CN106007699B - β-磷酸三钙/碳酸钙双相陶瓷材料及其制备方法 - Google Patents
β-磷酸三钙/碳酸钙双相陶瓷材料及其制备方法 Download PDFInfo
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- CN106007699B CN106007699B CN201610349122.0A CN201610349122A CN106007699B CN 106007699 B CN106007699 B CN 106007699B CN 201610349122 A CN201610349122 A CN 201610349122A CN 106007699 B CN106007699 B CN 106007699B
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- calcium carbonate
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- tricalcium phosphate
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- biphase ceramics
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- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 title claims abstract description 80
- 229910000019 calcium carbonate Inorganic materials 0.000 title claims abstract description 40
- 239000000463 material Substances 0.000 title claims abstract description 40
- 239000000919 ceramic Substances 0.000 title claims abstract description 39
- 239000001506 calcium phosphate Substances 0.000 title claims abstract description 29
- 229910000391 tricalcium phosphate Inorganic materials 0.000 title claims abstract description 27
- 229940078499 tricalcium phosphate Drugs 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000000654 additive Substances 0.000 claims abstract description 8
- 230000000996 additive effect Effects 0.000 claims abstract description 8
- 239000005365 phosphate glass Substances 0.000 claims abstract description 7
- 239000000203 mixture Substances 0.000 claims abstract description 5
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 239000011780 sodium chloride Substances 0.000 claims description 10
- 239000012153 distilled water Substances 0.000 claims description 7
- 239000011812 mixed powder Substances 0.000 claims description 7
- 238000005245 sintering Methods 0.000 claims description 7
- 238000010792 warming Methods 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 6
- 239000011734 sodium Substances 0.000 claims description 5
- 238000000465 moulding Methods 0.000 claims description 4
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims description 3
- 239000013078 crystal Substances 0.000 claims description 3
- 229920000126 latex Polymers 0.000 claims description 3
- 238000004080 punching Methods 0.000 claims description 3
- 238000007789 sealing Methods 0.000 claims description 3
- 238000004321 preservation Methods 0.000 claims description 2
- 238000003860 storage Methods 0.000 claims description 2
- 239000011574 phosphorus Substances 0.000 claims 2
- 229910052698 phosphorus Inorganic materials 0.000 claims 2
- 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 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims 1
- 238000005660 chlorination reaction Methods 0.000 claims 1
- 230000002706 hydrostatic effect Effects 0.000 claims 1
- 239000004615 ingredient Substances 0.000 claims 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-N phosphoric acid Substances OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims 1
- 229910052708 sodium Inorganic materials 0.000 claims 1
- 210000000988 bone and bone Anatomy 0.000 abstract description 26
- 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 abstract description 23
- 230000015556 catabolic process Effects 0.000 abstract description 10
- 238000006731 degradation reaction Methods 0.000 abstract description 10
- 230000007547 defect Effects 0.000 abstract description 5
- 230000002188 osteogenic effect Effects 0.000 abstract description 4
- 238000006467 substitution reaction Methods 0.000 abstract description 4
- 239000012620 biological material Substances 0.000 abstract description 3
- 230000012010 growth Effects 0.000 abstract description 3
- 238000006065 biodegradation reaction Methods 0.000 abstract description 2
- 229910052588 hydroxylapatite Inorganic materials 0.000 description 9
- 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 description 9
- 239000012071 phase Substances 0.000 description 9
- 229910019142 PO4 Inorganic materials 0.000 description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 6
- 239000010452 phosphate Substances 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 239000011521 glass Substances 0.000 description 5
- 239000011148 porous material Substances 0.000 description 5
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 4
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 4
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 229910010293 ceramic material Inorganic materials 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000009766 low-temperature sintering Methods 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 229910000389 calcium phosphate Inorganic materials 0.000 description 2
- 235000011010 calcium phosphates Nutrition 0.000 description 2
- 229960000935 dehydrated alcohol Drugs 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000000499 gel Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000010791 quenching Methods 0.000 description 2
- 230000000171 quenching effect Effects 0.000 description 2
- 235000010344 sodium nitrate Nutrition 0.000 description 2
- 239000004317 sodium nitrate Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- QKNYBSVHEMOAJP-UHFFFAOYSA-N 2-amino-2-(hydroxymethyl)propane-1,3-diol;hydron;chloride Chemical compound Cl.OCC(N)(CO)CO QKNYBSVHEMOAJP-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 102000008186 Collagen Human genes 0.000 description 1
- 108010035532 Collagen Proteins 0.000 description 1
- 206010013786 Dry skin Diseases 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 239000003462 bioceramic Substances 0.000 description 1
- 239000005312 bioglass Substances 0.000 description 1
- 210000002449 bone cell Anatomy 0.000 description 1
- 239000002639 bone cement Substances 0.000 description 1
- 230000008468 bone growth Effects 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000024245 cell differentiation Effects 0.000 description 1
- 229920001436 collagen Polymers 0.000 description 1
- 238000005056 compaction Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- JRBPAEWTRLWTQC-UHFFFAOYSA-N dodecylamine Chemical compound CCCCCCCCCCCCN JRBPAEWTRLWTQC-UHFFFAOYSA-N 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000000703 high-speed centrifugation Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 210000004409 osteocyte Anatomy 0.000 description 1
- 230000002138 osteoinductive effect Effects 0.000 description 1
- 229920000747 poly(lactic acid) Polymers 0.000 description 1
- 239000004626 polylactic acid Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229910052573 porcelain Inorganic materials 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 210000000130 stem cell Anatomy 0.000 description 1
- -1 β-TCP compound Chemical class 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/447—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on phosphates, e.g. hydroxyapatite
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61F—FILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
- A61F2/00—Filters implantable into blood vessels; Prostheses, i.e. artificial substitutes or replacements for parts of the body; Appliances for connecting them with the body; Devices providing patency to, or preventing collapsing of, tubular structures of the body, e.g. stents
- A61F2/02—Prostheses implantable into the body
- A61F2/28—Bones
-
- 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
- C03C3/00—Glass compositions
- C03C3/12—Silica-free oxide glass compositions
- C03C3/16—Silica-free oxide glass compositions containing phosphorus
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/013—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics containing carbon
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
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- C04B38/00—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof
- C04B38/007—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof characterised by the pore distribution, e.g. inhomogeneous distribution of pores
- C04B38/0074—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof characterised by the pore distribution, e.g. inhomogeneous distribution of pores expressed as porosity percentage
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61F—FILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
- A61F2/00—Filters implantable into blood vessels; Prostheses, i.e. artificial substitutes or replacements for parts of the body; Appliances for connecting them with the body; Devices providing patency to, or preventing collapsing of, tubular structures of the body, e.g. stents
- A61F2/02—Prostheses implantable into the body
- A61F2/28—Bones
- A61F2002/2835—Bone graft implants for filling a bony defect or an endoprosthesis cavity, e.g. by synthetic material or biological material
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61F—FILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
- A61F2310/00—Prostheses classified in A61F2/28 or A61F2/30 - A61F2/44 being constructed from or coated with a particular material
- A61F2310/00005—The prosthesis being constructed from a particular material
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- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3205—Alkaline earth oxides or oxide forming salts thereof, e.g. beryllium oxide
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- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3205—Alkaline earth oxides or oxide forming salts thereof, e.g. beryllium oxide
- C04B2235/3208—Calcium oxide or oxide-forming salts thereof, e.g. lime
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- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/44—Metal salt constituents or additives chosen for the nature of the anions, e.g. hydrides or acetylacetonate
- C04B2235/447—Phosphates or phosphites, e.g. orthophosphate or hypophosphite
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- Vascular Medicine (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Animal Behavior & Ethology (AREA)
- Geochemistry & Mineralogy (AREA)
- Heart & Thoracic Surgery (AREA)
- Transplantation (AREA)
- Oral & Maxillofacial Surgery (AREA)
- Cardiology (AREA)
- Orthopedic Medicine & Surgery (AREA)
- Inorganic Chemistry (AREA)
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Abstract
本发明公开了一种β‑磷酸三钙/碳酸钙双相陶瓷材料及其制备方法，属于生物材料领域。该β‑磷酸三钙/碳酸钙双相陶瓷材料由如下按重量百分比计的成分组成：10‑85wt％β‑磷酸三钙、10‑85wt％碳酸钙和5‑30wt％磷酸盐玻璃添加剂。本发明制备的β‑TCP/CC双相陶瓷体系不仅可提高人工骨的早期成骨活性，还能够解决人工骨材料降解速率与骨生长速率不匹配的问题，满足骨缺失修复和骨组织工程的需求。该材料具有优良的生物相容性、引导成骨活性和全生物降解特性，可用于人的骨缺损的修复和替代；通过调节材料的组成和结构，可以调节其生物降解速率，使之与骨组织的生长速度相匹配。
Description
技术领域
本发明属于生物材料技术领域，具体涉及一种β-磷酸三钙/碳酸钙双相陶瓷材料及其制备方法。
背景技术
目前，用于骨修复的产品约有数十种之多，其修复骨缺失的效果各异。除了同种异体骨和异种骨外，人工骨产品主要可归结为以下几种材料：羟基磷灰石(HAP)多孔陶瓷；β-磷酸三钙(β-TCP)多孔陶瓷；β-TCP/HAP双相多孔陶瓷；多孔生物活性玻璃陶瓷；硫酸钙固化体；磷酸钙骨水泥(固化产物以HAP为主晶相)；生物降解高分子材料(如胶原、聚乳酸等)与HAP或β-TCP复合的多孔材料等。近二十年来，随着骨组织工程学的发展，人们逐渐追求可在体内全生物降解，且降解速率与新骨生长速率匹配的骨引导或诱导材料，那些不降解或降解速度太慢或降解速度太快的材料体系在一定程度上受到了局限。由于磷酸钙类多孔陶瓷在组成、结构和力学性能等方面更接近于人体骨组织，且能诱导干细胞向骨细胞分化，因此，受到格外的关注。尤其是鉴于β-TCP/HAP多孔陶瓷良好的生物相容性和骨诱导性，发展了β-TCP/HAP双相多孔陶瓷，并在临床获得了广泛的应用。在这种双相材料中，β-TCP的局部降解引发了骨引、诱导性，HAP相则基本不降解而作为骨细胞粘附和生长的基质，因而获得良好的骨修复效果。但这一材料体系仍有不足之处，就是β-TCP相降解速度较慢，且其中HAP相仍难以降解。目前，临床上广泛使用的材料，如β-TCP多孔陶瓷和硫酸钙固化体均是可完全降解的生物材料，但前者降解速度较缓慢，而后者又降解速度过快。
发明内容
本发明的首要目的在于克服现有技术中的不足，提供一种β-磷酸三钙/碳酸钙双相陶瓷材料。该材料具有优良的生物相容性、引导成骨活性和全生物降解特性，可用于人的骨缺损的修复和替代；通过调节材料的组成和结构(孔结构和分布)，可以调节其生物降解速率，使之与骨组织的生长速度相匹配。
本发明的另一目的在于提供所述的β-磷酸三钙/碳酸钙双相陶瓷材料的制备方法。
本发明的目的通过下述技术方案实现：一种β-磷酸三钙/碳酸钙双相陶瓷材料，由如下按重量百分比计的成分组成：10-85wt％β-磷酸三钙(β-TCP)、10-85wt％碳酸钙(CC)和5-30wt％磷酸盐玻璃添加剂(PBG)。
所述的β-磷酸三钙/碳酸钙双相陶瓷材料具有两种结构：一种是致密型材料，气孔率<10％；另一种是多孔型材料，气孔率≥10％。
所述的β-磷酸三钙(β-TCP)和碳酸钙(CC)的粒径优选为2-8μm。
所述的磷酸盐玻璃添加剂(PBG)为Na2O-CaO-MgO-P2O5系生物玻璃，由如下按重量百分比计的成分组成：10-12wt％Na2O、5-8wt％CaO、1-2wt％MgO和79-81wt％P2O5。所述的Na2O-CaO-MgO-P2O5系生物玻璃可采用“高温熔融-水淬-细化”和“sol-gel法-煅烧-分散”两种工艺制备。
所述的β-磷酸三钙/碳酸钙双相陶瓷材料的制备方法，包括如下步骤：将10-85wt％β-磷酸三钙、10-85wt％碳酸钙和5-30wt％磷酸盐玻璃添加剂混合均匀，加入6-7wt％蒸馏水，混匀，密封存放至水分均匀，得到混合粉体；将氯化钠与所述的混合粉体按体积比5-6.5：5-3.5混合均匀，装入钢模中预压成型，然后装入乳胶袋，抽真空后密封，经200-250MPa的冷等静压成型坯体，脱模后干燥至120℃后置于气氛烧结炉中，以5℃/min的升温速率升温至650℃，保温20-40min后置于蒸馏水中，升温至80℃进行盐析，直至陶瓷中所有的氯化钠晶体全部溶出为止；将经盐析的β-TCP/CC双相生物陶瓷材料干燥至120℃，得到β-磷酸三钙/碳酸钙双相陶瓷材料。
所述的氯化钠的粒径优选为600-800μm。
所述的烧结优选在CO2气体保护下进行。
本发明相对于现有技术具有如下的优点及效果：本发明制备的β-TCP/CC双相陶瓷体系不仅可提高人工骨的早期成骨活性，还能够解决人工骨材料降解速率与骨生长速率不匹配的问题，满足骨缺失修复和骨组织工程的需求。该材料具有优良的生物相容性、引导成骨活性和全生物降解特性，可用于人的骨缺损的修复和替代；通过调节材料的组成和结构(孔结构和分布)，可以调节其生物降解速率，使之与骨组织的生长速度相匹配。
附图说明
图1为实施例3的β-TCP/CC双相陶瓷材料的显微结构示意图；
图2为实施例3的β-TCP/CC双相陶瓷材料的粉体、成型、液相烧结示意图。
具体实施方式
下面结合实施例对本发明作进一步详细的描述，但本发明的实施方式不限于此。
实施例1
磷酸盐生物玻璃低温烧结剂的制备(高温熔融法)
采用Na2O-CaO-MgO-P2O5系磷酸盐生物玻璃(PBG)高温熔融制备，具体步骤如下：
1)配方
组成范围为：Na2O：10-12wt％，CaO：5-8wt％，MgO：1-2wt％，P2O5：79-81wt％。
2)熔融制备
将配好的原料放入瓷研砵中捣碎、研细，过40目筛，然后将过筛粉体放入耐高温瓷坩埚中，置于碳化硅高温炉中，以10℃/min的升温速度升温至1000℃，保温1小时。
3)水淬、细化
将保温1小时的玻璃熔融坩埚从炉中取出，将熔化的玻璃液倒入盛有蒸馏水的搪瓷盆中水淬，然后捞出玻璃熔块，经干燥、研磨和气流粉碎至近亚微米级，得到磷酸盐生物玻璃低温烧结剂。
实施例2
磷酸盐生物玻璃低温烧结剂的制备(溶胶-凝胶法)
制备工艺步骤如下：
1)将一定量的无水乙醇与去离子水均匀混合后加入一定量的十二胺(DDA)，于恒温加热磁力搅拌器中搅拌10min形成混合溶液；
2)往上述溶液中加入磷酸三乙脂(TEP)，搅拌30min；
3)称取一定量的硝酸钙、硝酸钠、硝酸镁溶于一定量的去离子水中，搅拌30min后彻底溶解形成水溶液；
4)将含硝酸钙、硝酸钠、硝酸镁的水溶液缓慢加入悬浊液中，搅拌3h使各组分完成水解、混合均匀；
5)将混合均匀后的乳白色悬浊液静置陈化1d，高速离心后得到白色凝胶沉淀，并用无水乙醇和去离子水反复离心漂洗三遍得到湿的白色沉淀；
6)将湿的白色沉淀在恒温干燥箱中60℃干燥24h得到干的白色沉淀粉末；
7)将干的白色沉淀粉末置于高温炉中，经过550-800℃热处理1-3h，获得球形微纳米生物活性玻璃粉末，即为磷酸盐生物玻璃低温烧结剂。
实施例3-11β-TCP/CC双相生物陶瓷材料的制备
β-磷酸三钙/碳酸钙双相陶瓷材料的制备方法，包括如下步骤：将β-磷酸三钙、碳酸钙和磷酸盐生物玻璃添加剂采用干法球磨混合均匀，加入6-7wt％蒸馏水，混匀，密封存放至水分均匀，得到混合粉体；将氯化钠与所述的混合粉体按体积比6.5：3.5、6：4、5：5混合均匀，装入钢模中预压成型，然后装入乳胶袋，抽真空后密封，经200-250MPa的冷等静压成型坯体，脱模后干燥至120℃后置于气氛烧结炉中，以5℃/min的升温速率升温至650℃，保温20-40min后置于蒸馏水中，升温至80℃进行盐析，直至陶瓷中所有的氯化钠晶体全部溶出为止。将经盐析的β-TCP/CC双相生物陶瓷材料干燥至120℃，得到β-磷酸三钙/碳酸钙双相陶瓷材料。(以下面的实施例3、气孔率50％(氯化钠与所述的混合粉体按体积比5：5混合)的样品为例，陈述放在后面。)
所述的氯化钠的粒径为600-800μm。
所述的烧结在CO2气体保护下进行。
所述的β-磷酸三钙/碳酸钙双相陶瓷材料具有两种结构：一种是致密型材料，气孔率<10％；另一种是多孔型材料，气孔率≥10％。
所述的β-磷酸三钙(β-TCP)和碳酸钙(CC)的粒径为2-8μm。
以实施例3为配方，氯化钠与实施例3配方粉体按体积比5：5混合时，所成型、烧成的样品经检测，其主要性能指标如下：
气孔率：52-55％；
抗压强度：1.2-2MPa；
体外降解性能：试样在Tris-HCl缓冲液(0.05mol/L，25℃)中浸泡30天，质量损失达到2％，而纯β-TCP生物陶瓷的质量损失仅有1％，因此，其体外降解速率已提高一倍。
表1各实施例的β-TCP/CC双相陶瓷的组成配方
上述实施例为本发明较佳的实施方式，但本发明的实施方式并不受上述实施例的限制，其他的任何未背离本发明的精神实质与原理下所作的改变、修饰、替代、组合、简化，均应为等效的置换方式，都包含在本发明的保护范围之内。
Claims (4)
1.一种β-磷酸三钙/碳酸钙双相陶瓷材料，其特征在于，由如下按重量百分比计的成分组成：10-85wt％β-磷酸三钙、10-85wt％碳酸钙和5-30wt％磷酸盐玻璃添加剂；所述的β-磷酸三钙/碳酸钙双相陶瓷材料具有两种结构：一种是致密型材料，气孔率<10％；另一种是多孔型材料，气孔率≥10％；所述的磷酸盐玻璃添加剂为Na2O-CaO-MgO-P2O5系生物玻璃，由如下按重量百分比计的成分组成：10-12wt％Na2O、5-8wt％CaO、1-2wt％MgO和79-81wt％P2O5；所述的β-磷酸三钙/碳酸钙双相陶瓷材料的制备方法，包括如下步骤：将10-85wt％β-磷酸三钙、10-85wt％碳酸钙和5-30wt％磷酸盐玻璃添加剂混合均匀，加入6-7wt％蒸馏水，混匀，密封存放至水分均匀，得到混合粉体；将氯化钠与所述的混合粉体按体积比5-6.5：5-3.5混合均匀，装入钢模中预压成型，然后装入乳胶袋，抽真空后密封，经200-250MPa的冷等静压成型坯体，脱模后干燥至120℃后置于气氛烧结炉中，以5℃/min的升温速率升温至650℃，保温20-40min后置于蒸馏水中，升温至80℃进行盐析，直至陶瓷中所有的氯化钠晶体全部溶出为止；将经盐析的β-磷酸三钙/碳酸钙双相陶瓷材料干燥至120℃，得到β-磷酸三钙/碳酸钙双相陶瓷材料。
2.根据权利要求1所述的β-磷酸三钙/碳酸钙双相陶瓷材料，其特征在于，所述的β-磷酸三钙和碳酸钙的粒径为2-8μm。
3.根据权利要求1所述的β-磷酸三钙/碳酸钙双相陶瓷材料，其特征在于，所述的氯化钠的粒径为600-800μm。
4.根据权利要求1所述的β-磷酸三钙/碳酸钙双相陶瓷材料，其特征在于，所述的烧结在CO2气体保护下进行。
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