CN106747400A - 一种高性能生物陶瓷材料 - Google Patents
一种高性能生物陶瓷材料 Download PDFInfo
- Publication number
- CN106747400A CN106747400A CN201611029218.5A CN201611029218A CN106747400A CN 106747400 A CN106747400 A CN 106747400A CN 201611029218 A CN201611029218 A CN 201611029218A CN 106747400 A CN106747400 A CN 106747400A
- Authority
- CN
- China
- Prior art keywords
- parts
- reaction
- performance
- bioceramic material
- temperature
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000003462 bioceramic Substances 0.000 title claims abstract description 37
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims abstract description 38
- 239000008367 deionised water Substances 0.000 claims abstract description 26
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000002270 dispersing agent Substances 0.000 claims abstract description 25
- 239000004254 Ammonium phosphate Substances 0.000 claims abstract description 19
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims abstract description 19
- 229910052581 Si3N4 Inorganic materials 0.000 claims abstract description 19
- 229910000148 ammonium phosphate Inorganic materials 0.000 claims abstract description 19
- 235000019289 ammonium phosphates Nutrition 0.000 claims abstract description 19
- VTYYLEPIZMXCLO-UHFFFAOYSA-L calcium carbonate Substances [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims abstract description 19
- 229910000019 calcium carbonate Inorganic materials 0.000 claims abstract description 19
- 239000001110 calcium chloride Substances 0.000 claims abstract description 19
- 229910001628 calcium chloride Inorganic materials 0.000 claims abstract description 19
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 235000019353 potassium silicate Nutrition 0.000 claims abstract description 19
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims abstract description 19
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000002360 preparation method Methods 0.000 claims abstract description 15
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000002002 slurry Substances 0.000 claims description 36
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- 239000007789 gas Substances 0.000 claims description 14
- 238000002390 rotary evaporation Methods 0.000 claims description 13
- 238000005273 aeration Methods 0.000 claims description 8
- 238000001704 evaporation Methods 0.000 claims description 8
- 239000000725 suspension Substances 0.000 claims description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 7
- 125000004122 cyclic group Chemical group 0.000 claims description 7
- 230000008020 evaporation Effects 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- 210000002966 serum Anatomy 0.000 claims description 7
- 150000001336 alkenes Chemical class 0.000 claims 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 claims 1
- 238000003756 stirring Methods 0.000 claims 1
- 210000000988 bone and bone Anatomy 0.000 abstract description 6
- 239000012620 biological material Substances 0.000 abstract description 5
- 239000000919 ceramic Substances 0.000 abstract description 5
- 230000000844 anti-bacterial effect Effects 0.000 abstract description 3
- 230000003110 anti-inflammatory effect Effects 0.000 abstract description 3
- 239000000463 material Substances 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 5
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 5
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- 210000001519 tissue Anatomy 0.000 description 4
- 239000004068 calcium phosphate ceramic Substances 0.000 description 3
- 229910052588 hydroxylapatite Inorganic materials 0.000 description 3
- 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 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 239000001506 calcium phosphate Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 2
- 229910000391 tricalcium phosphate Inorganic materials 0.000 description 2
- 235000019731 tricalcium phosphate Nutrition 0.000 description 2
- 229940078499 tricalcium phosphate Drugs 0.000 description 2
- PXFBZOLANLWPMH-UHFFFAOYSA-N 16-Epiaffinine Natural products C1C(C2=CC=CC=C2N2)=C2C(=O)CC2C(=CC)CN(C)C1C2CO PXFBZOLANLWPMH-UHFFFAOYSA-N 0.000 description 1
- 206010054949 Metaplasia Diseases 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000000975 bioactive effect Effects 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000002513 implantation Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000015689 metaplastic ossification Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
Classifications
-
- 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
- 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
- A61L27/02—Inorganic materials
- A61L27/12—Phosphorus-containing materials, e.g. apatite
-
- 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
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
- C04B35/63—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B using additives specially adapted for forming the products, e.g.. binder binders
- C04B35/632—Organic additives
-
- 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
- A61L2300/00—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
- A61L2300/10—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices containing or releasing inorganic materials
- A61L2300/112—Phosphorus-containing compounds, e.g. phosphates, phosphonates
-
- 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
- A61L2300/00—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
- A61L2300/40—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices characterised by a specific therapeutic activity or mode of action
- A61L2300/404—Biocides, antimicrobial agents, antiseptic agents
-
- 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
- A61L2300/00—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
- A61L2300/40—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices characterised by a specific therapeutic activity or mode of action
- A61L2300/41—Anti-inflammatory agents, e.g. NSAIDs
-
- 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
- A61L2300/00—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
- A61L2300/40—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices characterised by a specific therapeutic activity or mode of action
- A61L2300/412—Tissue-regenerating or healing or proliferative agents
-
- 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
- A61L2430/00—Materials or treatment for tissue regeneration
- A61L2430/02—Materials or treatment for tissue regeneration for reconstruction of bones; weight-bearing implants
-
- 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
- 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
- C04B2235/32—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
- C04B2235/3206—Magnesium oxides or oxide-forming salts thereof
-
- 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
- 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
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3217—Aluminum oxide or oxide forming salts thereof, e.g. bauxite, alpha-alumina
-
- 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
- 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
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3231—Refractory metal oxides, their mixed metal oxides, or oxide-forming salts thereof
- C04B2235/3232—Titanium oxides or titanates, e.g. rutile or anatase
-
- 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
- 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
- C04B2235/34—Non-metal oxides, non-metal mixed oxides, or salts thereof that form the non-metal oxides upon heating, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3427—Silicates other than clay, e.g. water glass
-
- 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
- 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
- C04B2235/38—Non-oxide ceramic constituents or additives
- C04B2235/3852—Nitrides, e.g. oxynitrides, carbonitrides, oxycarbonitrides, lithium nitride, magnesium nitride
- C04B2235/3873—Silicon nitrides, e.g. silicon carbonitride, silicon oxynitride
-
- 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
- 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
- C04B2235/444—Halide containing anions, e.g. bromide, iodate, chlorite
-
- 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
- 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, hypophosphite
-
- 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
- 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
- C04B2235/46—Gases other than oxygen used as reactant, e.g. nitrogen used to make a nitride phase
-
- 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
- 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
- C04B2235/46—Gases other than oxygen used as reactant, e.g. nitrogen used to make a nitride phase
- C04B2235/465—Ammonia
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Health & Medical Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Organic Chemistry (AREA)
- Structural Engineering (AREA)
- Materials Engineering (AREA)
- Oral & Maxillofacial Surgery (AREA)
- General Health & Medical Sciences (AREA)
- Public Health (AREA)
- Veterinary Medicine (AREA)
- Animal Behavior & Ethology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Epidemiology (AREA)
- Transplantation (AREA)
- Medicinal Chemistry (AREA)
- Dermatology (AREA)
- Materials For Medical Uses (AREA)
Abstract
本发明公开了一种高性能生物陶瓷材料，其配方如下：磷酸铵30‑50份、氯化钙25‑35份、纳米碳酸钙8‑14份、氮化硅4‑10份、水玻璃10‑16份、氯化铝10‑15份、钛酸正丁酯11‑15份、分散剂3‑4份、去离子水20‑40份，并提供了制备方法。本发明的陶瓷生物相容性较好，生物活性较高，具有一定的抗炎杀菌性能，同时，具备良好的机械性能，可作为骨骼修复替代生物材料。
Description
技术领域
本发明属于骨骼修复技术领域，具体涉及一种高性能生物陶瓷材料。
背景技术
随着材料科技的发展，生物材料因其对机体组织进行修复、替代与再生的特殊性能，已经成为当今生物医学领域重要的研究方向之一。生物硬组织代用材料最早是使用体骨、动物骨，后来发展到采用不锈钢和塑料，由于不锈钢存在溶析、腐蚀和疲劳问题，塑料存在稳定性差和强度低的问题。因此造成生物材料发展的瓶颈，生物陶瓷的出现，改善了现有替代材料的不足，因其诸多优势，因此，生物陶瓷具有了广阔的发展前景。
磷酸钙陶瓷(CPC)是生物活性陶瓷材料中的重要种类，目前研究和应用最多的是羟基磷灰石(HA)和磷酸三钙(TCP)。磷酸钙陶瓷含有CaO和P2O5两种成份，是构成人体硬组织的重要无机物质，植入人体后，其表面同人体组织可通过键的结合，达到完全亲和。HA生物活性陶瓷是典型生物活性陶瓷，植入体内后能与组织在界面上形成化学键性结合,具有较高的力学性能，在人体生理环境中可溶解性较低。
发明内容
本发明的目的是提供一种高性能生物陶瓷材料，本发明的陶瓷生物相容性较好，生物活性较高，具有一定的抗炎杀菌性能，同时，具备良好的机械性能，可作为骨骼修复替代生物材料。
一种高性能生物陶瓷材料，其配方如下：
磷酸铵30-50份、氯化钙25-35份、纳米碳酸钙8-14份、氮化硅4-10份、水玻璃10-16份、氯化铝10-15份、钛酸正丁酯11-15份、分散剂3-4份、去离子水20-40份。
所述分散剂采用聚乙烯吡咯烷酮。
作为优选，各组分为磷酸铵35-45份、氯化钙28-33份、纳米碳酸钙9-11份、氮化硅6-8份、水玻璃13-15份、氯化铝11-14份、钛酸正丁酯13-14份、分散剂3-4份、去离子水30-35份。
作为优选，各组分为磷酸铵38份、氯化钙31份、纳米碳酸钙10份、氮化硅7份、水玻璃14份、氯化铝13份、钛酸正丁酯14份、分散剂4份、去离子水33份。
所述生物陶瓷材料的制备方法，其步骤如下：
步骤1，将磷酸铵和氯化钙加入至去离子水中，搅拌均匀，形成悬浊液；
步骤2，将纳米碳酸钙、氮化硅、水玻璃、氯化铝依次加入至去离子水中，搅拌均匀，形成混合浆液，
步骤3，将分散剂与钛酸正丁酯同时加入至浆液中进行搅拌处理，形成前驱浆液；
步骤4，将前驱浆液进行曝气反应3-5h；
步骤5，曝气反应结束后，放入旋蒸仪中进行旋转蒸发形成粘稠浆液；
步骤6，将粘稠浆液进行二次曝气反应2-4h，冷压成型，然后进行加压高温反应；
步骤7，反应结束后，自然冷却，即可得到生物陶瓷材料。
所述制备方法中的搅拌速度为300-1000r/min。
所述步骤4中的曝气反应采用氨气气体，所述曝气反应的气体流速为15-30mL/min，所述曝气反应为循环曝气反应，所述曝气反应的压力为0.5-1.2MPa，所述反应温度为室温。
所述步骤5中的旋转蒸发反应的温度为80-100℃，所述旋蒸蒸发的压力为0.2-0.5MPa
所述步骤6中的二次曝气反应的气体为氮气，所述二次曝气反应的温度为60-70℃，所述加压高温反应的压力为10-20MPa，所述温度为800-1000℃。
与现有技术相比，本发明具有以下有益效果：
1、本发明的陶瓷生物相容性较好，生物活性较高，具有一定的抗炎杀菌性能，同时，具备良好的机械性能，可作为骨骼修复替代生物材料。
2、本发明采用悬浊液与浆液作为前驱液，进行曝气、二次曝气反应，将能够将磷酸三钙、碳化硅、钛源材料紧密结合，具有良好的结合效果，同时经高温烧结后的材料生物活性稳步提高，机械强度得到进一步改善。
3、本发明对环境无特殊要求；材料纯度高，而且材料性能稳定，易于进行工业化生产。
具体实施方式
下面结合实施例对本发明做进一步描述：
实施例1
一种高性能生物陶瓷材料，其配方如下：
磷酸铵30份、氯化钙25份、纳米碳酸钙8份、氮化硅4份、水玻璃10份、氯化铝10份、钛酸正丁酯11份、分散剂3份、去离子水20份。
所述分散剂采用聚乙烯吡咯烷酮。
所述生物陶瓷材料的制备方法，其步骤如下：
步骤1，将磷酸铵和氯化钙加入至去离子水中，搅拌均匀，形成悬浊液；
步骤2，将纳米碳酸钙、氮化硅、水玻璃、氯化铝依次加入至去离子水中，搅拌均匀，形成混合浆液，
步骤3，将分散剂与钛酸正丁酯同时加入至浆液中进行搅拌处理，形成前驱浆液；
步骤4，将前驱浆液进行曝气反应3h；
步骤5，曝气反应结束后，放入旋蒸仪中进行旋转蒸发形成粘稠浆液；
步骤6，将粘稠浆液进行二次曝气反应2h，冷压成型，然后进行加压高温反应；
步骤7，反应结束后，自然冷却，即可得到生物陶瓷材料。
所述制备方法中的搅拌速度为300r/min。
所述步骤4中的曝气反应采用氨气气体，所述曝气反应的气体流速为15mL/min，所述曝气反应为循环曝气反应，所述曝气反应的压力为0.5MPa，所述反应温度为室温。
所述步骤5中的旋转蒸发反应的温度为80℃，所述旋蒸蒸发的压力为0.2MPa
所述步骤6中的二次曝气反应的气体为氮气，所述二次曝气反应的温度为60℃，所述加压高温反应的压力为10MPa，所述温度为800℃。
实施例2
一种高性能生物陶瓷材料，其配方如下：
磷酸铵50份、氯化钙35份、纳米碳酸钙14份、氮化硅10份、水玻璃16份、氯化铝15份、钛酸正丁酯15份、分散剂4份、去离子水40份。
所述分散剂采用聚乙烯吡咯烷酮。
所述生物陶瓷材料的制备方法，其步骤如下：
步骤1，将磷酸铵和氯化钙加入至去离子水中，搅拌均匀，形成悬浊液；
步骤2，将纳米碳酸钙、氮化硅、水玻璃、氯化铝依次加入至去离子水中，搅拌均匀，形成混合浆液，
步骤3，将分散剂与钛酸正丁酯同时加入至浆液中进行搅拌处理，形成前驱浆液；
步骤4，将前驱浆液进行曝气反应5h；
步骤5，曝气反应结束后，放入旋蒸仪中进行旋转蒸发形成粘稠浆液；
步骤6，将粘稠浆液进行二次曝气反应4h，冷压成型，然后进行加压高温反应；
步骤7，反应结束后，自然冷却，即可得到生物陶瓷材料。
所述制备方法中的搅拌速度为1000r/min。
所述步骤4中的曝气反应采用氨气气体，所述曝气反应的气体流速为30mL/min，所述曝气反应为循环曝气反应，所述曝气反应的压力为1.2MPa，所述反应温度为室温。
所述步骤5中的旋转蒸发反应的温度为100℃，所述旋蒸蒸发的压力为0.5MPa
所述步骤6中的二次曝气反应的气体为氮气，所述二次曝气反应的温度为70℃，所述加压高温反应的压力为10-20MPa，所述温度为1000℃。
实施例3
一种高性能生物陶瓷材料，其配方如下：
磷酸铵35份、氯化钙28份、纳米碳酸钙9份、氮化硅6份、水玻璃13份、氯化铝11份、钛酸正丁酯13份、分散剂3份、去离子水30份。
所述分散剂采用聚乙烯吡咯烷酮。
所述生物陶瓷材料的制备方法，其步骤如下：
步骤1，将磷酸铵和氯化钙加入至去离子水中，搅拌均匀，形成悬浊液；
步骤2，将纳米碳酸钙、氮化硅、水玻璃、氯化铝依次加入至去离子水中，搅拌均匀，形成混合浆液，
步骤3，将分散剂与钛酸正丁酯同时加入至浆液中进行搅拌处理，形成前驱浆液；
步骤4，将前驱浆液进行曝气反应4h；
步骤5，曝气反应结束后，放入旋蒸仪中进行旋转蒸发形成粘稠浆液；
步骤6，将粘稠浆液进行二次曝气反应3h，冷压成型，然后进行加压高温反应；
步骤7，反应结束后，自然冷却，即可得到生物陶瓷材料。
所述制备方法中的搅拌速度为500r/min。
所述步骤4中的曝气反应采用氨气气体，所述曝气反应的气体流速为18mL/min，所述曝气反应为循环曝气反应，所述曝气反应的压力为0.7MPa，所述反应温度为室温。
所述步骤5中的旋转蒸发反应的温度为90℃，所述旋蒸蒸发的压力为0.3MPa
所述步骤6中的二次曝气反应的气体为氮气，所述二次曝气反应的温度为65℃，所述加压高温反应的压力为13MPa，所述温度为900℃。
实施例4
一种高性能生物陶瓷材料，其配方如下：
磷酸铵45份、氯化钙33份、纳米碳酸钙11份、氮化硅8份、水玻璃15份、氯化铝14份、钛酸正丁酯14份、分散剂4份、去离子水35份。
所述分散剂采用聚乙烯吡咯烷酮。
所述生物陶瓷材料的制备方法，其步骤如下：
步骤1，将磷酸铵和氯化钙加入至去离子水中，搅拌均匀，形成悬浊液；
步骤2，将纳米碳酸钙、氮化硅、水玻璃、氯化铝依次加入至去离子水中，搅拌均匀，形成混合浆液，
步骤3，将分散剂与钛酸正丁酯同时加入至浆液中进行搅拌处理，形成前驱浆液；
步骤4，将前驱浆液进行曝气反应4h；
步骤5，曝气反应结束后，放入旋蒸仪中进行旋转蒸发形成粘稠浆液；
步骤6，将粘稠浆液进行二次曝气反应3h，冷压成型，然后进行加压高温反应；
步骤7，反应结束后，自然冷却，即可得到生物陶瓷材料。
所述制备方法中的搅拌速度为700r/min。
所述步骤4中的曝气反应采用氨气气体，所述曝气反应的气体流速为20mL/min，所述曝气反应为循环曝气反应，所述曝气反应的压力为0.7MPa，所述反应温度为室温。
所述步骤5中的旋转蒸发反应的温度为85℃，所述旋蒸蒸发的压力为0.4MPa
所述步骤6中的二次曝气反应的气体为氮气，所述二次曝气反应的温度为65℃，所述加压高温反应的压力为15MPa，所述温度为850℃。
实施例5
一种高性能生物陶瓷材料，其配方如下：
磷酸铵38份、氯化钙31份、纳米碳酸钙10份、氮化硅7份、水玻璃14份、氯化铝13份、钛酸正丁酯14份、分散剂4份、去离子水33份。
所述生物陶瓷材料的制备方法，其步骤如下：
步骤1，将磷酸铵和氯化钙加入至去离子水中，搅拌均匀，形成悬浊液；
步骤2，将纳米碳酸钙、氮化硅、水玻璃、氯化铝依次加入至去离子水中，搅拌均匀，形成混合浆液，
步骤3，将分散剂与钛酸正丁酯同时加入至浆液中进行搅拌处理，形成前驱浆液；
步骤4，将前驱浆液进行曝气反应3h；
步骤5，曝气反应结束后，放入旋蒸仪中进行旋转蒸发形成粘稠浆液；
步骤6，将粘稠浆液进行二次曝气反应3h，冷压成型，然后进行加压高温反应；
步骤7，反应结束后，自然冷却，即可得到生物陶瓷材料。
所述制备方法中的搅拌速度为800r/min。
所述步骤4中的曝气反应采用氨气气体，所述曝气反应的气体流速为25mL/min，所述曝气反应为循环曝气反应，所述曝气反应的压力为1.0 MPa，所述反应温度为室温。
所述步骤5中的旋转蒸发反应的温度为95℃，所述旋蒸蒸发的压力为0.4MPa
所述步骤6中的二次曝气反应的气体为氮气，所述二次曝气反应的温度为65℃，所述加压高温反应的压力为18MPa，所述温度为850℃。
实施例1-5的生物陶瓷材料进行测试
| 实施例 | 硬度（HV） | 压缩强度MPa | 抗弯强度MPa | 韧性MPa·m0.5 |
| 实施例1 | 840 | 1100 | 420 | 16 |
| 实施例2 | 870 | 1300 | 430 | 15 |
| 实施例3 | 850 | 1429 | 437 | 14 |
| 实施例4 | 867 | 1234 | 459 | 15 |
| 实施例5 | 890 | 1500 | 480 | 16 |
以上所述仅为本发明的一实施例，并不限制本发明，凡采用等同替换或等效变换的方式所获得的技术方案，均落在本发明的保护范围内。
Claims (9)
1.一种高性能生物陶瓷材料，其特征在于，其配方如下：
磷酸铵30-50份、氯化钙25-35份、纳米碳酸钙8-14份、氮化硅4-10份、水玻璃10-16份、氯化铝10-15份、钛酸正丁酯11-15份、分散剂3-4份、去离子水20-40份。
2.根据权利要求1所述的一种高性能生物陶瓷材料，其特征在于，所述分散剂采用聚乙烯吡咯烷酮。
3.根据权利要求1所述的一种高性能生物陶瓷材料，其特征在于，各组分为磷酸铵35-45份、氯化钙28-33份、纳米碳酸钙9-11份、氮化硅6-8份、水玻璃13-15份、氯化铝11-14份、钛酸正丁酯13-14份、分散剂3-4份、去离子水30-35份。
4.根据权利要求3所述的一种高性能生物陶瓷材料，其特征在于，各组分为磷酸铵38份、氯化钙31份、纳米碳酸钙10份、氮化硅7份、水玻璃14份、氯化铝13份、钛酸正丁酯14份、分散剂4份、去离子水33份。
5.根据权利要求1所述的一种高性能生物陶瓷材料，其特征在于，所述生物陶瓷材料的制备方法，其步骤如下：
步骤1，将磷酸铵和氯化钙加入至去离子水中，搅拌均匀，形成悬浊液；
步骤2，将纳米碳酸钙、氮化硅、水玻璃、氯化铝依次加入至去离子水中，搅拌均匀，形成混合浆液，
步骤3，将分散剂与钛酸正丁酯同时加入至浆液中进行搅拌处理，形成前驱浆液；
步骤4，将前驱浆液进行曝气反应3-5h；
步骤5，曝气反应结束后，放入旋蒸仪中进行旋转蒸发形成粘稠浆液；
步骤6，将粘稠浆液进行二次曝气反应2-4h，冷压成型，然后进行加压高温反应；
步骤7，反应结束后，自然冷却，即可得到生物陶瓷材料。
6.根据权利要求5所述的一种高性能生物陶瓷材料，其特征在于，所述制备方法中的搅拌速度为300-1000r/min。
7.根据权利要求5所述的一种高性能生物陶瓷材料，其特征在于，所述步骤4中的曝气反应采用氨气气体，所述曝气反应的气体流速为15-30mL/min，所述曝气反应为循环曝气反应，所述曝气反应的压力为0.5-1.2MPa，所述反应温度为室温。
8.根据权利要求5所述的一种高性能生物陶瓷材料，其特征在于，所述步骤5中的旋转蒸发反应的温度为80-100℃，所述旋蒸蒸发的压力为0.2-0.5MPa。
9.根据权利要求5所述的一种高性能生物陶瓷材料，其特征在于，所述步骤6中的二次曝气反应的气体为氮气，所述二次曝气反应的温度为60-70℃，所述加压高温反应的压力为10-20MPa，所述温度为800-1000℃。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611029218.5A CN106747400B (zh) | 2016-11-22 | 2016-11-22 | 一种高性能生物陶瓷材料 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611029218.5A CN106747400B (zh) | 2016-11-22 | 2016-11-22 | 一种高性能生物陶瓷材料 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106747400A true CN106747400A (zh) | 2017-05-31 |
| CN106747400B CN106747400B (zh) | 2020-08-18 |
Family
ID=58971603
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201611029218.5A Active CN106747400B (zh) | 2016-11-22 | 2016-11-22 | 一种高性能生物陶瓷材料 |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106747400B (zh) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101156964A (zh) * | 2007-11-08 | 2008-04-09 | 浙江大学 | 可缓释生物活性因子的类骨生物医用材料及其制备方法 |
| CN101880033A (zh) * | 2010-03-04 | 2010-11-10 | 上海纳米技术及应用国家工程研究中心有限公司 | 一种生物陶瓷用磷酸钙的制备方法 |
| CN104446432A (zh) * | 2014-11-10 | 2015-03-25 | 苏州维泰生物技术有限公司 | 一种磁性羟基磷灰石生物陶瓷及其制备方法 |
| CN104744028A (zh) * | 2015-03-31 | 2015-07-01 | 苏州维泰生物技术有限公司 | 一种磷酸三钙/碳化硅复合生物陶瓷及其制备方法 |
-
2016
- 2016-11-22 CN CN201611029218.5A patent/CN106747400B/zh active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101156964A (zh) * | 2007-11-08 | 2008-04-09 | 浙江大学 | 可缓释生物活性因子的类骨生物医用材料及其制备方法 |
| CN101880033A (zh) * | 2010-03-04 | 2010-11-10 | 上海纳米技术及应用国家工程研究中心有限公司 | 一种生物陶瓷用磷酸钙的制备方法 |
| CN104446432A (zh) * | 2014-11-10 | 2015-03-25 | 苏州维泰生物技术有限公司 | 一种磁性羟基磷灰石生物陶瓷及其制备方法 |
| CN104744028A (zh) * | 2015-03-31 | 2015-07-01 | 苏州维泰生物技术有限公司 | 一种磷酸三钙/碳化硅复合生物陶瓷及其制备方法 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106747400B (zh) | 2020-08-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106830899B (zh) | 一种复合陶瓷材料及其制备方法与应用 | |
| WO2003088925A3 (en) | Method of manufacturing hydroxyapatite and uses therefor in delivery of nucleic acids | |
| CN106083028A (zh) | 生物相容性较好的、用于骨缺损修复的复合生物陶瓷 | |
| CN108421085B (zh) | 石墨烯与羟基磷灰石复合仿生骨材料及其制备方法 | |
| CN104192817B (zh) | 利用模板法制备高比表面积介孔羟基磷灰石纳米粒子的方法 | |
| CN108689699A (zh) | 一种高柔韧性人工骨骼关节用陶瓷复合材料及制备方法 | |
| CN103285425B (zh) | 一种抗降解和抗菌性能良好的生物涂层及其制备方法 | |
| CN104803673B (zh) | 一种羟基磷灰石/钛酸钠复合生物陶瓷及其制备方法 | |
| CN104998301A (zh) | 碳纳米管增强介孔羟基磷灰石复合材料的制备方法 | |
| CN101376036A (zh) | 一种含锶和氟复合纳米羟基磷灰石及其制备方法 | |
| CN107162388B (zh) | 一种以树枝状聚乙烯亚胺为模板剂和催化剂制备大孔生物活性玻璃纳米簇的方法 | |
| CN106693052A (zh) | 一种纳米硅酸二钙/羟基磷灰石梯度钛种植体涂层及其制备方法和应用 | |
| CN106747400A (zh) | 一种高性能生物陶瓷材料 | |
| CN104803671B (zh) | 一种磷酸三钙/氧化锆生物陶瓷及其制备方法 | |
| CN104987058B (zh) | 一种原位反应制备羟基磷灰石基复合生物陶瓷材料的方法 | |
| CN104774004A (zh) | 一种稀土掺杂磷酸钙生物活性陶瓷及其制备方法 | |
| CN100560505C (zh) | 纳米氧化锆及羟基磷灰石复合粉体的原位制备方法 | |
| CN105967662A (zh) | 一种氧化铝/氧化锶生物陶瓷及其制备方法 | |
| CN104774861A (zh) | 一种利用平端连接法高效筛选阳性转化子的dna重组方法 | |
| CN101445247A (zh) | 一种微波合成生物活性β-硅酸二钙的制备方法 | |
| CN108002840A (zh) | 一种生物植入陶瓷材料及制备方法 | |
| CN107137772A (zh) | 碳纳米管增强羟基磷灰石复合材料的制备方法 | |
| CN106086764A (zh) | 一种在不锈钢表面形成氟掺杂羟基磷灰石纳米涂层的方法 | |
| CN1055061C (zh) | 人体骨骼修复用块状羟基磷灰石的制备方法 | |
| CN101264872A (zh) | 用天然骨粉制备α-,β-磷酸三钙的方法 |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| TA01 | Transfer of patent application right | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20200720 Address after: 312030 No. 1438 Wenchang Road, Lanting Street, Keqiao District, Shaoxing City, Zhejiang Province Applicant after: Shaoxing Dalengken Biotechnology Co.,Ltd. Address before: 312000 Xinchang County, Zhejiang Province, East Village, the village of Wang Ming, No. 271, No. Applicant before: Yu Chaojun |
|
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20231218 Address after: Room 0107-1, Building 11, Keqiao Xianghu County Community, Keqiao Street, Keqiao District, Shaoxing City, Zhejiang Province, 312030 Patentee after: Shaoxing Xinhui Biotechnology Co.,Ltd. Address before: 1438 Wenchang Road, Lanting street, Keqiao District, Shaoxing City, Zhejiang Province Patentee before: Shaoxing Dalengken Biotechnology Co.,Ltd. |
|
| PE01 | Entry into force of the registration of the contract for pledge of patent right | ||
| PE01 | Entry into force of the registration of the contract for pledge of patent right |
Denomination of invention: A high-performance bioceramic material Effective date of registration: 20231228 Granted publication date: 20200818 Pledgee: Shaoxing Branch of Zhejiang Tailong Commercial Bank Co.,Ltd. Pledgor: Shaoxing Xinhui Biotechnology Co.,Ltd. Registration number: Y2023980074769 |