CN103705977B - Containing doping type hydroxyapatite coating layer carbon/carbon compound material and preparation method thereof - Google Patents
Containing doping type hydroxyapatite coating layer carbon/carbon compound material and preparation method thereof Download PDFInfo
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- CN103705977B CN103705977B CN201310753100.7A CN201310753100A CN103705977B CN 103705977 B CN103705977 B CN 103705977B CN 201310753100 A CN201310753100 A CN 201310753100A CN 103705977 B CN103705977 B CN 103705977B
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- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 103
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 101
- 239000000463 material Substances 0.000 title claims abstract description 99
- 150000001722 carbon compounds Chemical class 0.000 title claims abstract description 86
- 229910052588 hydroxylapatite Inorganic materials 0.000 title claims abstract description 76
- 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 76
- 239000011247 coating layer Substances 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 239000011248 coating agent Substances 0.000 claims abstract description 44
- 238000000576 coating method Methods 0.000 claims abstract description 44
- 150000002500 ions Chemical class 0.000 claims abstract description 36
- 238000010335 hydrothermal treatment Methods 0.000 claims abstract description 30
- 238000010438 heat treatment Methods 0.000 claims abstract description 29
- FUFJGUQYACFECW-UHFFFAOYSA-L calcium hydrogenphosphate Chemical compound [Ca+2].OP([O-])([O-])=O FUFJGUQYACFECW-UHFFFAOYSA-L 0.000 claims abstract description 26
- 235000019700 dicalcium phosphate Nutrition 0.000 claims abstract description 26
- 239000002019 doping agent Substances 0.000 claims abstract description 22
- 239000012670 alkaline solution Substances 0.000 claims abstract description 15
- 230000006698 induction Effects 0.000 claims abstract description 11
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims abstract description 10
- 208000004434 Calcinosis Diseases 0.000 claims abstract description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 14
- 210000000988 bone and bone Anatomy 0.000 claims description 14
- 238000000151 deposition Methods 0.000 claims description 14
- 229910019142 PO4 Inorganic materials 0.000 claims description 13
- 239000007864 aqueous solution Substances 0.000 claims description 13
- 159000000007 calcium salts Chemical class 0.000 claims description 13
- 239000010452 phosphate Substances 0.000 claims description 13
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 239000000243 solution Substances 0.000 claims description 12
- 239000011734 sodium Substances 0.000 claims description 10
- 230000008021 deposition Effects 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- 229910052708 sodium Inorganic materials 0.000 claims description 8
- 229910021529 ammonia Inorganic materials 0.000 claims description 7
- 229910052710 silicon Inorganic materials 0.000 claims description 7
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 6
- 230000010355 oscillation Effects 0.000 claims description 6
- 230000008439 repair process Effects 0.000 claims description 6
- 239000000316 bone substitute Substances 0.000 claims description 5
- 239000001110 calcium chloride Substances 0.000 claims description 5
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 5
- 239000012634 fragment Substances 0.000 claims description 5
- 229910000403 monosodium phosphate Inorganic materials 0.000 claims description 5
- 235000019799 monosodium phosphate Nutrition 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 5
- 239000002510 pyrogen Substances 0.000 claims description 5
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 claims description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 4
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 claims description 4
- 229910052731 fluorine Inorganic materials 0.000 claims description 4
- 229910017604 nitric acid Inorganic materials 0.000 claims description 4
- 238000004062 sedimentation Methods 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 3
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 3
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- 239000005365 phosphate glass Substances 0.000 claims description 3
- 229910052700 potassium Inorganic materials 0.000 claims description 3
- 239000005368 silicate glass Substances 0.000 claims description 3
- 229910021293 PO 4 Inorganic materials 0.000 claims description 2
- VSGNNIFQASZAOI-UHFFFAOYSA-L calcium acetate Chemical compound [Ca+2].CC([O-])=O.CC([O-])=O VSGNNIFQASZAOI-UHFFFAOYSA-L 0.000 claims description 2
- 239000001639 calcium acetate Substances 0.000 claims description 2
- 229960005147 calcium acetate Drugs 0.000 claims description 2
- 235000011092 calcium acetate Nutrition 0.000 claims description 2
- 235000011148 calcium chloride Nutrition 0.000 claims description 2
- 229910052746 lanthanum Inorganic materials 0.000 claims description 2
- 229910000402 monopotassium phosphate Inorganic materials 0.000 claims description 2
- 235000019796 monopotassium phosphate Nutrition 0.000 claims description 2
- PJNZPQUBCPKICU-UHFFFAOYSA-N phosphoric acid;potassium Chemical compound [K].OP(O)(O)=O PJNZPQUBCPKICU-UHFFFAOYSA-N 0.000 claims description 2
- 229910052712 strontium Inorganic materials 0.000 claims description 2
- 239000011521 glass Substances 0.000 claims 1
- 238000010791 quenching Methods 0.000 claims 1
- 230000000171 quenching effect Effects 0.000 claims 1
- 239000003153 chemical reaction reagent Substances 0.000 abstract description 10
- 239000002131 composite material Substances 0.000 abstract description 9
- 230000008859 change Effects 0.000 abstract description 3
- 230000002503 metabolic effect Effects 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 230000004060 metabolic process Effects 0.000 description 5
- 231100000252 nontoxic Toxicity 0.000 description 5
- 230000003000 nontoxic effect Effects 0.000 description 5
- 210000001519 tissue Anatomy 0.000 description 5
- 229910052586 apatite Inorganic materials 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 238000001027 hydrothermal synthesis Methods 0.000 description 4
- 229910052698 phosphorus Inorganic materials 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical group 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 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 238000005485 electric heating Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 210000000963 osteoblast Anatomy 0.000 description 3
- 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 description 3
- 238000004506 ultrasonic cleaning Methods 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000004873 anchoring Methods 0.000 description 2
- 230000004071 biological effect Effects 0.000 description 2
- 239000012620 biological material Substances 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- CADZRPOVAQTAME-UHFFFAOYSA-L calcium;hydroxy phosphate Chemical compound [Ca+2].OOP([O-])([O-])=O CADZRPOVAQTAME-UHFFFAOYSA-L 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 239000007943 implant Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 231100000614 poison Toxicity 0.000 description 2
- 230000007096 poisonous effect Effects 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 208000006386 Bone Resorption Diseases 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- 201000010814 Synostosis Diseases 0.000 description 1
- IHTFTOGFXXXQBO-UHFFFAOYSA-B [C+4].[C+4].[C+4].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O Chemical compound [C+4].[C+4].[C+4].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O IHTFTOGFXXXQBO-UHFFFAOYSA-B 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000975 bioactive effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000024279 bone resorption Effects 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 150000001721 carbon Chemical class 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- -1 carboxy apatite Chemical compound 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 230000021615 conjugation Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 229960000935 dehydrated alcohol Drugs 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000005137 deposition process Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000008034 disappearance Effects 0.000 description 1
- 238000003717 electrochemical co-deposition Methods 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 235000012041 food component Nutrition 0.000 description 1
- 239000005417 food ingredient Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000001727 in vivo Methods 0.000 description 1
- 238000001802 infusion Methods 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- GJKFIJKSBFYMQK-UHFFFAOYSA-N lanthanum(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GJKFIJKSBFYMQK-UHFFFAOYSA-N 0.000 description 1
- 239000012567 medical material Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000002135 nanosheet Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
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- Materials For Medical Uses (AREA)
Abstract
The invention discloses a kind of preparation method containing doping type hydroxyapatite coating layer carbon/carbon compound material, induction heating is adopted to deposit calcium hydrogen phosphate coating at surface of carbon/carbon composite, by potassium hydroxide hydrothermal treatment consists, change pure ha coating into, then the bio-vitric added containing dopant ion carries out hydrothermal treatment consists in alkaline solution, obtains containing dopant ion hydroxyapatite coating layer carbon/carbon compound material.The present invention's bio-vitric substitutes chemical reagent and discharges ion needed for osteolith under hydrothermal conditions to adulterate to hydroxyapatite, high performance doping type hydroxyapatite coating layer can be obtained, overcome and directly use chemical reagent to carry out adulterating the bad compatibility and numerous and diverse metabolic problems that bring.
Description
Technical field
The invention belongs to technical field of biological material, particularly one is containing doping type hydroxyapatite coating layer carbon/carbon compound material and preparation method thereof.
Background technology
Hydroxyapatite is that skeleton organizes main component, and after it implants, calcium and the phosphorus material surface that can dissociate is systemically absorbed, and grows the tissue made new advances.Further, hydroxyapatite compared with other bioactive materials, the inorganic salt in its composition, structure and skeleton closer to, have and guide and the regeneration function of induction skeleton and the synostosis ability of raising skeleton; In vivo in non-bone environment, hydroxyapatite still can induce generation and the formation of bone, is one of main coating material of current biomaterial primary study and exploitation.But the fragility of hydroxyapatite limits its application in Bone Defect Repari and alternate material.So when hydroxyapatite is applied to the field of artificial bone, being applied on high tough medical material is the main path expanding its range of application; Wherein, application potential hydroxyapatite being applied to carbon/carbon compound material (C/C) surface is larger.
C/C belongs to bio-inert material, its good biocompatibility, comprehensive mechanical property is excellent, especially its modulus is suitable with skeleton, stress shielding phenomenon can be avoided, and reduce the bone resorption around embedded material, avoid prosthetic loosening, extend the service life of embedded material, reduce the misery that patient is twice replaced.Especially after surface applies hydroxyapatite, not give only the biological activity of C/C, and reduce because friction causes carbon granule to pollute tissue, causes the risk of hepatocarcinoma.Therefore this novel composite has good potentiality in bone implant material application.
But the osteolith in human body is not pure hydroxyapatite.Osteolith is a class non-quantitation ratio, fault of construction type hydroxyapatite, its pattern is nano-sheet, exist in one " tunnel " along six square shafts in structure, cause the hydroxyl ion in it easily to be replaced by other ion, thus contain a small amount of Na, K, Mg, Si, F, CO in apatite
3 2-, citrate plasma.Part calcium ion disappearance during the existence of these ions not only makes osteolith form, also affects the degree of crystallinity of apatite, and then affects the metabolism of bone, stability and mechanical property.In addition, the composition in osteolith, ratio, degree of crystallinity are different and different with age, position, and these changes make skeleton have different functions and performance.Therefore exploitation contains the apatite of doping type ion as Bone Defect Repari and alternate material to be main attack goal in research in recent years.
At present, the method preparing doping type hydroxyapatite coating layer mainly contains three kinds, one, infusion method: after preparing hydroxyapatite coating layer by cathodic electrochemical deposition, hydroxyapatite coating layer is soaked in lanthanum nitrate hexahydrate a period of time, sample is taken out dry, obtain La doped carboxy apatite composite coating; Two, coprecipitation: adopt NH
4h
2pO
4, Ca (NO
3)
2and NaNO
3for raw material, with the standby hydroxyapatite coating layer mixing sodium form of electrochemical co-deposition legal system; Three, hydro-thermal method: adopt sodium silicate as raw material, carbon containing/carbonate hydroxyapatite coating is carried out hydrothermal treatment consists, obtains hydroxyapatite that is siliceous, sodium ion.But above-mentioned three kinds of methods are all using chemical reagent as doped raw material to obtain doped hydroxyapatite.In these reagent, part is poisonous to skeleton, or these reagent are except containing except dopant ion, also attach other ion, add subsequent treatment, even bring the serious problems of biocompatibility.
Summary of the invention
The object of the invention is to the above-mentioned deficiency overcoming prior art, there is provided a kind of containing doping type hydroxyapatite coating layer carbon/carbon compound material preparation method, using solve in prior art due to adopt chemical reagent to cause as doped raw material poisonous, be doped with foreign ion and increase the process of subsequent treatment, the problem of poor biocompatibility.
Another object of the present invention is to provide a kind of non-toxic and safe, be easy to metabolism and biocompatibility good containing doping type hydroxyapatite coating layer carbon/carbon compound material.
Another object of the present invention is to provide a kind of and be used as bone repair and bone replacement material containing doping type hydroxyapatite coating layer carbon/carbon compound material.
In order to realize foregoing invention object, technical scheme of the present invention is as follows:
Containing a preparation method for the carbon/carbon compound material of doping type hydroxyapatite coating layer, comprise the steps:
Carbon/carbon compound material is placed in salpeter solution and carries out room temperature process, the time is 5 ~ 10 minutes, and wherein, described carbon/carbon compound material should be immersed in concentrated nitric acid;
Carbon/carbon compound material after above-mentioned hydrothermal treatment consists is placed in the mixed aqueous solution containing calcium salt and dihydric phosphate of flowing, the flow velocity of described mixed aqueous solution is 200ml/min ~ 2L/min, and sedimentation time is 15 minutes ~ 2 hours, and temperature is 100 ~ 200 DEG C; Eddy-current heating, described eddy-current heating is by induction heating power pyrogenicity, the frequency of oscillation of described induction heating power is 1KHz ~ 400KHz, output is 0.1KW ~ 10KW, its surface deposition is made to go out calcium hydrogen phosphate coating, wherein, above-mentioned calcium salt is 0.5 ~ 1:0.3 ~ 0.6 with the mole ratio of dihydric phosphate;
The above-mentioned carbon/carbon compound material depositing calcium hydrogen phosphate coating is placed in the first alkaline solution and carries out hydrothermal treatment consists, the time is 24 ~ 96 hours, and temperature is 100 ~ 220 DEG C, obtains the carbon/carbon compound material of hydroxyl apatite coating; Wherein, described in deposit calcium hydrogen phosphate coating carbon/carbon compound material should be immersed in alkali liquor completely, its volume ratio is 50 ~ 10:1;
The carbon/carbon compound material of above-mentioned hydroxyl apatite coating is placed in the second alkaline solution with the bio-vitric containing dopant ion and carries out hydrothermal treatment consists, temperature is 100 ~ 220 DEG C, time is 24 ~ 96 hours, described bio-vitric is at least one in silicate glass, phosphate glass, obtains above-mentioned containing doping type hydroxyapatite coating layer carbon/carbon compound material.
And, a kind of containing doping type hydroxyapatite coating layer carbon/carbon compound material, prepared by the preparation method of above-mentioned doping type hydroxyapatite coating layer carbon/carbon compound material.
And the above-mentioned doping type hydroxyapatite coating layer carbon/carbon compound material that contains is applied to bone repair and bone replacement material field.
The present invention adopts induction heating to deposit calcium hydrogen phosphate coating at surface of carbon/carbon composite containing the preparation method of doping type hydroxyapatite coating layer carbon/carbon compound material, by alkaline solution hydrothermal treatment consists, change pure ha coating into, then the bio-vitric added containing dopant ion carries out hydrothermal treatment consists in alkaline solution, obtains containing dopant ion hydroxyapatite coating layer carbon/carbon compound material.The present invention's bio-vitric substitutes chemical reagent and discharges ion needed for osteolith under hydrothermal conditions to adulterate to hydroxyapatite, high performance dopant ion hydroxyapatite coating layer can be obtained, overcome and directly use chemical reagent to carry out the adulterate bad compatibility brought and the problem increasing subsequent treatment owing to being doped with foreign ion.
Of the present invention containing dopant ion hydroxyapatite coating layer carbon/carbon compound material non-toxic and safe, be easy to metabolism, with organism there is the good compatibility, can be applicable to the hard tissue such as bone repair and bone replacement material Material Field.
Accompanying drawing explanation
Below in conjunction with drawings and Examples, the invention will be further described, in accompanying drawing:
Fig. 1 is the process flow diagram that the embodiment of the present invention contains the preparation method of doping type hydroxyapatite coating layer carbon/carbon compound material;
Fig. 2 is the HA coating surface Calvarial osteoblast adhesion figure after Na, Si that adulterates in example 2 of the present invention.
Detailed description of the invention
In order to make the technical problem to be solved in the present invention, technical scheme and beneficial effect clearly understand, below in conjunction with embodiment and accompanying drawing, the present invention is further elaborated.Should be appreciated that specific embodiment described herein only in order to explain the present invention, be not intended to limit the present invention.
The embodiment of the present invention provides a kind of non-toxic and safe, be easy to that metabolism and the good condition of biocompatibility easily control containing doping type hydroxyapatite coating layer carbon/carbon compound material preparation method, comprise the steps:
S01: carbon/carbon compound material is immersed in salpeter solution and carries out room temperature process, the time is 5min-10min;
S02: the mixed aqueous solution containing calcium salt and the dihydric phosphate carbon/carbon compound material after hydrothermal treatment consists in step S01 being placed in flowing, eddy-current heating, make its surface deposition go out calcium hydrogen phosphate coating, wherein calcium salt is 0.5 ~ 1:0.3 ~ 0.6 with the mole ratio of dihydric phosphate;
S03: the carbon/carbon compound material depositing calcium hydrogen phosphate coating obtained in step S02 is placed in alkaline solution and carries out hydrothermal treatment consists, obtain the carbon/carbon compound material of hydroxyl apatite coating; Wherein, described in deposit calcium hydrogen phosphate coating carbon/carbon compound material should be immersed in alkali liquor completely, its volume ratio is 50 ~ 10:1.
S04: the carbon/carbon compound material of the hydroxyl apatite coating obtained in step S03 is placed in alkaline solution with the bio-vitric material containing dopant ion and carries out hydrothermal treatment consists, obtains above-mentioned containing dopant ion hydroxyapatite coating layer carbon/carbon compound material.
Particularly, in above-mentioned steps S01, carbon/carbon compound material is block, and preferred diameter is the carbon/carbon compound material of 12*12mm.In this preferred carbon/carbon compound material, carbon element content is higher than 99%, and density is low, has extremely strong affinity, and wear resistance is good, and has excellent biocompatibility, its biomechanical property, as very close with skeleton in elastic modelling quantity etc.Further, above-mentioned strong acid solution is concentrated nitric acid, all selects commercially available product.Adopt this preferred strong acid solution to carry out surface treatment to above-mentioned carbon/carbon compound material, make the c h bond of surface of carbon/carbon composite be oxidized to oxygen-containing functional group, contribute to making the calcium hydrogen phosphate of subsequent deposition to be evenly distributed, granule is more tiny.In a preferred embodiment, the volume of this carbon/carbon compound material and nitric acid is preferably 1:5.
In this step S01, before carrying out hydrothermal treatment consists, also comprise the step of a cleaning, drying: above-mentioned carbon/carbon compound material is placed in deionized water, acetone or dehydrated alcohol ultrasonic cleaning, then dries.
In this step S01, the reaction of hydrothermal treatment consists can be carried out in water heating kettle, and the response time is 24 ~ 96 hours, and temperature is 100 ~ 220 DEG C, preferably hydro-thermal reaction 24 hours at 140 DEG C.
Particularly, in above-mentioned steps S02, first the carbon/carbon compound material after complete for step S01 hydrothermal treatment consists is taken out and be placed in distilled water ultrasonic waves for cleaning, oven dry; Then be placed in the mixed aqueous solution eddy-current heating containing calcium salt and dihydric phosphate that flow velocity is 200ml/min ~ 2L/min, at 100 ~ 200 DEG C, deposit 15 minutes ~ 2 hours, deposit calcium hydrogen phosphate coating; Being preferably at flow velocity is eddy-current heating in the above-mentioned mixed aqueous solution of 1ml/min, at 170 DEG C, deposit 15 minutes.Further, the step of above-mentioned eddy-current heating is by induction heating power pyrogenicity, and arranging frequency of oscillation is 1KHz ~ 400KHz, and output is 0.1KW ~ 10KW; In a preferred embodiment, the frequency of oscillation arranging this eddy-current heating is 280KHz, and output is 0.7KW.This preferred eddy-current heating and deposition process parameters make that the efficiency of heating surface is high, speed is fast, and low consumption environment protection, make the calcium hydrogen phosphate coating conjugation of carbon/carbon compound material and surface deposition better.
In this step S02, above-mentioned calcium salt is at least one in calcium chloride, calcium acetate, lime nitrate, and above-mentioned dihydric phosphate is at least one in sodium dihydrogen phosphate, potassium dihydrogen phosphate, Ammonium biphosphate; This calcium salt is preferably calcium chloride, and dihydric phosphate is preferably Ammonium biphosphate.Further, the above-mentioned mixed aqueous solution containing calcium salt and dihydric phosphate can by mole than be the calcium salt of 0.5 ~ 1:0.3 ~ 0.6, dihydric phosphate and water is uniformly mixed and obtains, also can be mixed to get by the sodium dihydrogen phosphate of molal weight to be the calcium chloride solution of 0.5 ~ 1M and molal weight be 0.3 ~ 0.6M.The mixed aqueous solution of this calcium salt and dihydric phosphate carries out reaction and generates calcium hydrogen phosphate in the condition of eddy-current heating, and better in surface of carbon/carbon composite deposition under flow regime, forms compact calcium hydrogen phosphate coating further.
Particularly, in above-mentioned steps S03, the carbon/carbon compound material depositing calcium hydrogen phosphate coating obtained is taken out, be placed in water heating kettle and be soaked in the first alkaline solution and carry out hydrothermal treatment consists in step S02, react 24 ~ 96 hours at 100 ~ 220 DEG C, be preferably and react 24 hours at 140 DEG C.Further, this first alkaline solution is any one in potassium hydroxide solution, sodium hydroxide solution, ammonia, and pH value is 10 ~ 12; Be preferably the potassium hydroxide solution of 0.01M.At 140 DEG C, the calcium hydrogen phosphate of surface of carbon/carbon composite starts that dehydration occurs and forms hydroxyapatite.In a preferred embodiment, when temperature be 140 DEG C, pH value be 10 time, the purity that calcium hydrogen phosphate changes into hydroxyapatite is the highest, obtains the carbon/carbon compound material of the best hydroxyl apatite coating of effect.This hydroxyapatite coating layer can give surface of carbon/carbon composite biological activity, improves the bond strength of carbon/carbon compound material and surrounding tissue, reduces the generation of free carbon granules; Meanwhile, carbon/carbon compound material has good biocompatibility and biomechanical property, improves the fragility of hydroxyapatite.
Particularly, in above-mentioned steps S04, the bottom of another water heating kettle will be placed in containing the bio-vitric being doped with ion, then being taken out by the carbon/carbon compound material of the hydroxyl apatite coating obtained in step S03 is placed on this bio-vitric, add the second alkaline solution, build kettle cover, carry out hydrothermal treatment consists.This second alkaline solution is any one in potassium hydroxide solution, sodium hydroxide solution, ammonia, and pH value is 10 ~ 12; Be preferably ammonia.The time of this hydrothermal treatment consists is 24 ~ 96 hours, and temperature is 100 ~ 220 DEG C; Be preferably and react 24 hours at 140 DEG C.
In this step S04, above-mentioned bio-vitric is at least one in silicate glass, phosphate glass, is preferably the bio-vitric of silicate or phosphate material.The main component of this bio-vitric is had an appointment 45%Na
2o, 25%CaO, 25%SiO
2with 5%P
2o
5, this food ingredient is bionical, can generate calcium hydroxy phosphate after combination reaction, directly can be combined with body bone tissue, plays that to repair osseous tissue, the effect of recovery, biocompatibility very good, and nontoxic, safety.By the various ion that adulterates as required in this bio-vitric, such as can adulterate La, Sr, Na, K, Mg, Si, F, Ca, PO
4 3-in at least one ion, then hydro-thermal reaction is carried out with the carbon/carbon compound material of above-mentioned hydroxyl apatite coating, calcium hydroxy phosphate can be combined with the carbon/carbon compound material of hydroxyl apatite coating well, is combined by the carbon/carbon compound material of ion doping wherein to hydroxyl apatite coating simultaneously.
In this step S04, after hydro-thermal reaction, also comprise cooling and dry process: by obtain containing after dopant ion hydroxyapatite coating layer carbon/carbon compound material natural cooling, be placed in electric heating bellows, at 120 DEG C dry 20 minutes.
The embodiment of the present invention is containing the preparation method of doping type hydroxyapatite coating layer carbon/carbon compound material, induction heating is adopted to deposit calcium hydrogen phosphate coating at surface of carbon/carbon composite, by alkaline solution hydrothermal treatment consists, change pure ha coating into, then the bio-vitric added containing dopant ion carries out hydrothermal treatment consists in alkaline solution, obtains containing doping type hydroxyapatite coating layer carbon/carbon compound material.The present invention's bio-vitric substitutes chemical reagent and discharges ion needed for osteolith under hydrothermal conditions to adulterate to hydroxyapatite, high performance dopant ion hydroxyapatite coating layer can be obtained, overcome and directly use chemical reagent to carry out the adulterate bad compatibility brought and the problem increasing subsequent treatment owing to being doped with foreign ion.
The embodiment of the present invention containing doping type hydroxyapatite coating layer carbon/carbon compound material non-toxic and safe, be easy to metabolism, with organism there is the good compatibility, can be applicable to the hard tissue such as bone repair and bone replacement material Material Field.
Illustrate above-mentioned containing dopant ion hydroxyapatite coating layer carbon/carbon compound material preparation method below by way of multiple embodiment.
Embodiment 1
A kind of containing doping type hydroxyapatite coating layer carbon/carbon compound material preparation method, comprise the steps:
S11: by diameter
carbon/carbon compound material be placed in water heating kettle, molal weight is that 0.1M salpeter solution carries out hydrothermal treatment consists, then take out, with distilled water ultrasonic cleaning totally and dry;
S12: the carbon/carbon compound material after hydrothermal treatment consists in step S11 is placed in the mixed aqueous solution that flow velocity is 500ml/min, it is the calcium chloride of 0.2M and the sodium dihydrogen phosphate of 0.15M that this mixed aqueous solution comprises molal weight, by induction heating power pyrogenicity carbon/carbon compound material, arrange that frequency of oscillation is 200KHz, output is 0.7KW, make its surface deposition go out calcium hydrogen phosphate coating, sedimentation time is 30min;
S13: the carbon/carbon compound material depositing calcium hydrogen phosphate coating obtained in step S12 is placed in the potassium hydroxide solution that concentration is 0.01M, carries out 24 hours hydrothermal treatment consists at 140 DEG C, and what must deposit calcium hydrogen phosphate coating arrives carbon/carbon compound material;
S14: by obtain in step S13 containing treating that the bio-vitric fragment of dopant ion is placed in bottom water heating kettle, this bio-vitric is the bio-vitric comprising following formula: Na
2o24.5wt%, CaO24.5wt%, P
2o56.0wt%, SiO
245wt%; Then hydroxyapatite coating layer carbon/carbon compound material is placed on this bio-vitric fragment, pours ammonia into, regulates pH to 10, builds kettle cover, is 150 DEG C in temperature, under the time is the condition of 36 hours, carries out hydrothermal treatment consists; After natural cooling, in electric heating bellows dry 20min at 120 DEG C, obtain the carbon/carbon compound material mixing sodium, silicon type hydroxyapatite coating layer; After tested, this anchoring strength of coating reaches critical load 110N, and coating has the good Calvarial osteoblast compatibility, sees Fig. 2
Embodiment 2
A kind of containing dopant ion hydroxyapatite coating layer carbon/carbon compound material preparation method, comprise the steps:
S21: by diameter
carbon/carbon compound material be placed in water heating kettle, molal weight is that 0.1M salpeter solution carries out hydrothermal treatment consists, then take out, with distilled water ultrasonic cleaning totally and dry;
S22: the carbon/carbon compound material after hydrothermal treatment consists in step S21 is placed in the mixed aqueous solution that flow velocity is 500ml/min, it is the calcium chloride of 0.3M and the sodium dihydrogen phosphate of 0.25M that this mixed aqueous solution comprises molal weight, by induction heating power pyrogenicity carbon/carbon compound material, arrange that frequency of oscillation is 300KHz, output is 0.5KW, make its surface deposition go out calcium hydrogen phosphate coating, sedimentation time is 40min;
S23: the carbon/carbon compound material depositing calcium hydrogen phosphate coating obtained in step S22 is placed in the potassium hydroxide solution that concentration is 0.01M, carries out 24 hours hydrothermal treatment consists at 140 DEG C, and what must deposit calcium hydrogen phosphate coating arrives carbon/carbon compound material;
S24: by obtain in step S23 containing treating that the bio-vitric fragment of dopant ion is placed in bottom water heating kettle, this bio-vitric is the bio-vitric comprising following formula: Na
2o4.8wt%, F1.0wt%, MgO2.9wt%, CaO33.4wt%, P
2o
5, 11.7%; Then hydroxyapatite coating layer carbon/carbon compound material is placed on this bio-vitric fragment, pours ammonia into, regulates pH to 10, builds kettle cover, is 200 DEG C in temperature, under the time is the condition of 36 hours, carries out hydrothermal treatment consists; After natural cooling, in electric heating bellows at 120 DEG C dry 28 hours, obtain the carbon/carbon compound material mixing sodium, fluorine, silicon type hydroxyapatite coating layer; After tested, this anchoring strength of coating reaches critical load 105N.As shown in Figure 2, it is the HA coating surface Calvarial osteoblast adhesion figure after being doped with Na, Si.
The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, all any amendments done within the spirit and principles in the present invention, equivalent replacement and improvement etc., all should be included within protection scope of the present invention.
Claims (6)
1., containing a preparation method for the carbon/carbon compound material of doping type hydroxyapatite coating layer, comprise the steps:
Carbon/carbon compound material is placed in salpeter solution and carries out room temperature process, the time is 5 ~ 10 minutes, and wherein, described carbon/carbon compound material should be immersed in concentrated nitric acid;
Carbon/carbon compound material after described hydrothermal treatment consists is placed in the mixed aqueous solution containing calcium salt and dihydric phosphate of flowing, the flow velocity of described mixed aqueous solution is 200ml/min ~ 2L/min, and sedimentation time is 15 minutes ~ 2 hours, and temperature is 100 ~ 200 DEG C; Eddy-current heating, described eddy-current heating is by induction heating power pyrogenicity, the frequency of oscillation of described induction heating power is 1KHz ~ 400KHz, output is 0.1KW ~ 10KW, its surface deposition is made to go out calcium hydrogen phosphate coating, wherein, described calcium salt is 0.5 ~ 1:0.3 ~ 0.6 with the mole ratio of dihydric phosphate;
The described carbon/carbon compound material depositing calcium hydrogen phosphate coating is placed in the first alkaline solution and carries out hydrothermal treatment consists, the time is 24 ~ 96 hours, and temperature is 100 ~ 220 DEG C, obtains the carbon/carbon compound material of hydroxyl apatite coating; Wherein, described in deposit calcium hydrogen phosphate coating carbon/carbon compound material should be immersed in alkali liquor completely, its volume ratio is 50 ~ 10:1;
The carbon/carbon compound material of described hydroxyl apatite coating is placed in the second alkaline solution with the bio-vitric containing dopant ion and carries out hydrothermal treatment consists, pH value is 10 ~ 12, temperature is 100 ~ 220 DEG C, time is 24 ~ 96 hours, described bio-vitric is at least one in silicate glass, phosphate glass, obtain described containing dopant ion hydroxyapatite coating layer carbon/carbon compound material, wherein glass is fragment of quenching, and volume accounts for 1/3 ~ 1/2 of final Treatment Solution.
2. the preparation method of the carbon/carbon compound material containing doping type hydroxyapatite coating layer according to claim 1, is characterized in that: described dopant ion is La, Sr, Na, K, Mg, Si, F, Ca, PO
4 3-in at least one.
3. the preparation method of the carbon/carbon compound material containing doping type hydroxyapatite coating layer according to claim 1, is characterized in that: described first aqueous slkali is any one in potassium hydroxide solution, sodium hydroxide solution, ammonia, and pH value is 10 ~ 12;
Or described second aqueous slkali is any one in potassium hydroxide solution, sodium hydroxide solution, ammonia.
4. the preparation method of the carbon/carbon compound material containing doping type hydroxyapatite coating layer according to claim 1, is characterized in that: described calcium salt is at least one in calcium chloride, calcium acetate, lime nitrate; Described dihydric phosphate is at least one in sodium dihydrogen phosphate, potassium dihydrogen phosphate, Ammonium biphosphate.
5., containing a doping type hydroxyapatite coating layer carbon/carbon compound material, prepared by the preparation method of the carbon/carbon compound material of dopant ion hydroxyapatite coating layer described in Claims 1 to 4.
6. the application of dopant ion hydroxyapatite coating layer carbon/carbon compound material in bone repair and bone replacement material prepared by the preparation method of the carbon/carbon compound material containing doping type hydroxyapatite coating layer described in Claims 1 to 4.
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