CN101554491B - 液相热喷涂制备生物活性玻璃涂层的方法 - Google Patents
液相热喷涂制备生物活性玻璃涂层的方法 Download PDFInfo
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- CN101554491B CN101554491B CN200910302658A CN200910302658A CN101554491B CN 101554491 B CN101554491 B CN 101554491B CN 200910302658 A CN200910302658 A CN 200910302658A CN 200910302658 A CN200910302658 A CN 200910302658A CN 101554491 B CN101554491 B CN 101554491B
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- potassium
- sodium
- calcium
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- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 70
- 239000008367 deionised water Substances 0.000 claims description 65
- 229910021641 deionized water Inorganic materials 0.000 claims description 65
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- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 claims description 62
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 54
- 238000007750 plasma spraying Methods 0.000 claims description 48
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 claims description 45
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- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 claims description 38
- 239000011777 magnesium Substances 0.000 claims description 28
- 239000011734 sodium Substances 0.000 claims description 27
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- 239000004317 sodium nitrate Substances 0.000 claims description 27
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- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 25
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- 238000006460 hydrolysis reaction Methods 0.000 claims description 22
- 238000005507 spraying Methods 0.000 claims description 22
- 229910052700 potassium Inorganic materials 0.000 claims description 21
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 19
- 229910052710 silicon Inorganic materials 0.000 claims description 19
- 239000010703 silicon Substances 0.000 claims description 19
- 229910052782 aluminium Inorganic materials 0.000 claims description 18
- 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 16
- 239000010936 titanium Substances 0.000 claims description 15
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 14
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 14
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 14
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 14
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 14
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 14
- 229910052731 fluorine Inorganic materials 0.000 claims description 14
- 239000011737 fluorine Substances 0.000 claims description 14
- 229910052749 magnesium Inorganic materials 0.000 claims description 14
- 239000011591 potassium Substances 0.000 claims description 14
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 13
- 230000015572 biosynthetic process Effects 0.000 claims description 13
- 229910052791 calcium Inorganic materials 0.000 claims description 13
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 12
- 239000001488 sodium phosphate Substances 0.000 claims description 12
- 235000011008 sodium phosphates Nutrition 0.000 claims description 12
- 229910052719 titanium Inorganic materials 0.000 claims description 12
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 claims description 12
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 12
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 11
- 239000011574 phosphorus Substances 0.000 claims description 11
- 229910000162 sodium phosphate Inorganic materials 0.000 claims description 11
- 238000007751 thermal spraying Methods 0.000 claims description 11
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 10
- 229910001069 Ti alloy Inorganic materials 0.000 claims description 10
- 239000004323 potassium nitrate Substances 0.000 claims description 10
- 235000010333 potassium nitrate Nutrition 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 9
- 239000002585 base Substances 0.000 claims description 8
- 229910004261 CaF 2 Inorganic materials 0.000 claims description 7
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 6
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 6
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 6
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 6
- FUFJGUQYACFECW-UHFFFAOYSA-L calcium hydrogenphosphate Chemical compound [Ca+2].OP([O-])([O-])=O FUFJGUQYACFECW-UHFFFAOYSA-L 0.000 claims description 6
- 239000001506 calcium phosphate Substances 0.000 claims description 6
- 229910000389 calcium phosphate Inorganic materials 0.000 claims description 6
- 235000011010 calcium phosphates Nutrition 0.000 claims description 6
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 claims description 6
- 235000019700 dicalcium phosphate Nutrition 0.000 claims description 6
- ZPWVASYFFYYZEW-UHFFFAOYSA-L dipotassium hydrogen phosphate Chemical compound [K+].[K+].OP([O-])([O-])=O ZPWVASYFFYYZEW-UHFFFAOYSA-L 0.000 claims description 6
- 235000019797 dipotassium phosphate Nutrition 0.000 claims description 6
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical compound Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 claims description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 6
- 229910000160 potassium phosphate Inorganic materials 0.000 claims description 6
- 235000011009 potassium phosphates Nutrition 0.000 claims description 6
- 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 description 6
- 229910045601 alloy Inorganic materials 0.000 claims description 5
- 239000000956 alloy Substances 0.000 claims description 5
- 229910000396 dipotassium phosphate Inorganic materials 0.000 claims description 5
- 239000010935 stainless steel Substances 0.000 claims description 5
- 229910001220 stainless steel Inorganic materials 0.000 claims description 5
- 239000007789 gas Substances 0.000 claims description 4
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 3
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 3
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 3
- KVBCYCWRDBDGBG-UHFFFAOYSA-N azane;dihydrofluoride Chemical compound [NH4+].F.[F-] KVBCYCWRDBDGBG-UHFFFAOYSA-N 0.000 claims description 3
- NKWPZUCBCARRDP-UHFFFAOYSA-L calcium bicarbonate Chemical compound [Ca+2].OC([O-])=O.OC([O-])=O NKWPZUCBCARRDP-UHFFFAOYSA-L 0.000 claims description 3
- 229910000020 calcium bicarbonate Inorganic materials 0.000 claims description 3
- 239000001110 calcium chloride Substances 0.000 claims description 3
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 3
- JXRVKYBCWUJJBP-UHFFFAOYSA-L calcium;hydrogen sulfate Chemical compound [Ca+2].OS([O-])(=O)=O.OS([O-])(=O)=O JXRVKYBCWUJJBP-UHFFFAOYSA-L 0.000 claims description 3
- 229910010293 ceramic material Inorganic materials 0.000 claims description 3
- APGUSRKQFBWUPZ-UHFFFAOYSA-K disulfooxyalumanyl hydrogen sulfate Chemical compound [Al+3].OS([O-])(=O)=O.OS([O-])(=O)=O.OS([O-])(=O)=O APGUSRKQFBWUPZ-UHFFFAOYSA-K 0.000 claims description 3
- QWDJLDTYWNBUKE-UHFFFAOYSA-L magnesium bicarbonate Chemical compound [Mg+2].OC([O-])=O.OC([O-])=O QWDJLDTYWNBUKE-UHFFFAOYSA-L 0.000 claims description 3
- 235000014824 magnesium bicarbonate Nutrition 0.000 claims description 3
- 239000002370 magnesium bicarbonate Substances 0.000 claims description 3
- 229910000022 magnesium bicarbonate Inorganic materials 0.000 claims description 3
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- 235000011147 magnesium chloride Nutrition 0.000 claims description 3
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims description 3
- 235000019341 magnesium sulphate Nutrition 0.000 claims description 3
- FXBYOMANNHFNQV-UHFFFAOYSA-L magnesium;hydrogen sulfate Chemical compound [Mg+2].OS([O-])(=O)=O.OS([O-])(=O)=O FXBYOMANNHFNQV-UHFFFAOYSA-L 0.000 claims description 3
- 239000011736 potassium bicarbonate Substances 0.000 claims description 3
- 235000015497 potassium bicarbonate Nutrition 0.000 claims description 3
- 229910000028 potassium bicarbonate Inorganic materials 0.000 claims description 3
- CHKVPAROMQMJNQ-UHFFFAOYSA-M potassium bisulfate Chemical compound [K+].OS([O-])(=O)=O CHKVPAROMQMJNQ-UHFFFAOYSA-M 0.000 claims description 3
- 229910000343 potassium bisulfate Inorganic materials 0.000 claims description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 3
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- VKJKEPKFPUWCAS-UHFFFAOYSA-M potassium chlorate Chemical compound [K+].[O-]Cl(=O)=O VKJKEPKFPUWCAS-UHFFFAOYSA-M 0.000 claims description 3
- 239000001103 potassium chloride Substances 0.000 claims description 3
- 235000011164 potassium chloride Nutrition 0.000 claims description 3
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims description 3
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 claims description 3
- 229910052939 potassium sulfate Inorganic materials 0.000 claims description 3
- 235000011151 potassium sulphates Nutrition 0.000 claims description 3
- FDNAPBUWERUEDA-UHFFFAOYSA-N silicon tetrachloride Chemical compound Cl[Si](Cl)(Cl)Cl FDNAPBUWERUEDA-UHFFFAOYSA-N 0.000 claims description 3
- WBHQBSYUUJJSRZ-UHFFFAOYSA-M sodium bisulfate Chemical compound [Na+].OS([O-])(=O)=O WBHQBSYUUJJSRZ-UHFFFAOYSA-M 0.000 claims description 3
- 229910000342 sodium bisulfate Inorganic materials 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- 235000017550 sodium carbonate Nutrition 0.000 claims description 3
- 239000011780 sodium chloride Substances 0.000 claims description 3
- 235000002639 sodium chloride Nutrition 0.000 claims description 3
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 3
- 235000011152 sodium sulphate Nutrition 0.000 claims description 3
- WVMSIBFANXCZKT-UHFFFAOYSA-N triethyl(hydroxy)silane Chemical compound CC[Si](O)(CC)CC WVMSIBFANXCZKT-UHFFFAOYSA-N 0.000 claims description 3
- AAPLIUHOKVUFCC-UHFFFAOYSA-N trimethylsilanol Chemical compound C[Si](C)(C)O AAPLIUHOKVUFCC-UHFFFAOYSA-N 0.000 claims description 3
- 230000008569 process Effects 0.000 abstract description 32
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- QFXZANXYUCUTQH-UHFFFAOYSA-N ethynol Chemical group OC#C QFXZANXYUCUTQH-UHFFFAOYSA-N 0.000 description 1
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Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
- C23C4/12—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the method of spraying
- C23C4/123—Spraying molten metal
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/28—Materials for coating prostheses
- A61L27/30—Inorganic materials
- A61L27/32—Phosphorus-containing materials, e.g. apatite
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
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Abstract
本发明属于生物医用材料领域,涉及一种液相热喷涂制备生物活性玻璃涂层的方法。本发明要解决的技术问题是现有的粉末喷涂法中粉末原料制备过程复杂、周期长的缺陷,和溶胶凝胶等湿化学法中制备涂层厚度薄、生产效率低的缺点。解决上述问题的技术方案是提出新制备方法。该方法中,首先按照生物活性玻璃的化学组成称量有机和无机原料,制得溶胶或悬浮液先驱液;然后将此溶胶或悬浮液作为热喷涂原料进行热喷涂,经过液态原料在高温下最后沉积到作为基底的生物医用材料表面形成生物活性玻璃涂层。本发明方法可用于制备生物活性玻璃涂层,具有操作简单,工艺流程少,制备效率高,成本低廉,适合于工业化生产等优点。
Description
技术领域
本发明属于生物医用材料领域,具体涉及液相热喷涂制备生物活性玻璃涂层的方法。
背景技术
生物活性玻璃最早是由美国佛罗里达大学Hench等1971年开发研究出来的【L.L.Hench,R J Splinter,W C Allen.,J.Biomed.Mater.Res.Symp.,1971,(2):117~141.】。由于生物活性玻璃生物活性高,与骨和软组织都有良好的结合,作为人工骨材料长期植入体内是安全稳定的,在骨科、牙科、耳等部位的伤害均可进行修复治疗,以至康复,具有可观的应用前景【L.L.Hench,Bioceramics,J.Am,Ceram.Soc.,1998,(81):1705~1728.】。目前生物活性玻璃已通过美国食品与药物管理局(FDA)的认证。然而,生物活性玻璃存在着脆性大、韧性低、机械强度不足的缺点,从而制约了它的应用。在钛及钛合金表面涂覆生物活性玻璃涂层是改善医疗植入器械表面生物活性的主要方法之一,它综合了钛及钛合金良好的机械性能和生物活性玻璃良好的生物相容性、生物活性、骨传导性和骨诱导性,在临床上广泛用于骨替代及缺损修复。
在钛及钛合金表面涂覆生物活性玻璃涂层的方法有很多,如粉末冶金烧结法、酸碱处理法、激光熔覆法、脉冲激光沉积法、磁控溅射法、电泳沉积法、溶胶-凝胶法和粉末等离子喷涂法等,其中溶胶-凝胶法和粉末等离子喷涂法是目前最为常用和广为研究的方法。溶胶-凝胶法中,首先将有机醇盐水解,然后加入无机盐溶液制得溶胶,溶胶陈化一段时间后,将溶胶涂覆到预先处理好的作为基底的钛及钛合金上,再将涂好溶胶的基底在一定温度下烘干,然后重复涂覆-烘干,最后将其在一定温度下烧结制得生物活性玻璃涂层【L.D.Piveteau,M.I.Girona,L.Schlapbach,et al.,Materials Science:Materials inMedicine,1999,(10):161-167】。粉末等离子喷涂法是热喷涂方法中的一种。在粉末等离子喷涂法中,对喷涂用粉末原料的制备有较高的要求,首先采用熔融-冷却法或者溶胶-凝胶法制备生物活性玻璃块体或粉末,再将块体或粉末进行粉碎、球磨、分筛以制备粉末等离子喷涂所用的喷涂原料,然后将制得的粉末原料装入等离子喷涂设备特定的给料机构中,粉末原料在压力的作用下经过管道传送至等离子喷枪旁的粉末喷嘴,最后从粉末喷嘴直接喷射到等离子体火焰中,在高温等离子体火焰中迅速熔融并沉积到作为基底的钛及钛合金上形成生物活性玻璃涂层【T.M.Lee,E.Chang,et.al.,Surface and Coatings Technology,1996,(79):170-177】。
溶胶-凝胶法制备生物活性玻璃涂层反应温度低,反应过程易于控制,制品的均匀度、纯度高,化学计量准确,易于改性,掺杂的范围宽,所制得的涂层生物活性高。然而,溶胶-凝胶法制备生物活性玻璃涂层处理过程时间较长,所得涂层厚度很薄,多在10微米左右,且涂层易产生开裂,涂层与基底结合强度低,而且工艺复杂,生产效率低,不适合规模化生产。粉末等离子喷涂法是目前国内外应用最为广泛的方法之一,也是迄今唯一取得成功的商业化技术,用这种方法制备生物活性玻璃涂层喷涂效率高,涂层厚度可以控制,涂层与基底结合强度高。然而喷涂对所用的生物玻璃粉末原料要求较高,多采用熔融-冷却法,首先将各成分氧化物混合在一起在高温下熔融,再经快速冷却制得生物活性玻璃块体或粉末,最后将块体或粉末进行粉碎、球磨、分筛以制备粉末等离子喷涂所用的喷涂原料,制备工艺繁复,制备时间较长,因而生产效率较低,成本也较高。
发明内容
本发明的目的在于针对现有的粉末喷涂法中粉末原料制备过程复杂、周期长的缺陷,和溶胶-凝胶等湿化学法中制备涂层厚度薄、生产效率低的缺点,提出一种制备生物活性玻璃涂层的新方法。
该方法包括以下步骤:
a、准备液态生物活性玻璃先驱液;
b、使用液态生物活性玻璃先驱液进行热喷涂,沉积到作为基底的生物医用材料的表面形成生物活性玻璃涂层。
其中,上述方法步骤a中的生物活性玻璃先驱液由以下配比的组分组成:
按折合成氧化物质量含量为SiO230~60wt%,P2O51~40wt%,CaO 20~45wt%,Na2O 0~25wt%,MgO 0~20wt%,Al2O30~3wt%,K2O 0~8wt%,CaF20~15wt%分别量取硅源、磷源、钙源、钠源、镁源、铝源、钾源、氟源;
按照摩尔比为硅源∶乙醇=1∶2~5,硅源∶H2O=1∶4~8分别量取乙醇和去离子水;
按照质量比为钙源∶H2O=1∶1~2,钠源∶H2O=1∶1~2,镁源∶H2O=1∶1~2,铝源∶H2O=1∶1.5~2,钾源∶H2O=1∶3~5,氟源∶H2O=1∶1~2分别量取去离子水。
其中,上述液态生物活性玻璃先驱液按下述方法制备而成:
①将量取好的硅源和乙醇混合并搅拌均匀,然后加入去离子水;
②调节pH值至1~3,硅源水解形成溶胶,溶液完全澄清后搅拌均匀;
③加入磷源并搅拌均匀;
④将钙源、钠源、镁源、铝源、钾源和氟源分别加入到去离子水中,完全溶解后加入到水解好的溶胶中,搅拌均匀后即制得热喷涂所用的酸性生物活性玻璃先驱液。
其中,上述液态生物活性玻璃先驱液按下述方法制备而成:
①将量取好的硅源和乙醇混合并搅拌均匀,然后加入去离子水;
②调节pH值至9~11,硅源水解形成悬浮液,溶液完全浑浊后搅拌均匀;
③加入磷酸三乙酯并搅拌5~10min;
④将钙源、钠源、镁源、铝源、钾源和氟源分别加入到去离子水中,完全溶解后加入到水解好的悬浮液中,搅拌均匀后即制得热喷涂所用的碱性生物活性玻璃先驱液。
其中,上述硅源为正硅酸乙酯、三甲基硅醇、三乙基硅醇或四氯化硅中的至少一种;
其中,上述磷源为磷酸三乙酯、磷酸钙、磷酸钠、磷酸氢钙、磷酸氢钠、磷酸钾或磷酸氢钾中的至少一种;
其中,上述钙源为硝酸钙、而应包括氯化钙、碳酸氢钙、硫酸钙、硫酸氢钙、磷酸钙或磷酸氢钙中的至少一种;
其中,上述钠源为硝酸钠、氯化钠、碳酸钠、碳酸氢钠、硫酸钠、硫酸氢钠、磷酸钠或磷酸氢钠中的至少一种;
其中,上述镁源为硝酸镁、氯化镁、碳酸氢镁、硫酸镁或硫酸氢镁中的至少一种;
其中,上述铝源为硝酸铝、氯化铝、硫酸铝或硫酸氢铝中的至少一种;
其中,上述钾源为硝酸钾,而应包括氯化钾,碳酸钾,碳酸氢钾,硫酸钾,硫酸氢钾,氯酸钾,次氯酸钾,磷酸钾或磷酸氢钾中的至少一种;
其中,上述氟源为氟化铵、氟化氢铵或氟化氢中的至少一种。
其中,上述方法步骤a中的组分优选为:硅源为正硅酸乙酯;磷源为磷酸三乙酯;钙源为硝酸钙;钠源为硝酸钠;镁源为硝酸镁;铝源为硝酸铝;钾源为硝酸钾;氟源为氟化铵。
其中,上述制备生物活性玻璃涂层的方法,其特征在于:步骤b中所述的热喷涂为等离子喷涂、超音速火焰热喷涂、电弧热喷涂、气体爆炸热喷涂或氧乙炔火焰热喷涂。
其中,上述步骤b中的热喷涂为等离子喷涂,生物活性玻璃液体先驱液原料用50~200微米小直径导管以直线型射流的方式,直接径向注入等离子火焰中心的高温区域。
进一步的,上述步骤b中的等离子喷涂时等离子喷枪口与作为基底的生物医用材料表面之间的距离为10~25cm。所述步骤b中等离子喷涂的功率为24~60KW。
其中,上述作为基底的生物医用材料为生物医用钛,或生物医用钛合金,或生物医用不锈钢,或生物医用钴基合金,或其它生物医用金属材料,或含金属的生物医用复合材料,或生物医用陶瓷材料,或含陶瓷的生物医用复合材料。
本发明方法中,首先用湿化学法制得溶胶或悬浮液,再将溶胶或悬浮液直接作为喷涂原料传送到等离子火焰中,经过液态原料在高温下的细化、蒸发、燃烧、分解、熔融等一系列过程并沉积到作为基底的生物医用材料形成生物活性玻璃涂层。本发明方法中作为基底的生物医用材料为生物医用钛,或生物医用钛合金,或生物医用不锈钢,或生物医用钴基合金,或其它生物医用金属材料,或含金属的生物医用复合材料,或生物医用陶瓷材料,或含陶瓷的生物医用复合材料。材料的选择以能承受等离子喷涂时的温度为宜。
本发明方法中制备先驱液所使用的硅源应不限于正硅酸乙酯,而应包括三甲基硅醇,三乙基硅醇,四氯化硅等其它含硅有机物或无机物;磷源应不限于磷酸三乙酯,而应包括亚磷酸三乙酯,磷酸钙,磷酸钠,磷酸氢钙,磷酸氢钠,磷酸钾,磷酸氢钾等其它含磷有机物或无机物;钙源应不限于硝酸钙,而应包括氯化钙,碳酸氢钙,硫酸钙,硫酸氢钙,磷酸钙,磷酸氢钙等其它含钙无机物;钠源应不限于硝酸钠,而应包括氯化钠,碳酸钠,碳酸氢钠,硫酸钠,硫酸氢钠,磷酸钠,磷酸氢钠等其它含钠无机物;镁源应不限于硝酸镁,而应包括氯化镁,碳酸氢镁,硫酸镁,硫酸氢镁等其它含镁无机物;铝源应不限于硝酸铝,而应包括氯化铝,硫酸铝,硫酸氢铝等其它含铝无机物;钾源应不限于硝酸钾,而应包括氯化钾,碳酸钾,碳酸氢钾,硫酸钾,硫酸氢钾,氯酸钾,次氯酸钾,磷酸钾,磷酸氢钾等其它含钾无机物;氟源应不限于氟化铵,而应包括氟化氢铵,氟化氢等其它含氟无机物。本发明中制备酸性先驱液时调节pH值的酸不限于硝酸,而可使用氢氟酸,盐酸,硫酸,醋酸等其它酸;制备碱性先驱液时调节pH值的碱不限于氨水,可使用氢氧化钠,氢氧化钾等其它碱。
本发明方法结合了粉末等离子喷涂法和溶胶凝胶法的优点并克服了其相应缺点,它大大简化了粉末等离子喷涂中繁琐的粉末原料制备过程及相对高昂的成本,而且缩短了溶胶凝胶法中漫长的处理时间及克服了溶胶凝胶法制备涂层很薄的弱点,具有工艺简单,生产效率高的优点,适合于工业化生产。
具体来说,本发明方法采用等离子喷涂时可按以下步骤进行:
(1)生物活性玻璃液体先驱液原料的制备
a)、首先按照不同生物活性玻璃组成折合成氧化物质量含量SiO230~60wt%,P2O51~40wt%,CaO20~45wt%,Na2O0~25wt%,MgO0~20wt%,Al2O30~3wt%,K2O 0~8wt%,CaF20~15wt%分别量取正硅酸乙酯(TEOS)、磷酸三乙酯(TEP)、硝酸钙(Ca(NO3)2·4H2O)、硝酸钠(NaNO3)、硝酸镁(Mg(NO3)2·6H2O)、硝酸铝(Al(NO3)3·9H2O)、硝酸钾(KNO3)、氟化铵(NH4F),按照摩尔比为TEOS∶乙醇(EtOH)=1∶2~5,TEOS∶去离子水(H2O)=1∶4~8分别量取乙醇和去离子水,按照质量比为Ca(NO3)2·4H2O∶H2O=1∶1~2,NaNO3∶H2O=1∶1~2,Mg(NO3)2·6H2O=1∶1~2,Al(NO3)3·9H2O∶H2O=1∶1.5~2,KNO3∶H2O=1∶3~5,NH4F∶H2O=1∶1~2量取去离子水;
b)、将量取好的正硅酸乙酯和乙醇混合并置于磁力搅拌器上搅拌,调节转速为350~700转/分,搅拌5~10min后加入去离子水;
c)、加入硝酸调节PH值至1~3,溶液完全澄清后继续搅拌10~20min;
或者:
加入氨水调节PH值至9~11,溶液完全浑浊后继续搅拌10~20min;
e)、加入磷酸三乙酯并搅拌5~10min;
f)、将硝酸钙、硝酸钠、硝酸镁、硝酸铝、硝酸钾和氟化铵加入到去离子水中,完全溶解后加入到水解好的溶胶或悬浮液中,搅拌20~30min后即制得等离子喷涂所用的生物活性玻璃先驱液;
(2)生物活性玻璃液体先驱液原料的传输及注入
利于电子蠕动泵作为液体原料传输的动力装置,调节蠕动泵转速为5~20转/分,将生物活性玻璃先驱液用直径为3~8mm的导管传输到等离子喷枪口的注入装置中,注入装置采用50~200微米小直径导管以直线型射流的方式,将生物活性玻璃液体先驱液直接径向注入等离子火焰中心的高温区域;
(3)液相等离子喷涂及生物活性玻璃涂层的生成
调节等离子喷涂功率为24~60KW,等离子喷枪口与作为基底的生物医用材料之间的距离为10~25cm,喷涂次数为5~15次,生物活性玻璃液体先驱液原料通过步骤(1)制备,步骤(2)传输及注入,最后以一定的速度射入到高温等离子火焰中,经过液态原料在高温下的细化、蒸发、燃烧、分解、熔融等一系列过程并沉积到作为基底的生物医用材料表面形成生物活性玻璃涂层。
本发明方法与现有技术相比具有以下有益技术效果:
1、本发明方法采用热喷涂技术制备生物玻璃涂层,直接将制得的溶胶或悬浮液液体原料在高温下的细化、蒸发、燃烧、分解、熔融等一系列过程并沉积到医用金属基底表面形成生物活性玻璃涂层;与溶胶-凝胶法相比,省略了漫长的陈化时间,缩短了繁琐的热处理过程,提高了生产效率。
2、本发明方法采用液相溶胶或悬浮液作为热喷涂的原料,其原料的制备与粉末热喷涂相比,省略了氧化物原料的高温熔融、快速冷却制得生物活性玻璃块体或粉末,及块体或粉末原料的粉碎、球磨、分筛等一系列繁琐的工艺环节,极大地提高了生产效率,降低了生产成本。现有的制备生物玻璃涂层的凝胶溶胶法必须要制备成溶胶后才能制备涂层,而使用本发明方法,既可以将原料制成溶胶后使用,也可以将原料制成悬浮液使用,更加方便快捷。
3、本发明方法采用液相热喷涂法制备生物玻璃涂层,所制得的涂层与溶胶-凝胶法制得的涂层相比,涂层较厚,可达100~300μm及更高,而溶胶-凝胶法制得的涂层一般为10~30μm,因此生产效率得到了极大的提高,适合于工业化生产。
4、本发明方法所制得的涂层与溶胶-凝胶法制得的涂层相比,涂层结合牢固,涂层不会开裂,且不易引入杂质,制得的涂层纯度较高,提高了涂层的质量。
5、本发明的液相热喷涂过程中采用蠕动泵或压力罐作为传输装置,并用3~8毫米的导管直接将液相原料传输到注入装置,并利用50~200微米小直径导管将原料注入高温区域中,与现有粉末热喷涂法采用的气压粉末传输装置相比,使用液相先驱液传输装置设备简单,操作简洁,流量控制精确,能进一步提高生产效率,降低生产成本。
附图说明
图1为本发明的工艺流程示意图;
图2为实施例2制备的生物活性玻璃涂层的100倍扫描电镜(SEM)图像;
图3为实施例2制备的生物活性玻璃涂层的100000倍SEM图像;
图4为实施例2制备的生物活性玻璃涂层在人体模拟体液(SBF)中浸泡7天后的SEM图像
图5为实施例2制备的生物活性玻璃涂层的X射线衍射(XRD)图谱;图谱中的结晶峰为基底材料钛(Ti)的结晶相,涂层主要是由无定形相组成。
图6为实施例2制备的生物活性玻璃涂层在SBF中浸泡7天后的XRD图谱。
具体实施方式
下面通过实施例,进一步阐明本发明实质性的特点和显著的进步,但本发明的内容绝非限于实施例中所涉及的内容。
本发明液相等离子喷涂法制备生物活性玻璃涂层,依次按照工艺流程图1进行,包括以下主要的工艺步骤:
(1)生物活性玻璃液体先驱液原料的制备;
(2)生物活性玻璃液体先驱液原料的传输及注入;
(3)液相等离子喷涂及生物活性玻璃涂层的生成。
实施例1:
首先按照折合成氧化物质量含量SiO230wt%,P2O520%,CaO 30wt%,Na2O 20wt%,分别量取正硅酸乙酯(TEOS)、磷酸三乙酯(TEP)、硝酸钙(Ca(NO3)2·4H2O)、硝酸钠(NaNO3),按照摩尔比为TEOS∶EtOH=1∶2,TEOS∶H2O=1∶8分别量取乙醇和去离子水,按照质量比为Ca(NO3)2·4H2O∶H2O=1∶2,NaNO3∶H2O=1∶1,量取去离子水;将量取好的正硅酸乙酯和乙醇混合并置于磁力搅拌器上搅拌,调节转速为350转/分,搅拌5min后加入去离子水,加入硝酸调节PH值至2,溶液完全澄清后继续搅拌10min;加入磷酸三乙酯并搅拌5min;将硝酸钙、硝酸钠加入到去离子水中完全溶解后加入到水解好的溶胶中,搅拌20min后即制得等离子喷涂所用的生物活性玻璃先驱液。
利于电子蠕动泵作为液体原料传输的动力装置,调节蠕动泵转速为5转/分,将生物活性玻璃先驱液用直径为3mm的导管传输到等离子喷枪口的注入装置中,注入装置采用50微米小直径导管以直线型射流的方式,将生物活性玻璃液体先驱液直接径向注入等离子火焰中心的高温区域。
调节等离子喷涂功率为24KW,等离子喷枪口与医用金属基底之间的距离为10cm,喷涂次数为5次,生物活性玻璃液体先驱液原料在高温等离子火焰中,经过液体的燃烧、蒸发、快速凝胶、熔融并沉积到作为基底的生物医用钛合金表面形成生物活性玻璃涂层。
实施例2:
首先按照折合成氧化物质量含量SiO245wt%,P2O56wt%,CaO24.5wt%,Na2O 24.5wt%,分别量取正硅酸乙酯(TEOS)、磷酸三乙酯(TEP)、硝酸钙(Ca(NO3)2·4H2O)、硝酸钠(NaNO3),按照摩尔比为TEOS∶EtOH=1∶3,TEOS∶H2O=1∶7分别量取乙醇和去离子水,按照质量比为Ca(NO3)2·4H2O∶H2O=1∶1,NaNO3∶H2O=1∶2,量取去离子水;将量取好的正硅酸乙酯和乙醇混合并置于磁力搅拌器上搅拌,调节转速为400转/分,搅拌6min后加入去离子水;加入氨水调节PH值至10,溶液完全浑浊后继续搅拌11min;加入磷酸三乙酯并搅拌6min;将硝酸钙、硝酸钠加入到去离子水中,完全溶解后加入到水解好的悬浮液中,搅拌21min后即制得等离子喷涂所用的生物活性玻璃先驱液。
利于电子蠕动泵作为液体原料传输的动力装置,调节蠕动泵转速为6转/分,将生物活性玻璃先驱液用直径为4mm的导管传输到等离子喷枪口的注入装置中,注入装置采用60微米小直径导管以直线型射流的方式,将生物活性玻璃液体先驱液直接径向注入等离子火焰中心的高温区域。
调节等离子喷涂功率为36KW,等离子喷枪口与医用金属基底之间的距离为12cm,喷涂次数为10次,生物活性玻璃液体先驱液原料在高温等离子火焰中,经过液体的燃烧、蒸发、快速凝胶、熔融并沉积到生物医用钛表面形成生物活性玻璃涂层。
实施例3:
首先按照折合成氧化物质量含量SiO250wt%,P2O55wt%,CaO20wt%,Na2O 20wt%,MgO5wt%,分别量取正硅酸乙酯(TEOS)、磷酸三乙酯(TEP)、硝酸钙(Ca(NO3)2·4H2O)、硝酸钠(NaNO3)、硝酸镁(Mg(NO3)2·6H2O),按照摩尔比为TEOS∶EtOH=1∶4,TEOS∶H2O=1∶6分别量取乙醇和去离子水,按照质量比为Ca(NO3)2·4H2O∶H2O=1∶1,NaNO3∶H2O=1∶1,Mg(NO3)2·6H2O=1∶2,量取去离子水;将量取好的正硅酸乙酯和乙醇混合并置于磁力搅拌器上搅拌,调节转速为450转/分,搅拌7min后加入去离子水;加入硝酸调节PH值至3,溶液完全澄清后继续搅拌12min;加入磷酸三乙酯并搅拌7min;将硝酸钙、硝酸钠、硝酸镁加入到去离子水中,完全溶解后加入到水解好的溶胶中,搅拌22min后即制得等离子喷涂所用的生物活性玻璃先驱液。
利于电子蠕动泵作为液体原料传输的动力装置,调节蠕动泵转速为7转/分,将生物活性玻璃先驱液用直径为5mm的导管传输到等离子喷枪口的注入装置中,注入装置采用70微米小直径导管以直线型射流的方式,将生物活性玻璃液体先驱液直接径向注入等离子火焰中心的高温区域。
调节等离子喷涂功率为40KW,等离子喷枪口与医用金属基底之间的距离为14cm,喷涂次数为15次,生物活性玻璃液体先驱液原料在高温等离子火焰中,经过液体的燃烧、蒸发、快速凝胶、熔融并沉积到生物医用不锈钢表面形成生物活性玻璃涂层。
实施例4:
首先按照折合成氧化物质量含量SiO253.9wt%,P2O51.7wt%,CaO21.8wt%,Na2O22.6wt%,分别量取正硅酸乙酯(TEOS)、磷酸三乙酯(TEP)、硝酸钙(Ca(NO3)2·4H2O)、硝酸钠(NaNO3),按照摩尔比为TEOS∶EtOH=1∶5,TEOS∶H2O=1∶5分别量取乙醇和去离子水,按照质量比为Ca(NO3)2·4H2O∶H2O=1∶2,NaNO3∶H2O=1∶1,量取去离子水;将量取好的正硅酸乙酯和乙醇混合并置于磁力搅拌器上搅拌,调节转速为500转/分,搅拌8min后加入去离子水;加入氨水调节PH值至9,溶液完全浑浊后继续搅拌13min;加入磷酸三乙酯并搅拌8min;将硝酸钙、硝酸钠加入到去离子水中,完全溶解后加入到水解好的悬浮液中,搅拌23min后即制得等离子喷涂所用的生物活性玻璃先驱液。
利于电子蠕动泵作为液体原料传输的动力装置,调节蠕动泵转速为8转/分,将生物活性玻璃先驱液用直径为6mm的导管传输到等离子喷枪口的注入装置中,注入装置采用80微米小直径导管以直线型射流的方式,将生物活性玻璃液体先驱液直接径向注入等离子火焰中心的高温区域。
调节等离子喷涂功率为45KW,等离子喷枪口与医用金属基底之间的距离为16cm,喷涂次数为14次,生物活性玻璃液体先驱液原料在高温等离子火焰中,经过液体的燃烧、蒸发、快速凝胶、熔融并沉积到生物医用钴基合金表面形成生物活性玻璃涂层。
实施例5:
首先按照折合成氧化物质量含量SiO246wt%,P2O51wt%,CaO 27wt%,Na2O 15wt%,MgO7wt%,K2O 4wt%,分别量取正硅酸乙酯(TEOS)、磷酸三乙酯(TEP)、硝酸钙(Ca(NO3)2·4H2O)、硝酸钠(NaNO3)、硝酸镁(Mg(NO3)2·6H2O)、硝酸钾(KNO3),按照摩尔比为TEOS∶EtOH=1∶4,TEOS∶H2O=1∶4分别量取乙醇和去离子水,按照质量比为Ca(NO3)2·4H2O∶H2O=1∶1,NaNO3∶H2O=1∶2,Mg(NO3)2·6H2O=1∶1,KNO3∶H2O=1∶5,量取去离子水;将量取好的正硅酸乙酯和乙醇混合并置于磁力搅拌器上搅拌,调节转速为550转/分,搅拌9min后加入去离子水;加入硝酸调节PH值至1,溶液完全澄清后继续搅拌14min;加入磷酸三乙酯并搅拌9min;将硝酸钙、硝酸钠、硝酸镁、硝酸钾加入到去离子水中,完全溶解后加入到水解好的溶胶中,搅拌24min后即制得等离子喷涂所用的生物活性玻璃先驱液。
利于电子蠕动泵作为液体原料传输的动力装置,调节蠕动泵转速为9转/分,将生物活性玻璃先驱液用直径为7mm的导管传输到等离子喷枪口的注入装置中,注入装置采用90微米小直径导管以直线型射流的方式,将生物活性玻璃液体先驱液直接径向注入等离子火焰中心的高温区域。
调节等离子喷涂功率为50KW,等离子喷枪口与医用金属基底之间的距离为18cm,喷涂次数为13次,生物活性玻璃液体先驱液原料在高温等离子火焰中,经过液体的燃烧、蒸发、快速凝胶、熔融并沉积到生物医用氧化锆陶瓷表面形成生物活性玻璃涂层。
实施例6:
首先按照折合成氧化物质量含量SiO260wt%,P2O54wt%,CaO20wt%,Na2O 16wt%,分别量取正硅酸乙酯(TEOS)、磷酸三乙酯(TEP)、硝酸钙(Ca(NO3)2·4H2O)、硝酸钠(NaNO3),按照摩尔比为TEOS∶EtOH=1∶3,TEOS∶H2O=1∶5分别量取乙醇和去离子水,按照质量比为Ca(NO3)2·4H2O∶H2O=1∶1,NaNO3∶H2O=1∶1,量取去离子水;将量取好的正硅酸乙酯和乙醇混合并置于磁力搅拌器上搅拌,调节转速为600转/分,搅拌10min后加入去离子水;加入氨水调节PH值至11,溶液完全浑浊后继续搅拌15min;加入磷酸三乙酯并搅拌10min;将硝酸钙、硝酸钠加入到去离子水中,完全溶解后加入到水解好的悬浮液中,搅拌25min后即制得等离子喷涂所用的生物活性玻璃先驱液。
利于电子蠕动泵作为液体原料传输的动力装置,调节蠕动泵转速为10转/分,将生物活性玻璃先驱液用直径为8mm的导管传输到等离子喷枪口的注入装置中,注入装置采用100微米小直径导管以直线型射流的方式,将生物活性玻璃液体先驱液直接径向注入等离子火焰中心的高温区域。
调节等离子喷涂功率为55KW,等离子喷枪口与医用金属基底之间的距离为20cm,喷涂次数为12次,生物活性玻璃液体先驱液原料在高温等离子火焰中,经过液体的燃烧、蒸发、快速凝胶、熔融并沉积到生物医用氧化铝陶瓷表面形成生物活性玻璃涂层。
实施例7:
首先按照折合成氧化物质量含量SiO240wt%,P2O52wt%,CaO30wt%,Na2O 25wt%,Al2O33wt%,分别量取正硅酸乙酯(TEOS)、磷酸三乙酯(TEP)、硝酸钙(Ca(NO3)2·4H2O)、硝酸钠(NaNO3)、硝酸铝(Al(NO3)3·9H2O)按照摩尔比为TEOS∶EtOH=1∶2,TEOS∶H2O=1∶6分别量取乙醇和去离子水,按照质量比为Ca(NO3)2·4H2O∶H2O=1∶1,NaNO3∶H2O=1∶1,Al(NO3)3·9H2O∶H2O=1∶2,量取去离子水;将量取好的正硅酸乙酯和乙醇混合并置于磁力搅拌器上搅拌,调节转速为650转/分,搅拌9min后加入去离子水;或者加入硝酸调节PH值至1,溶液完全澄清后继续搅拌16min;加入磷酸三乙酯并搅拌9min;将硝酸钙、硝酸钠、硝酸铝加入到去离子水中,完全溶解后加入到水解好的溶胶中,搅拌26min后即制得等离子喷涂所用的生物活性玻璃先驱液。
利于电子蠕动泵作为液体原料传输的动力装置,调节蠕动泵转速为12转/分,将生物活性玻璃先驱液用直径为7mm的导管传输到等离子喷枪口的注入装置中,注入装置采用120微米小直径导管以直线型射流的方式,将生物活性玻璃液体先驱液直接径向注入等离子火焰中心的高温区域。
调节等离子喷涂功率为60KW,等离子喷枪口与医用金属基底之间的距离为21cm,喷涂次数为11次,生物活性玻璃液体先驱液原料在高温等离子火焰中,经过液体的燃烧、蒸发、快速凝胶、熔融并沉积到生物医用钛表面形成生物活性玻璃涂层。
实施例8:
首先按照折合成氧化物质量含量SiO230wt%,P2O540wt%,CaO26wt%,MgO 3wt%,CaF21wt%分别量取正硅酸乙酯(TEOS)、磷酸三乙酯(TEP)、硝酸钙(Ca(NO3)2·4H2O)、硝酸镁(Mg(NO3)2·6H2O)、氟化铵(NH4F),按照摩尔比为TEOS∶EtOH=1∶3,TEOS∶H2O=1∶7分别量取乙醇和去离子水,按照质量比为Ca(NO3)2·4H2O∶H2O=1∶1,Mg(NO3)2·6H2O=1∶2,NH4F∶H2O=1∶2量取去离子水;将量取好的正硅酸乙酯和乙醇混合并置于磁力搅拌器上搅拌,调节转速为700转/分,搅拌8min后加入去离子水;加入氨水调节PH值至9,溶液完全浑浊后继续搅拌17min;加入磷酸三乙酯并搅拌8min;将硝酸钙、硝酸镁、氟化铵加入到去离子水中,完全溶解后加入到水解好的悬浮液中,搅拌27min后即制得等离子喷涂所用的生物活性玻璃先驱液。
利于电子蠕动泵作为液体原料传输的动力装置,调节蠕动泵转速为14转/分,将生物活性玻璃先驱液用直径为6mm的导管传输到等离子喷枪口的注入装置中,注入装置采用140微米小直径导管以直线型射流的方式,将生物活性玻璃液体先驱液直接径向注入等离子火焰中心的高温区域。
调节等离子喷涂功率为35KW,等离子喷枪口与医用金属基底之间的距离为23cm,喷涂次数为9次,生物活性玻璃液体先驱液原料在高温等离子火焰中,经过液体的燃烧、蒸发、快速凝胶、熔融并沉积到医用生物医用钛合金表面形成生物活性玻璃涂层。
实施例9:
首先按照折合成氧化物质量含量SiO234wt%,P2O516.2wt%,CaO44.7wt%,MgO4.6wt%,CaF20.5wt%分别量取正硅酸乙酯(TEOS)、磷酸三乙酯(TEP)、硝酸钙(Ca(NO3)2·4H2O)、硝酸镁(Mg(NO3)2·6H2O)、氟化铵(NH4F),按照摩尔比为TEOS∶EtOH=1∶4,TEOS∶H2O=1∶8分别量取乙醇和去离子水,按照质量比为Ca(NO3)2·4H2O∶H2O=1∶1,Mg(NO3)2·6H2O=1∶1,NH4F∶H2O=1∶2量取去离子水;将量取好的正硅酸乙酯和乙醇混合并置于磁力搅拌器上搅拌,调节转速为650转/分,搅拌7min后加入去离子水;或者加入硝酸调节PH值至2,溶液完全澄清后继续搅拌18min;加入磷酸三乙酯并搅拌7min;将硝酸钙、硝酸镁、氟化铵加入到去离子水中,完全溶解后加入到水解好的溶胶中,搅拌28min后即制得等离子喷涂所用的生物活性玻璃先驱液。
利用电子蠕动泵作为液体原料传输的动力装置,调节蠕动泵转速为16转/分,将生物活性玻璃先驱液用直径为5mm的导管传输到等离子喷枪口的注入装置中,注入装置采用160微米小直径导管以直线型射流的方式,将生物活性玻璃液体先驱液直接径向注入等离子火焰中心的高温区域。
调节等离子喷涂功率为38KW,等离子喷枪口与医用金属基底之间的距离为25cm,喷涂次数为8次,生物活性玻璃液体先驱液原料在高温等离子火焰中,经过液体的燃烧、蒸发、快速凝胶、熔融并沉积到生物医用不锈钢表面形成生物活性玻璃涂层。
实施例10:
首先按照折合成氧化物质量含量SiO240wt%,P2O510wt%,CaO30wt%,Na2O 5wt%,MgO3wt%,K2O 2wt%,分别量取正硅酸乙酯(TEOS)、磷酸三乙酯(TEP)、硝酸钙(Ca(NO3)2·4H2O)、硝酸钠(NaNO3)、硝酸镁(Mg(NO3)2·6H2O)、硝酸铝(Al(NO3)3·9H2O)、硝酸钾(KNO3)、氟化铵(NH4F),按照摩尔比为TEOS∶EtOH=1∶5,TEOS∶H2O=1∶7分别量取乙醇和去离子水,按照质量比为Ca(NO3)2·4H2O∶H2O=1∶1,NaNO3∶H2O=1∶2,Mg(NO3)2·6H2O=1∶2,KNO3∶H2O=1∶3,量取去离子水;将量取好的正硅酸乙酯和乙醇混合并置于磁力搅拌器上搅拌,调节转速为600转/分,搅拌6min后加入去离子水;加入氨水调节PH值至10,溶液完全浑浊后继续搅拌19min;加入磷酸三乙酯并搅拌6min;将硝酸钙、硝酸钠、硝酸镁、硝酸钾加入到去离子水中,完全溶解后加入到水解好的悬浮液中,搅拌29min后即制得等离子喷涂所用的生物活性玻璃先驱液。
利于电子蠕动泵作为液体原料传输的动力装置,调节蠕动泵转速为18转/分,将生物活性玻璃先驱液用直径为4mm的导管传输到等离子喷枪口的注入装置中,注入装置采用180微米小直径导管以直线型射流的方式,将生物活性玻璃液体先驱液直接径向注入等离子火焰中心的高温区域。
调节等离子喷涂功率为42KW,等离子喷枪口与医用金属基底之间的距离为11cm,喷涂次数为7次,生物活性玻璃液体先驱液原料在高温等离子火焰中,经过液体的燃烧、蒸发、快速凝胶、熔融并沉积到生物医用钴基合金表面形成生物活性玻璃涂层。
实施例11:
首先按照折合成氧化物质量含量SiO244.3wt%,P2O511.2wt%,CaO31.9wt%,Na2O4.6wt%,MgO 2.8wt%,K2O 0.2wt%,CaF25wt%分别量取正硅酸乙酯(TEOS)、磷酸三乙酯(TEP)、硝酸钙(Ca(NO3)2·4H2O)、硝酸钠(NaNO3)、硝酸镁(Mg(NO3)2·6H2O)、硝酸钾(KNO3)、氟化铵(NH4F),按照摩尔比为TEOS∶EtOH=1∶4,TEOS∶H2O=1∶6分别量取乙醇和去离子水,按照质量比为Ca(NO3)2·4H2O∶H2O=1∶1,NaNO3∶H2O=1∶2,Mg(NO3)2·6H2O=1∶1,KNO3∶H2O=1∶5,NH4F∶H2O=1∶1量取去离子水;将量取好的正硅酸乙酯和乙醇混合并置于磁力搅拌器上搅拌,调节转速为550转/分,搅拌5min后加入去离子水;加入硝酸调节PH值至3,溶液完全澄清后继续搅拌20min;加入磷酸三乙酯并搅拌5min;将硝酸钙、硝酸钠、硝酸镁、硝酸钾、氟化铵加入到去离子水中,完全溶解后加入到水解好的溶胶中,搅拌30min后即制得等离子喷涂所用的生物活性玻璃先驱液。
利于电子蠕动泵作为液体原料传输的动力装置,调节蠕动泵转速为20转/分,将生物活性玻璃先驱液用直径为3mm的导管传输到等离子喷枪口的注入装置中,注入装置采用200微米小直径导管以直线型射流的方式,将生物活性玻璃液体先驱液直接径向注入等离子火焰中心的高温区域。
调节等离子喷涂功率为30KW,等离子喷枪口与医用金属基底之间的距离为13cm,喷涂次数为6次,生物活性玻璃液体先驱液原料在高温等离子火焰中,经过液体的燃烧、蒸发、快速凝胶、熔融并沉积到生物医用氧化锆陶瓷表面形成生物活性玻璃涂层。
实施例12:
首先按照折合成氧化物质量含量SiO235wt%,P2O57wt%,CaO20wt%,Na2O 15wt%,K2O8wt%,CaF215wt%分别量取正硅酸乙酯(TEOS)、磷酸三乙酯(TEP)、硝酸钙(Ca(NO3)2·4H2O)、硝酸钠(NaNO3)、硝酸钾(KNO3)、氟化铵(NH4F),按照摩尔比为TEOS∶EtOH=1∶3,TEOS∶H2O=1∶5分别量取乙醇和去离子水,按照质量比为Ca(NO3)2·4H2O∶H2O=1∶2,NaNO3∶H2O=1∶1,KNO3∶H2O=1∶4,NH4F∶H2O=1∶2量取去离子水;将量取好的正硅酸乙酯和乙醇混合并置于磁力搅拌器上搅拌,调节转速为500转/分,搅拌6min后加入去离子水;加入氨水调节PH值至11,溶液完全浑浊后继续搅拌15min;加入磷酸三乙酯并搅拌6min;将硝酸钙、硝酸钠、硝酸钾、氟化铵加入到去离子水中,完全溶解后加入到水解好的悬浮液中,搅拌29min后即制得等离子喷涂所用的生物活性玻璃先驱液。
利于电子蠕动泵作为液体原料传输的动力装置,调节蠕动泵转速为17转/分,将生物活性玻璃先驱液用直径为4mm的导管传输到等离子喷枪口的注入装置中,注入装置采用110微米小直径导管以直线型射流的方式,将生物活性玻璃液体先驱液直接径向注入等离子火焰中心的高温区域。
调节等离子喷涂功率为48KW,等离子喷枪口与医用金属基底之间的距离为15cm,喷涂次数为5次,生物活性玻璃液体先驱液原料在高温等离子火焰中,经过液体的燃烧、蒸发、快速凝胶、熔融并沉积到生物医用氧化铝陶瓷形成生物活性玻璃涂层。
实施例13
将实施例2制备的生物活性玻璃涂层在扫描电镜(SEM)下观察,结果表明涂层均匀,致密牢固,涂层厚度达100~300μm。(100倍SEM图像见图2,100000倍SEM图像见图3)。
将实施例2制备的生物活性玻璃涂层在人体模拟体液(SBF)中浸泡7天后再在SEM下进行观察(见图4),图像显示浸泡7天后,生物活性玻璃涂层表面被大量的羟基磷灰石(HA)晶体覆盖,这说明用这种液相等离子喷涂法制得的生物活性玻璃涂层具有较高的生物活性;
将实施例2制备的生物活性玻璃涂层进行X射线衍射(XRD)分析(XRD图谱见图5);图谱中除了基底材料钛(Ti)的结晶峰外,无其他结晶峰出现,表明涂层主要是由无定形相组成;
将实施例2制备的生物活性玻璃涂层在SBF中浸泡7天后再在XRD下观察(XRD图谱见图6);图谱中除了基底材料Ti的结晶相,还出现了很多羟基磷灰石(HA)的结晶相,这与SEM图像相符,进一步说明用这种液相等离子喷涂法制得的生物活性玻璃涂层具有较高的生物活性。
Claims (4)
1.一种制备生物活性玻璃涂层的方法,其特征在于包括以下步骤:
a、准备液态生物活性玻璃先驱液;
b、使用液态生物活性玻璃先驱液进行等离子喷涂,沉积到作为基底的生物医用材料的表面形成生物活性玻璃涂层;
所述步骤a中的液态生物活性玻璃先驱液由以下配比的组分组成:
按折合成氧化物质量含量为SiO2 30~60wt%,P2O5 1~40wt%,CaO 20~45wt%,Na2O 0~25wt%,MgO 0~20wt%,Al2O3 0~3wt%,K2O 0~8wt%,CaF2 0~15wt%分别量取硅源、磷源、钙源、钠源、镁源、铝源、钾源、氟源;
按照摩尔比为硅源∶乙醇=1∶2~5,硅源∶H2O=1∶4~8分别量取乙醇和去离子水;
按照质量比为钙源∶H2O=1∶1~2,钠源∶H2O=1∶1~2,镁源∶H2O=1∶1~2,铝源∶H2O=1∶1.5~2,钾源∶H2O=1∶3~5,氟源∶H2O=1∶1~2分别量取去离子水;
所述步骤a中的液态生物活性玻璃先驱液按下述方法制备而成:
①将量取好的硅源和乙醇混合并搅拌均匀,然后加入去离子水;
②调节pH值至1~3,硅源水解形成溶胶,溶液完全澄清后搅拌均匀;
③加入磷源并搅拌均匀;
④将钙源、钠源、镁源、铝源、钾源和氟源分别加入到去离子水中,完全溶解后加入到水解好的溶胶中,搅拌均匀后即制得热喷涂所用的生物活性玻璃酸性先驱液。
或者,步骤a中所述的生物活性玻璃先驱液按下述方法制备而成:
①将量取好的硅源和乙醇混合并搅拌均匀,然后加入去离子水;
②调节pH值至9~11,硅源水解形成悬浮液,溶液完全浑浊后搅拌均匀;
③加入磷源并搅拌均匀;
④将钙源、钠源、镁源、铝源、钾源和氟源分别加入到去离子水中,完全溶解后加入到水解好的悬浮液中,搅拌均匀后即制得热喷涂所用的生物活性玻璃碱性先驱液;
所述步骤b中等离子喷涂的生物活性玻璃液体先驱液原料用50~200微米小直径导管以直线型射流的方式,直接径向注入等离子火焰中心的高温区域;等离子喷枪口与作为基底的生物医用材料表面之间的距离为10~25cm;等离子喷涂的功率为24~60KW。
2.根据权利要求1所述的制备生物活性玻璃涂层的方法,其特征在于:所述硅源为正硅酸乙酯、三甲基硅醇、三乙基硅醇或四氯化硅中的至少一种;
所述磷源为磷酸三乙酯、磷酸钙、磷酸钠、磷酸氢钙、磷酸氢钠、磷酸钾或磷酸氢钾中的至少一种;
所述钙源为硝酸钙、氯化钙、碳酸氢钙、硫酸钙、硫酸氢钙、磷酸钙或磷酸氢钙中的至少一种;
所述钠源为硝酸钠、氯化钠、碳酸钠、碳酸氢钠、硫酸钠、硫酸氢钠、磷酸钠或磷酸氢钠中的至少一种;
所述镁源为硝酸镁、氯化镁、碳酸氢镁、硫酸镁或硫酸氢镁中的至少一种;
所述铝源为硝酸铝、氯化铝、硫酸铝或硫酸氢铝中的至少一种;
所述钾源为硝酸钾,氯化钾,碳酸钾,碳酸氢钾,硫酸钾,硫酸氢钾,氯酸钾,次氯酸钾,磷酸钾或磷酸氢钾中的至少一种;
所述氟源为氟化铵、氟化氢铵或氟化氢中的至少一种。
3.根据权利要求2任一项所述的制备生物活性玻璃涂层的方法,其特征在于:所述硅源为正硅酸乙酯;所述磷源为磷酸三乙酯;所述钙源为硝酸钙;所述钠源为硝酸钠;所述镁源为硝酸镁;所述铝源为硝酸铝;所述钾源为硝酸钾;所述氟源为氟化铵。
4.根据权利要求1所述的制备生物活性玻璃涂层的方法,其特征在于:所述的作为基底的生物医用材料为生物医用钛、生物医用钛合金、生物医用不锈钢、生物医用钴基合金、生物医用陶瓷材料、含金属的生物医用复合材料或含陶瓷的生物医用复合材料。
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US10207312B2 (en) | 2010-06-14 | 2019-02-19 | Ati Properties Llc | Lubrication processes for enhanced forgeability |
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CN106904962B (zh) * | 2017-02-28 | 2020-05-22 | 华南理工大学 | 一种生物活性氧化锆牙科陶瓷材料的制备方法 |
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US20200299845A1 (en) * | 2019-03-21 | 2020-09-24 | University Of Connecticut | Coated combustion component from liquid precursor thermal spraying |
CN110484028B (zh) * | 2019-06-27 | 2020-11-10 | 浙江大学 | 一种光催化抑菌防污的无机防腐涂层及其涂覆方法 |
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