CN100352517C - Double-phase medical coating with double-layer structure and production thereof - Google Patents
Double-phase medical coating with double-layer structure and production thereof Download PDFInfo
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- CN100352517C CN100352517C CNB2006100497715A CN200610049771A CN100352517C CN 100352517 C CN100352517 C CN 100352517C CN B2006100497715 A CNB2006100497715 A CN B2006100497715A CN 200610049771 A CN200610049771 A CN 200610049771A CN 100352517 C CN100352517 C CN 100352517C
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- 238000000576 coating method Methods 0.000 title claims abstract description 62
- 239000011248 coating agent Substances 0.000 title claims abstract description 58
- 238000004519 manufacturing process Methods 0.000 title 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 claims abstract description 46
- 239000001506 calcium phosphate Substances 0.000 claims abstract description 43
- 229910000389 calcium phosphate Inorganic materials 0.000 claims abstract description 31
- 235000011010 calcium phosphates Nutrition 0.000 claims abstract description 31
- 239000011575 calcium Substances 0.000 claims abstract description 30
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 18
- 239000000203 mixture Substances 0.000 claims abstract description 16
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 13
- 239000010452 phosphate Substances 0.000 claims abstract description 13
- -1 phosphorus ions Chemical class 0.000 claims abstract description 13
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 12
- 238000002360 preparation method Methods 0.000 claims abstract description 11
- 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 abstract description 9
- 238000004528 spin coating Methods 0.000 claims abstract description 8
- 238000010438 heat treatment Methods 0.000 claims abstract description 7
- 239000005457 ice water Substances 0.000 claims abstract description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 7
- 239000007788 liquid Substances 0.000 claims abstract description 6
- 159000000007 calcium salts Chemical class 0.000 claims abstract description 5
- 229910052588 hydroxylapatite Inorganic materials 0.000 claims description 22
- 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 description 21
- 239000011159 matrix material Substances 0.000 claims description 14
- 235000019731 tricalcium phosphate Nutrition 0.000 claims description 12
- 229910000391 tricalcium phosphate Inorganic materials 0.000 claims description 12
- 229940078499 tricalcium phosphate Drugs 0.000 claims description 12
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 10
- 238000003618 dip coating Methods 0.000 claims description 9
- 238000010992 reflux Methods 0.000 claims description 8
- FUFJGUQYACFECW-UHFFFAOYSA-L calcium hydrogenphosphate Chemical compound [Ca+2].OP([O-])([O-])=O FUFJGUQYACFECW-UHFFFAOYSA-L 0.000 claims description 7
- 235000019700 dicalcium phosphate Nutrition 0.000 claims description 7
- 230000032050 esterification Effects 0.000 claims description 6
- 238000005886 esterification reaction Methods 0.000 claims description 6
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 5
- 239000000843 powder Substances 0.000 claims description 5
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 claims description 4
- 229910052587 fluorapatite Inorganic materials 0.000 claims description 4
- 229940077441 fluorapatite Drugs 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
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical class CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 3
- ZQBZAOZWBKABNC-UHFFFAOYSA-N [P].[Ca] Chemical compound [P].[Ca] ZQBZAOZWBKABNC-UHFFFAOYSA-N 0.000 claims description 3
- 230000015572 biosynthetic process Effects 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
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 claims description 3
- BDZBKCUKTQZUTL-UHFFFAOYSA-N triethyl phosphite Chemical compound CCOP(OCC)OCC BDZBKCUKTQZUTL-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
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 2
- XTTGYFREQJCEML-UHFFFAOYSA-N tributyl phosphite Chemical compound CCCCOP(OCCCC)OCCCC XTTGYFREQJCEML-UHFFFAOYSA-N 0.000 claims description 2
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 claims description 2
- 239000010410 layer Substances 0.000 abstract description 12
- 229910052586 apatite Inorganic materials 0.000 abstract description 5
- 238000000151 deposition Methods 0.000 abstract description 3
- 230000008021 deposition Effects 0.000 abstract description 3
- 238000004090 dissolution Methods 0.000 abstract 1
- 238000001035 drying Methods 0.000 abstract 1
- 239000002355 dual-layer Substances 0.000 abstract 1
- 238000002513 implantation Methods 0.000 abstract 1
- 239000011858 nanopowder Substances 0.000 abstract 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 abstract 1
- 150000003016 phosphoric acids Chemical class 0.000 abstract 1
- 239000011574 phosphorus Substances 0.000 abstract 1
- 229910052698 phosphorus Inorganic materials 0.000 abstract 1
- 229910052751 metal Inorganic materials 0.000 description 10
- 239000002184 metal Substances 0.000 description 10
- 239000007943 implant Substances 0.000 description 7
- 210000000988 bone and bone Anatomy 0.000 description 5
- 230000005923 long-lasting effect Effects 0.000 description 5
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 4
- 230000001476 alcoholic effect Effects 0.000 description 4
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 4
- 229910052731 fluorine Inorganic materials 0.000 description 4
- 239000011737 fluorine Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- FFBHFFJDDLITSX-UHFFFAOYSA-N benzyl N-[2-hydroxy-4-(3-oxomorpholin-4-yl)phenyl]carbamate Chemical compound OC1=C(NC(=O)OCC2=CC=CC=C2)C=CC(=C1)N1CCOCC1=O FFBHFFJDDLITSX-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 125000001153 fluoro group Chemical group F* 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000003915 cell function Effects 0.000 description 2
- 239000011247 coating layer Substances 0.000 description 2
- 230000010354 integration Effects 0.000 description 2
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 2
- 210000001519 tissue Anatomy 0.000 description 2
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- 229910001069 Ti alloy Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000004071 biological effect Effects 0.000 description 1
- 210000001124 body fluid Anatomy 0.000 description 1
- 239000010839 body fluid Substances 0.000 description 1
- 210000002449 bone cell Anatomy 0.000 description 1
- VSGNNIFQASZAOI-UHFFFAOYSA-L calcium acetate Chemical compound [Ca+2].CC([O-])=O.CC([O-])=O VSGNNIFQASZAOI-UHFFFAOYSA-L 0.000 description 1
- 239000001639 calcium acetate Substances 0.000 description 1
- 229960005147 calcium acetate Drugs 0.000 description 1
- 235000011092 calcium acetate Nutrition 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- JHLCADGWXYCDQA-UHFFFAOYSA-N calcium;ethanolate Chemical compound [Ca+2].CC[O-].CC[O-] JHLCADGWXYCDQA-UHFFFAOYSA-N 0.000 description 1
- 210000004027 cell Anatomy 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 231100000915 pathological change Toxicity 0.000 description 1
- 230000036285 pathological change Effects 0.000 description 1
- 238000007750 plasma spraying Methods 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
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- Materials For Medical Uses (AREA)
Abstract
The present invention discloses a dual-phase medical coating with a dual-layer structure, which is provided with a bottom layer made of insoluble calcium phosphate and a dual-phase calcium phosphate top layer formed by the insoluble calcium phosphate and soluble calcium phosphate. The preparation process comprises the following steps: step 1, phosphate or partially esterified phosphoric acid compounds are mixed with nitrogenous compounds in an icewater bath environment, calcium salt which can be dissolved in liquid alcohol is dropped and added, and the mixed liquor is heated and reflowed for 24 hours to form sol A; step 2, nano powder of soluble calcium phosphate is added to the sol A, and the mixture is dispersed by ultrasonic waves to form sol B; step 3, the sol A is coated on the surface of a basal body by an impregnating pulling method or a spin-coating method, and a base layer of the coating is obtained after the drying and the heat treatment; step 4, repeating the procedure of the step 3 on the base layer of the coating by using the sol B, and the top layer of the coating is obtained. The soluble calcium phosphate in the coating of the present invention can release calcium and phosphorus ions at the early stage of the implantation to promote the cell deposition and the osteoid apatite deposition, and the insoluble calcium phosphate provides good dissolution resistant property and long effectiveness at the middle and late stages.
Description
Technical field
The present invention relates to a kind of medical bio coating and preparation method thereof, especially a kind of that insoluble and solubility calcium phosphate is formed by having, have double-deck biphase calcium phosphor hydrochlorate medical coating and preparation method thereof.
Background technology
The reparation of and pathological changes damaged for sclerous tissueses such as bone and tooth carryings position at present adopts the medical metal implants so that necessary mechanical property to be provided more.In actual applications, metal implant must produce good integration with contiguous osseous tissue, for reaching this purpose, prepares the coating that one deck has excellent biological compatibility and bone conformability in the metal surface and has been proved to be a kind of good method.The now hydroxyapatite that adopt of coating material, method adopts plasma spraying method more more.Adopt plasma spray coating process to prepare one deck hydroxyapatite coating layer as Chinese patent CN1064610 in tooth section metal surface.In addition, Chinese patent CN1270841 adopts hydro-thermal method also to prepare the nano-hydroxyapatite biological coating.But simple hydroxyapatite coating layer exists several significant disadvantage: at first, coating long-lasting bad, this is that coating may be dissolved in a large number behind the life-time service because itself dissolubility is bigger.Secondly, its activity is still strong inadequately, is difficult to promote the interaction of implant and tissue.Discover that effectively the early stage release of calcium ion can be played effectively and promote bone cell function and accelerate material and the quick purpose of integrating of osseous tissue.This is hinting that again being dissolved with of coating is beneficial to the integration of implant and osseous tissue.As can be seen, practical application contradiction that the requirement of the material of coating is had: coating will have bigger early stage dissolving and less long-term dissolving concurrently.Obviously, homogenous material is difficult to reach this requirement.
Fluoridated hydroxyapatite has been proved to be has biocompatibility and the biological activity close with hydroxyapatite, but its dissolubility is obviously much smaller.But this has also caused fluoridated hydroxyapatite or fluor-apatite (hydroxyl that can regard as in the fluoridated hydroxyapatite is replaced by fluorine fully) cellular function with high fluorine content that some adverse effects are arranged.Therefore, adopt the mode introduce a kind of easily molten calcium phosphate phase therein, required early stage dissolving can effectively be provided, the while is long-lasting to be guaranteed because of the very little dissolubility of fluoridated hydroxyapatite itself again.
In addition, the bond strength of coating and metallic matrix also is to influence a long-lasting key factor of medical implant, and the bond strength deficiency will be quoted coating and come off under humoral effect, to such an extent as to cause the inefficacy of implant.Because the existence of fluorine at the interface, the fluoridated hydroxyapatite coating has been proved to be has good and bond strength metallic matrix, and this helps preparing a kind of efficient and long lasting coating more.
Summary of the invention
What the purpose of this invention is to provide a kind of function admirable has double-deck double-phase medical coating and preparation method thereof.
Of the present invention have double-deck double-phase medical coating and be made up of bottom and top layer, bottom is insoluble calcium phosphate layer, top layer is the biphase calcium phosphor silicate layer that insoluble calcium phosphate and soluble calcium phosphate are formed, above-mentioned insoluble calcium phosphate is fluor-apatite or fluoridated hydroxyapatite, soluble calcium phosphate is α phase tricalcium phosphate, β phase tricalcium phosphate, hydroxyapatite or calcium hydrogen phosphate, and the calcium in the insoluble calcium phosphate of top layer and the mol ratio of the calcium in the solubility calcium phosphate are 0.01: 1～2: 1.
The gross thickness of coating of the present invention is 0.2 micron～30 microns.
Preparation method of the present invention is to adopt the alcosol of the fluorine-containing calcium phosphate presoma of preparation, and adds soluble calcium phosphate therein, prepares coating with dip-coating method or spin-coating method at the medical metal matrix surface, through repeatedly repeating to reach desired thickness.Concrete steps are as follows:
1) under ice water bath environment with the phosphate mixture of phosphate ester or partial esterification and fluorochemical F: P=0.01 in molar ratio: 1～2: 3 mix, Ca: P=1.4 in molar ratio therein again: drip the calcium salt that dissolve in liquid alcohol at 1～2.0: 1, after being added dropwise to complete, the mixed liquor reflux was formed Sol A in 24 hours;
2) in Sol A, add the phosphatic nanometer powder of soluble calcium, and with ultrasonic dispersing formation sol B, wherein the mol ratio of the Ca in Ca in the Sol A and the soluble calcium phosphate is 0.01: 1～2: 1, and said soluble calcium phosphate is nanometer α phase tricalcium phosphate, nanometer β phase tricalcium phosphate, nanometer hydroxyapatite or nanometer calcium hydrogen phosphate;
3) with dip-coating method or spin-coating method with Sol A in the matrix surface coating, through 100～200 ℃ of oven dry,, obtain the bottom of coating again 500 ℃～750 ℃ heat treatments 5～30 minutes;
4) with sol B repeating step 3 on the bottom of coating) described process, obtain the top layer of coating.
Among the present invention, a kind of mixture to three kinds in the phosphate mixture of said phosphate ester or the partial esterification phosphoric acid that can be tributyl phosphate, triethyl phosphate, tributyl phosphite, NSC 5284 or part of O H be replaced by ethanol based or butanols base.Said fluorochemical is hexafluorophosphoric acid (HPF
6), ammonium hexafluorophosphate (NH
4PF
H), trifluoroacetic acid (CF
3COOH) or single fluorophosphoric acid (H
2PO
3F).The said calcium salt that dissolves in liquid alcohol is meant the nitrate of calcium or the acetate of calcium, and the liquid alcohol here can be methanol, ethanol, propanol or butanols.
The present invention is when adopting dip-coating method and spin-coating method to prepare coating, and film forming for the benefit of should be placed on relative humidity all the time and be lower than in 55% the atmosphere, absorbs moisture content to suppress dried glued membrane.The pull rate of dip-coating method is generally 1～20 cm per minute, and the spin-coating method rotating speed is generally 2500～4500 rev/mins.
Beneficial effect of the present invention is:
Of the present invention have double-deck double-phase medical coating and compare with general calcium phosphate coating, with the body fluid contact process in, implant early stage coating top layer and have bigger dissolving to discharge calcium, phosphonium ion, promote cell attachment and osteoid apatite deposition; At middle and late stage then owing to the existence of the insoluble calcium phosphate of coating bottom has antilysis preferably, thereby have good long-lasting.This coating can prepare at the medical metal matrix, comprises the surface of Titanium, titanium alloy, cochrome and medical stainless steel etc.
The specific embodiment
Further specify the present invention below in conjunction with example.
Example 1
1) phosphorus pentoxide is dissolved in ethanol and forms that part of O H group is replaced by alcohol radical, molecular formula such as PO (OH)
X(OR)
3-XConcentration be the phosphoric acid of 1mol/L, and reflux and formed the phosphate mixture of partial esterification in 24 hours.Under ice water bath environment with this phosphate mixture and hexafluorophosphoric acid F: P=0.01 in molar ratio: 1 mixes, Ca: P=1.67 in molar ratio therein again: 1 drips the lime nitrate alcoholic solution of 1mol/L, after being added dropwise to complete, the mixed liquor reflux was formed Sol A in 24 hours;
2) add nanometer β phase tricalcium phosphate in Sol A, the Ca in the Sol A and nanometer the β mol ratio of the Ca in the tricalcium phosphate powder mutually are 0.01: 1, and form the coating sol B after 20 minutes with ultrasonic dispersing;
3) with Sol A at metal base surface with dip-coating method (pull rate 3 cm per minute) in the matrix surface coating, 150 ℃ of down oven dry, 600 ℃ of heat treatments 15 minutes, obtain fluoro-containing apatite coating bottom again.
4) adopt sol B to repeat 3 having on the metallic matrix of bottom) described process 1 time, can obtain thickness 1.5 microns, by fluoro-containing apatite and β mutually tricalcium phosphate form, have a double-deck biphase calcium phosphor chromate coatings.
Example 2
1) NSC 5284 being dissolved in ethanol formation concentration is the solution of 1.5mol/L, under ice water bath environment this solution is mixed F in molar ratio: P=0.9 with hexafluorophosphoric acid: 3 mix, Ca: P=1.60 in molar ratio therein again: 1 drips the lime nitrate alcoholic solution of 1mol/L, after being added dropwise to complete, the mixed liquor reflux was formed Sol A in 24 hours;
2) add nanometer α phase tricalcium phosphate in Sol A, the Ca in the Sol A and nanometer the α mol ratio of the Ca in the tricalcium phosphate powder mutually are 1: 1, and form the coating sol B after 25 minutes with ultrasonic dispersing;
3) with Sol A at metal base surface with dip-coating method (pull rate 4 cm per minute) in the matrix surface coating, after 150 ℃ of oven dry,, obtain having the coating bottom of fluoridated hydroxyapatite again 600 ℃ of heat treatments 20 minutes.
4) adopt sol B to repeat 3 having on the metallic matrix of bottom) described process 2 times, can obtain thickness 5 microns, by have fluoridated hydroxyapatite and α mutually tricalcium phosphate form, have a double-deck biphase calcium phosphor chromate coatings.
Example 3
1) tributyl phosphate is dissolved in the phosphoric acid that ethanol forms 2.0mol/L, under ice water bath environment with this solution and ammonium hexafluorophosphate F: P=1 in molar ratio: 3 mix, Ca: P=1.70 in molar ratio therein again: 1 drips the calcium ethoxide alcoholic solution of 1mol/L, after being added dropwise to complete, the mixed liquor reflux was formed Sol A in 24 hours;
2) add nanometer hydroxyapatite in Sol A, the mol ratio of the Ca in Ca in the Sol A and the nanometer hydroxyapatite powder art is 1.1: 1, and forms the coating sol B after 20 minutes with ultrasonic dispersing;
3) with Sol A at metal base surface with spin-coating method (3000 rev/mins) in the matrix surface coating, through 150 ℃ of oven dry, 600 ℃ of heat treatments 15 minutes, obtain fluoro-containing apatite coating bottom again.
4) adopt sol B to repeat 3 having on the metallic matrix of bottom) described process 1 time, can obtain thickness 2.5 microns, that form by fluor-apatite and hydroxyapatite, have a double-deck biphase calcium phosphor chromate coatings.
Example 4
1) 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 reflux and formed the phosphate mixture of partial esterification in 24 hours.Under ice water bath environment this phosphate mixture is mixed F in molar ratio: P=0.8 with single fluorophosphoric acid: 3 mix, Ca: P=1.67 in molar ratio therein again: 1 drips the calcium acetate alcoholic solution of 2mol/L, after being added dropwise to complete, the mixed liquor reflux was formed Sol A in 24 hours;
2) add the nanometer calcium hydrogen phosphate in Sol A, the mol ratio of the Ca in Ca in the Sol A and the nanometer calcium hydrogen phosphate powder is 0.3: 1, and forms the coating sol B after 15 minutes with ultrasonic dispersing;
3) with Sol A at metal base surface with dip-coating method (pull rate 7 cm per minute) in the matrix surface coating, through 150 ℃ of oven dry,, obtain having the coating bottom of fluoridated hydroxyapatite again 600 ℃ of heat treatments 15 minutes;
4) adopt sol B to repeat 3 having on the metallic matrix of bottom) described process 1 time, can obtain thickness 1.2 microns, that fluoridated hydroxyapatite and calcium hydrogen phosphate are formed by having, have a double-deck biphase calcium phosphor chromate coatings.
Claims (6)
1. has double-deck double-phase medical coating, it is characterized in that forming by bottom and top layer, bottom is insoluble calcium phosphate layer, top layer is the biphase calcium phosphor silicate layer that insoluble calcium phosphate and soluble calcium phosphate are formed, above-mentioned insoluble calcium phosphate is fluor-apatite or fluoridated hydroxyapatite, soluble calcium phosphate is α phase tricalcium phosphate, β phase tricalcium phosphate, hydroxyapatite or calcium hydrogen phosphate, and the calcium in the insoluble calcium phosphate of top layer and the mol ratio of the calcium in the solubility calcium phosphate are 0.01: 1～2: 1.
2. according to claim 1 have a double-deck double-phase medical coating, it is characterized in that total coating thickness is 0.2 micron～30 microns.
3. the preparation method with double-deck double-phase medical coating according to claim 1 is characterized in that may further comprise the steps:
1) under ice water bath environment with the phosphate mixture of phosphate ester or partial esterification and fluorochemical F: P=0.01 in molar ratio: 1～2: 3 mix, Ca: P=1.4 in molar ratio therein again: drip the calcium salt that dissolve in liquid alcohol at 1～2.0: 1, after being added dropwise to complete, the mixed liquor reflux was formed Sol A in 24 hours;
2) in Sol A, add the phosphatic nanometer powder of soluble calcium, and with ultrasonic dispersing formation sol B, wherein the mol ratio of the Ca in Ca in the Sol A and the soluble calcium phosphate is 0.01: 1～2: 1, and said soluble calcium phosphate is nanometer α phase tricalcium phosphate, nanometer β phase tricalcium phosphate, nanometer hydroxyapatite or nanometer calcium hydrogen phosphate;
3) in relative humidity is lower than 55% atmosphere, use Sol A in the matrix surface coating with dip-coating method or spin-coating method, through 100～200 ℃ of oven dry, again 500 ℃～750 ℃ heat treatments 5～30 minutes, obtain the bottom of coating, the pull rate of dip-coating method is 1～20 cm per minute, and the rotating speed of spin-coating method is 2500～4500 rev/mins;
4) with sol B repeating step 3 on the bottom of coating) described process, obtain the top layer of coating.
4. a kind of mixture to three kinds in the preparation method with double-deck double-phase medical coating according to claim 3, the phosphate mixture that it is characterized in that said phosphate ester or the partial esterification phosphoric acid that to be tributyl phosphate, triethyl phosphate, tributyl phosphite, NSC 5284 or part of O H replaced by ethanol based or butanols base.
5. the preparation method with double-deck double-phase medical coating according to claim 3 is characterized in that said fluorochemical is hexafluorophosphoric acid, ammonium hexafluorophosphate, trifluoroacetic acid or single fluorophosphoric acid.
6. the preparation method with double-deck double-phase medical coating according to claim 3 is characterized in that the said calcium salt that dissolves in liquid alcohol is the nitrate of calcium or the acetate of calcium.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100497715A CN100352517C (en) | 2006-03-10 | 2006-03-10 | Double-phase medical coating with double-layer structure and production thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100497715A CN100352517C (en) | 2006-03-10 | 2006-03-10 | Double-phase medical coating with double-layer structure and production thereof |
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|---|---|
| CN1817372A CN1817372A (en) | 2006-08-16 |
| CN100352517C true CN100352517C (en) | 2007-12-05 |
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| CN110775953B (en) * | 2019-11-27 | 2023-03-31 | 中山市科信生物技术有限公司 | Method for synthesizing thermodynamically stable hydroxyapatite with microscopic kinetic reaction limitation |
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| WO2004103424A1 (en) * | 2003-05-21 | 2004-12-02 | Dentium Co., Ltd | Biocompatible implant coated with biocompatible fluor-hydroxyapatite and a coating method of the same |
| CN1228097C (en) * | 2003-08-08 | 2005-11-23 | 浙江大学 | Medical fluorinated calcium phosphate coating material and its prepn process |
| CN1743014A (en) * | 2005-09-28 | 2006-03-08 | 浙江大学 | Biological medical material with biological responding coating and preparing method |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004103424A1 (en) * | 2003-05-21 | 2004-12-02 | Dentium Co., Ltd | Biocompatible implant coated with biocompatible fluor-hydroxyapatite and a coating method of the same |
| CN1228097C (en) * | 2003-08-08 | 2005-11-23 | 浙江大学 | Medical fluorinated calcium phosphate coating material and its prepn process |
| CN1743014A (en) * | 2005-09-28 | 2006-03-08 | 浙江大学 | Biological medical material with biological responding coating and preparing method |
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