forms concentration in 1.0mol/L calcium precursor; Triethyl phosphate is dissolved in the ethanol to form concentration be the phosphorus precursor of 0.5mol/L; With calcium precursor, phosphorus precursor Ca/P=1.65 mixed in molar ratio, form mixed liquor A;
In hexafluorophosphoric acid F/Ca=0.067 adding in molar ratio mixed liquor A, and refluxed 36 hours, form mixed liquid B; N: F=2 in molar ratio in mixed liquid B: 1 adds diethylenetriamine, lights colloidal sol until forming the dry glue powder end, and the 650 ℃ of heat treatments in dry glue powder end promptly became the fluoridated hydroxyapatite nano powder in 4 hours, and nominal molecular formula is Ca
9.9(PO
4)
6(OH)
1.337F
0.663, the crystal grain mean size is 68nm.
Claims (6)
1. method for preparing fluor-apatite/hydroxyapatite sosoloid nanometer powder is characterized in that may further comprise the steps:
1) to be dissolved in and to form concentration in the liquid alcohol be the calcium precursor of 0.5mol/L～3.5mol/L to the calcium compounds that will dissolve in liquid alcohol;
2) phosphoric acid 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), form mixed liquor A with calcium precursor, phosphorus precursor Ca/P=1.55～1.67 mixed in molar ratio;
4) fluorochemical is added in the mixed liquor A F/Ca=0.01～0.20 in molar ratio, and refluxed 12 hours～48 hours, form mixed liquid B;
5) in mixed liquid B in molar ratio N/F=1～2 add organic amines, said organic amine is an ethanolamine, diethanolamine, triethanolamine, diethylenetriamine or hexamethylenetetramine;
6) heating makes the mixed liquor spontaneous combustion of step 5) gained or directly lights step 5) gained mixed liquor, becomes the dry glue powder end to the solution bone dry;
7) with 500 ℃～700 ℃ heat treatment dry glue powders end 20 minutes～5 hours, obtain fluor-apatite/hydroxyapatite sosoloid nanometer powder.
2. the preparation method of fluor-apatite according to claim 1/hydroxyapatite sosoloid nanometer powder is characterized in that said liquid alcohol is methanol, ethanol, propanol or butanols.
3. the preparation method of fluor-apatite according to claim 1/hydroxyapatite sosoloid nanometer powder is characterized in that said calcium compounds is lime nitrate or calcium acetate.
4. the preparation method of fluor-apatite according to claim 1/hydroxyapatite sosoloid nanometer powder is characterized in that said phosphate ester is tributyl phosphate or triethyl phosphate.
5. the preparation method of fluor-apatite according to claim 1/hydroxyapatite sosoloid nanometer powder, the phosphoric acid that it is characterized in that said partial esterification are that molecular formula is PO (OH)
X(OR)
3-XPhosphoric acid, R is ethyl or butyl in the formula, X equals 1 or 2.
6. the preparation method of fluor-apatite according to claim 1/hydroxyapatite sosoloid nanometer powder is characterized in that said fluorochemical is trifluoroacetic acid, hexafluorophosphoric acid, ammonium hexafluorophosphate, single fluorophosphoric acid or ammonium fluoride.
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| CN2008100624870A CN101293113B (en) | 2008-06-12 | 2008-06-12 | Method for preparing fluorapatite/hydroxyapatite sosoloid nano-powder |
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|---|---|---|---|
| CN2008100624870A CN101293113B (en) | 2008-06-12 | 2008-06-12 | Method for preparing fluorapatite/hydroxyapatite sosoloid nano-powder |
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| CN105293461B (en) * | 2015-11-18 | 2017-08-29 | 湖北工业大学 | A kind of preparation method of Oil soluble hydroxy apatite nanometer sheet |
| CN106317031B (en) * | 2016-08-19 | 2018-10-02 | 淮阴师范学院 | A method of synthesis 2- (4,6- bis- (2,4- xylyls) -1,3,5- triazine -2- bases) -5- glycidol ether phenol |
| CN108609593B (en) * | 2018-04-27 | 2020-09-08 | 武汉亚洲生物材料有限公司 | Hydroxyapatite and preparation method and application thereof |
| CN114014288B (en) * | 2021-11-09 | 2022-12-13 | 中南大学 | Calcium fluoride modified hydroxyapatite powder and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1308016A (en) * | 2000-11-10 | 2001-08-15 | 中国科学院上海硅酸盐研究所 | Preparation of low temperature sinterable hydroxyapatite powder |
| EP1462130A1 (en) * | 2003-03-28 | 2004-09-29 | Ethicon, Inc. | Implantable medical devices having lubricated surfaces and methods for making same |
| CN1775309A (en) * | 2005-09-28 | 2006-05-24 | 浙江大学 | Method for preparing calcium phosphate coating on medical transplant by flame heat treatment |
-
2008
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1308016A (en) * | 2000-11-10 | 2001-08-15 | 中国科学院上海硅酸盐研究所 | Preparation of low temperature sinterable hydroxyapatite powder |
| EP1462130A1 (en) * | 2003-03-28 | 2004-09-29 | Ethicon, Inc. | Implantable medical devices having lubricated surfaces and methods for making same |
| CN1775309A (en) * | 2005-09-28 | 2006-05-24 | 浙江大学 | Method for preparing calcium phosphate coating on medical transplant by flame heat treatment |
Non-Patent Citations (1)
| Title |
|---|
| 赵朝霞等.含氟羟基磷灰石薄膜的溶胶-凝胶制备和溶解特性研究.《材料科学与工程学报》.2005,第23卷(第2期),226-229. * |
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