CN114516720A - Bioactive glass and method for manufacturing bioactive glass three-dimensional product - Google Patents
Bioactive glass and method for manufacturing bioactive glass three-dimensional product Download PDFInfo
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- CN114516720A CN114516720A CN202011295270.1A CN202011295270A CN114516720A CN 114516720 A CN114516720 A CN 114516720A CN 202011295270 A CN202011295270 A CN 202011295270A CN 114516720 A CN114516720 A CN 114516720A
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- 239000005313 bioactive glass Substances 0.000 title claims abstract description 126
- 238000000034 method Methods 0.000 title claims abstract description 21
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 16
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 16
- 239000011230 binding agent Substances 0.000 claims abstract description 15
- -1 ferrous metal oxide Chemical class 0.000 claims abstract description 15
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052751 metal Inorganic materials 0.000 claims abstract description 9
- 239000002184 metal Substances 0.000 claims abstract description 8
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 8
- 239000010949 copper Substances 0.000 claims abstract description 7
- 229910052742 iron Inorganic materials 0.000 claims abstract description 7
- 229910052802 copper Inorganic materials 0.000 claims abstract description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000011651 chromium Substances 0.000 claims abstract description 5
- 239000000758 substrate Substances 0.000 claims abstract description 5
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 4
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 4
- 239000010941 cobalt Substances 0.000 claims abstract description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 4
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 17
- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 claims description 16
- 238000000149 argon plasma sintering Methods 0.000 claims description 13
- 230000005855 radiation Effects 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 11
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 10
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims description 10
- 229910001948 sodium oxide Inorganic materials 0.000 claims description 10
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 8
- 239000000292 calcium oxide Substances 0.000 claims description 8
- 239000011159 matrix material Substances 0.000 claims description 7
- 239000000377 silicon dioxide Substances 0.000 claims description 7
- VSAISIQCTGDGPU-UHFFFAOYSA-N tetraphosphorus hexaoxide Chemical compound O1P(O2)OP3OP1OP2O3 VSAISIQCTGDGPU-UHFFFAOYSA-N 0.000 claims description 6
- JNDMLEXHDPKVFC-UHFFFAOYSA-N aluminum;oxygen(2-);yttrium(3+) Chemical compound [O-2].[O-2].[O-2].[Al+3].[Y+3] JNDMLEXHDPKVFC-UHFFFAOYSA-N 0.000 claims description 3
- 229910001392 phosphorus oxide Inorganic materials 0.000 claims description 3
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 3
- 229910019901 yttrium aluminum garnet Inorganic materials 0.000 claims description 3
- 239000000853 adhesive Substances 0.000 abstract description 2
- 230000001070 adhesive effect Effects 0.000 abstract description 2
- 239000000463 material Substances 0.000 description 22
- 238000012360 testing method Methods 0.000 description 18
- 239000000843 powder Substances 0.000 description 14
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 13
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 12
- 238000000110 selective laser sintering Methods 0.000 description 12
- 230000000694 effects Effects 0.000 description 11
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 8
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 6
- 235000013980 iron oxide Nutrition 0.000 description 6
- 238000005245 sintering Methods 0.000 description 6
- 238000005238 degreasing Methods 0.000 description 5
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 5
- 229920001903 high density polyethylene Polymers 0.000 description 5
- 239000004700 high-density polyethylene Substances 0.000 description 5
- 239000004372 Polyvinyl alcohol Substances 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 210000000988 bone and bone Anatomy 0.000 description 4
- 238000004113 cell culture Methods 0.000 description 4
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 150000004706 metal oxides Chemical class 0.000 description 4
- UPWOEMHINGJHOB-UHFFFAOYSA-N oxo(oxocobaltiooxy)cobalt Chemical compound O=[Co]O[Co]=O UPWOEMHINGJHOB-UHFFFAOYSA-N 0.000 description 4
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 4
- LFGREXWGYUGZLY-UHFFFAOYSA-N phosphoryl Chemical compound [P]=O LFGREXWGYUGZLY-UHFFFAOYSA-N 0.000 description 4
- 229920001610 polycaprolactone Polymers 0.000 description 4
- 239000004632 polycaprolactone Substances 0.000 description 4
- 229920002451 polyvinyl alcohol Polymers 0.000 description 4
- MBBWTVUFIXOUBE-UHFFFAOYSA-L zinc;dicarbamodithioate Chemical compound [Zn+2].NC([S-])=S.NC([S-])=S MBBWTVUFIXOUBE-UHFFFAOYSA-L 0.000 description 4
- 239000005751 Copper oxide Substances 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- NJFMNPFATSYWHB-UHFFFAOYSA-N ac1l9hgr Chemical compound [Fe].[Fe] NJFMNPFATSYWHB-UHFFFAOYSA-N 0.000 description 3
- 239000011575 calcium Substances 0.000 description 3
- 230000003833 cell viability Effects 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- AYTAKQFHWFYBMA-UHFFFAOYSA-N chromium(IV) oxide Inorganic materials O=[Cr]=O AYTAKQFHWFYBMA-UHFFFAOYSA-N 0.000 description 3
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical class [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 3
- 229910000431 copper oxide Inorganic materials 0.000 description 3
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(i) oxide Chemical compound [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 210000001161 mammalian embryo Anatomy 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- GNMQOUGYKPVJRR-UHFFFAOYSA-N nickel(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Ni+3].[Ni+3] GNMQOUGYKPVJRR-UHFFFAOYSA-N 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 229920001606 poly(lactic acid-co-glycolic acid) Polymers 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 235000012239 silicon dioxide Nutrition 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 230000004083 survival effect Effects 0.000 description 3
- 238000010146 3D printing Methods 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- 229910021541 Vanadium(III) oxide Inorganic materials 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 238000003556 assay Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 238000003570 cell viability assay Methods 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 229910000424 chromium(II) oxide Inorganic materials 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- NFFYXVOHHLQALV-UHFFFAOYSA-N copper(iii) oxide Chemical compound [O-2].[O-2].[O-2].[Cu].[Cu] NFFYXVOHHLQALV-UHFFFAOYSA-N 0.000 description 2
- 239000007943 implant Substances 0.000 description 2
- 239000002609 medium Substances 0.000 description 2
- 239000013642 negative control Substances 0.000 description 2
- RQFLGKYCYMMRMC-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O.CCCCCCCCCCCCCCCCCC(O)=O RQFLGKYCYMMRMC-UHFFFAOYSA-N 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000013641 positive control Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000004626 scanning electron microscopy Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- RKQOSDAEEGPRER-UHFFFAOYSA-L zinc diethyldithiocarbamate Chemical compound [Zn+2].CCN(CC)C([S-])=S.CCN(CC)C([S-])=S RKQOSDAEEGPRER-UHFFFAOYSA-L 0.000 description 2
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- 229910021542 Vanadium(IV) oxide Inorganic materials 0.000 description 1
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 239000000560 biocompatible material Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910000423 chromium oxide Inorganic materials 0.000 description 1
- IAQWMWUKBQPOIY-UHFFFAOYSA-N chromium(4+);oxygen(2-) Chemical compound [O-2].[O-2].[Cr+4] IAQWMWUKBQPOIY-UHFFFAOYSA-N 0.000 description 1
- IUYLTEAJCNAMJK-UHFFFAOYSA-N cobalt(2+);oxygen(2-) Chemical compound [O-2].[Co+2] IUYLTEAJCNAMJK-UHFFFAOYSA-N 0.000 description 1
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 description 1
- 231100000433 cytotoxic Toxicity 0.000 description 1
- 230000001472 cytotoxic effect Effects 0.000 description 1
- 230000003013 cytotoxicity Effects 0.000 description 1
- 231100000135 cytotoxicity Toxicity 0.000 description 1
- ALKZAGKDWUSJED-UHFFFAOYSA-N dinuclear copper ion Chemical compound [Cu].[Cu] ALKZAGKDWUSJED-UHFFFAOYSA-N 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- VBMVTYDPPZVILR-UHFFFAOYSA-N iron(2+);oxygen(2-) Chemical class [O-2].[Fe+2] VBMVTYDPPZVILR-UHFFFAOYSA-N 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- 231100001083 no cytotoxicity Toxicity 0.000 description 1
- 231100000065 noncytotoxic Toxicity 0.000 description 1
- 230000002020 noncytotoxic effect Effects 0.000 description 1
- PZFKDUMHDHEBLD-UHFFFAOYSA-N oxo(oxonickeliooxy)nickel Chemical compound O=[Ni]O[Ni]=O PZFKDUMHDHEBLD-UHFFFAOYSA-N 0.000 description 1
- KFAFTZQGYMGWLU-UHFFFAOYSA-N oxo(oxovanadiooxy)vanadium Chemical compound O=[V]O[V]=O KFAFTZQGYMGWLU-UHFFFAOYSA-N 0.000 description 1
- XVOFZWCCFLVFRR-UHFFFAOYSA-N oxochromium Chemical compound [Cr]=O XVOFZWCCFLVFRR-UHFFFAOYSA-N 0.000 description 1
- DUSYNUCUMASASA-UHFFFAOYSA-N oxygen(2-);vanadium(4+) Chemical compound [O-2].[O-2].[V+4] DUSYNUCUMASASA-UHFFFAOYSA-N 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 210000004872 soft tissue Anatomy 0.000 description 1
- 229910019655 synthetic inorganic crystalline material Inorganic materials 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- IBYSTTGVDIFUAY-UHFFFAOYSA-N vanadium monoxide Chemical compound [V]=O IBYSTTGVDIFUAY-UHFFFAOYSA-N 0.000 description 1
- 229910001935 vanadium oxide Inorganic materials 0.000 description 1
Images
Classifications
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- 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
- C03C4/00—Compositions for glass with special properties
- C03C4/0007—Compositions for glass with special properties for biologically-compatible glass
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y70/00—Materials specially adapted for additive manufacturing
- B33Y70/10—Composites of different types of material, e.g. mixtures of ceramics and polymers or mixtures of metals and biomaterials
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B19/00—Other methods of shaping glass
- C03B19/06—Other methods of shaping glass by sintering, e.g. by cold isostatic pressing of powders and subsequent sintering, by hot pressing of powders, by sintering slurries or dispersions not undergoing a liquid phase reaction
-
- 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
- C03C3/04—Glass compositions containing silica
- C03C3/062—Glass compositions containing silica with less than 40% silica by weight
-
- 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
- C03C4/00—Compositions for glass with special properties
- C03C4/0007—Compositions for glass with special properties for biologically-compatible glass
- C03C4/0021—Compositions for glass with special properties for biologically-compatible glass for dental use
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/25—Process efficiency
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Molecular Biology (AREA)
- Manufacturing & Machinery (AREA)
- Ceramic Engineering (AREA)
- Civil Engineering (AREA)
- Composite Materials (AREA)
- Structural Engineering (AREA)
- Oral & Maxillofacial Surgery (AREA)
- Dispersion Chemistry (AREA)
- Glass Compositions (AREA)
Abstract
The invention provides bioactive glass, which is used for solving the problem that a large amount of adhesive needs to be mixed in the existing bioactive glass. The bioactive glass comprises: 60-80% by weight of a substrate, 10-30% by weight of a binder and 1-10% by weight of a non-ferrous metal oxide, the non-ferrous metal oxide comprising a metal element, and the metal element may be a transition metal element selected from the group consisting of one or more of vanadium, chromium, iron, cobalt, nickel and copper. The invention further relates to a method for manufacturing a bioactive glass three-dimensional product by using the bioactive glass.
Description
Technical Field
The present invention relates to a bioactive glass, in particular a bioactive glass for selective laser sintering, and further relates to a method for manufacturing a bioactive glass three-dimensional product by using the bioactive glass.
Background
Bioactive glass (BAG) is a biocompatible material that can be dissolved in an aqueous medium and is capable of dissolving in an aqueous mediumCan be connected with bone tissue and soft tissue, and is widely applied to the manufacture of dental fillers (dental filling materials) and bone implants (bone implants). The composition of the existing bioactive glass comprises silicon dioxide (SiO)2) Sodium oxide (Na)2O), calcium oxide (CaO) and phosphorus pentoxide (P)2O5) For example, 45S5 bioactive glass comprises, in weight percent, 45% silica, 24.5% sodium oxide, 24.5% calcium oxide, and 6% phosphorus pentoxide, wherein the molar ratio of calcium to phosphorus (molar ratio) is 5: 1.
three-dimensional printing (3D printing), also called Additive Manufacturing (AM), refers to a processing technique of melting material powder by using different energy sources under computer control, and stacking the material powder layer by layer after melting and curing to form a printed product. In the Selective Laser Sintering (SLS) method developed in recent years, laser sintering material powder is used, and after a low-melting-point binder added to the material powder is heated and melted, the material powder is bonded with high-melting-point powder such as ceramic or metal, and the high-melting-point powder and the ceramic or metal are sequentially stacked layer by layer until the printing operation of a three-dimensional object is completed, so that the method has the advantages of wide applicable materials, high molding efficiency, high material utilization rate and the like; however, when bioactive glass is used as the material powder in the selective laser sintering method, it is often necessary to add a large amount of binder due to its high melting point, for example, stearic acid (stearic acid), polyvinyl alcohol (PVA), Polycaprolactone (PCL), polylactic-co-glycolic acid (PLGA), etc. are used to assist the formation of the product, and the addition amount of the additive even needs to be more than 50%, which not only greatly affects the biocompatibility of the formed three-dimensional object, after forming into a three-dimensional object, degreasing and sintering (sintering) at high temperature is additionally required, holes may be formed on the surface of the formed three-dimensional object, resulting in insufficient structural strength (structural strength) of the formed three-dimensional object, in other words, the existing bioactive glass is not suitable for the material powder used as the selective laser sintering method.
In view of the above, there is a need for a novel bioactive glass and a method for producing a three-dimensional bioactive glass product using the bioactive glass.
Disclosure of Invention
In order to solve the above problems, the present invention provides a bioactive glass suitable for being formed into a bioactive glass three-dimensional product with a predetermined shape by a selective laser sintering method.
Another object of the present invention is to provide a selective laser sintering method, which uses the bioactive glass to form a three-dimensional bioactive glass product with a predetermined shape.
The bioactive glass of the present invention may comprise: 60-80% of a matrix, 10-30% of a binder and 1-10% of a non-ferrous metal oxide by weight percentage, wherein the non-ferrous metal oxide contains a metal element.
Therefore, the bioactive glass can greatly improve the absorption efficiency of the bioactive glass to laser energy by adding the nonferrous metal oxide, so that the dosage of the adhesive is reduced to 10-30%, and therefore, when the bioactive glass is used as material powder of a selective laser sintering method, holes on a formed bioactive glass three-dimensional product after degreasing and sintering can be effectively reduced, the structural strength of the formed bioactive glass three-dimensional product is improved, and the effect of the bioactive glass three-dimensional product is achieved.
The bioactive glass of the present invention, wherein the metal element may be a transition metal element; for example, the transition metal element may be selected from the group consisting of one or more of vanadium, chromium, iron, cobalt, nickel, and copper.
The bioactive glass of the present invention wherein the substrate may comprise a silicon oxide, a sodium oxide, a calcium oxide and a phosphorus oxide; for example, the matrix comprises 35-40% by weight of silicon dioxide, 5-10% by weight of sodium oxide, 39-43% by weight of calcium oxide and 10-15% by weight of phosphorus pentoxide.
The method for manufacturing the bioactive glass three-dimensional product can comprise the following steps: providing a bioactive glass as described above; performing laser sintering on the bioactive glass by using a laser with a wavelength of 400-1200 nm to form a rough blank; and carrying out heat treatment on the rough blank to remove the binder in the rough blank so as to obtain a bioactive glass three-dimensional product.
Therefore, according to the manufacturing method of the bioactive glass three-dimensional product, the bioactive glass is used as the material powder, the radiation energy released by the laser with the wavelength between 400 nm and 1200nm can be effectively absorbed by the bioactive glass, the adhesion forming effect of the bioactive glass is improved, the generation of holes after high-temperature degreasing and sintering is reduced, and the bioactive glass three-dimensional product formed by the bioactive glass has good biocompatibility and good structural strength, so that the effect of the invention is achieved.
The method for manufacturing the bioactive glass three-dimensional product can carry out the heat treatment on the rough blank at 1050-1150 ℃ for 1-3 hours.
The method for producing a three-dimensional bioactive glass product of the present invention can be used in an amount of 1 to 3cal/cm2The laser sintering is performed at the radiation energy density.
The invention relates to a method for manufacturing a three-dimensional bioactive glass product, wherein a laser for performing laser sintering on the bioactive glass is a neodymium-doped yttrium aluminum garnet laser.
Drawings
FIG. 1 is a flow chart of a method of making a three-dimensional article of bioactive glass according to one embodiment of the present invention;
FIG. 2 shows the analysis results of the test pieces subjected to laser sintering at different powers and different radiation energy densities in test (A);
FIG. 3 is a bar graph showing the compressive strength of the bioactive glass three-dimensional articles of groups B1-B3 in test (B);
FIG. 4a scanning electron microscope analysis of a three-dimensional article of bioactive glass from group B1 in test (B);
FIG. 4B scanning electron microscopy analysis of a three-dimensional article of bioactive glass from group B2 in test (B);
FIG. 4c scanning electron microscopy analysis of a three-dimensional article of bioactive glass from group B3 of trial (B);
FIG. 5 is a bar graph of the cell viability assay of the three-dimensional articles of bioactive glass from groups C0 to C5 in assay (C);
FIG. 6 is a bar graph of the cell viability assay of the three-dimensional articles of bioactive glass from groups D0-D5 in assay (D).
Description of the reference numerals
[ invention ] to provide
S1 Material providing step
S2 laser sintering step
S3, heat treatment step.
Detailed Description
In order to make the aforementioned and other objects, features and advantages of the present invention comprehensible, preferred embodiments accompanied with figures are described in detail below:
the bioactive glass of an embodiment of the present invention may include a matrix (substrate), a binder (binder) and a colored metal oxide (colored metal oxide) in specific proportions, which may be used as material powder for a selective laser sintering method, and sequentially pass through a material providing step S1, a laser sintering step S2 and a heat treatment step S3 to obtain a bioactive glass three-dimensional article having a predetermined shape.
In detail, in the sample providing step S1, the bioactive glass may include a matrix in an amount of 60 to 80% by weight, for example, the matrix may include an oxide type of silicon (silicon, Si), sodium (Na), calcium (Ca), and phosphorus (P), for example, the silicon oxide containing silicon may be silicon dioxide (SiO )2) And silicon monoxide (SiO), and sodium oxide (sodium oxide, N)a2O), etc., the calcium oxide containing calcium element may be calcium oxide (CaO), etc., and the phosphorus oxide containing phosphorus element may be phosphorus (V) oxide, P2O5) Phosphorus (III) oxide, P2O3) And phosphorus monoxide (PO), which will be understood by those skilled in the art and will not be described herein. In this embodiment, the matrix may include 35-40% by weight of silica, 5-10% by weight of sodium oxide, 39-43% by weight of calcium oxide, and 10-15% by weight of phosphorus pentoxide.
The bioactive glass may further include 10-30 wt% of a binder, which may be any binder suitable for the selective laser sintering method, for example, stearic acid (stearic acid), polyvinyl alcohol (PVA), Polycaprolactone (PCL), poly (lactic-co-glycolic acid) (PLGA), etc., without limitation.
The bioactive glass also comprises 1-10 wt% of non-ferrous metal oxide, and the non-ferrous metal oxide can be identified as non-transparent and non-white colors (namely, various colors except white) by naked eyes under natural light (native light) irradiation, so that the transmittance of light sources with different wavelengths can be reduced, and the absorption efficiency of the material to the light sources can be improved.
The non-ferrous metal oxide contains a metal element, which may be a transition metal element containing a transition metal element, such as vanadium (V), chromium (Cr), iron (iron, Fe), cobalt (Co), nickel (Ni), and copper (copper) belonging to the fourth period (period 4). For example, the vanadium oxide includes vanadium (II) oxide, VO, vanadium (III) oxide, V2O3) Vanadium (iv) oxide, VO2) And vanadium (V) oxide, V2O5) Etc. chromium oxide packageContaining chromium (II) oxide, CrO, chromium (III) oxide, Cr2O3) Chromium (IV) oxide, CrO2) Chromium (vi) oxide, CrO3) And chromium (VI) oxide peroxides, the iron oxides including iron (iron) (II) oxide, FeO, and iron (iron) (III) oxide, Fe2O3) The cobalt oxides include cobalt (II) oxide, CoO and cobalt (III) oxide, Co2O3) The nickel oxide includes nickel (II) oxide, NiO and nickel (III) oxide, Ni2O3) Etc., the copper oxide comprises copper (I) oxide, Cu2O), copper (ii) oxide (CuO), copper peroxide (CuO)2) And copper (III) oxide (Cu)2O3) And the like. In this embodiment, the worker can also mix oxides of a plurality of transition metal elements as the non-ferrous metal oxide.
Then, in the laser sintering step S2, the worker can use a laser with a wavelength of 400-1200 nm, preferably, the worker can use a laser with a wavelength of 1000-1200 nm to perform laser sintering on the bioactive glass, so that the bioactive glass is melted by the radiation energy (laser) of the laser to form a blank (blank). In this embodiment, the laser may be a neodymium-doped yttrium aluminum garnet laser (Yd: YAG laser), which has a general operating wavelength of about 1064nm and can convert the laser wavelength to a visible light region through a nonlinear crystal, so that the laser can be effectively absorbed by the non-ferrous metal oxide in the bioactive glass, thereby increasing the forming rate of the bioactive glass.
Also, the laser may have a radiation energy density (radiation energy density) which may be in a range of 1 to 3cal/cm2When the radiation energy density is too low, the radiation energy generated by the laser is not enough to make the bioactive glass becomeThe shaped raw blank is burnt (out) when the radiant energy density is too high.
After the bioactive glass is formed into the blank, the heat treatment step S3 is performed to perform a heat treatment on the blank at a high temperature to remove the binder in the blank, so as to obtain a bioactive glass three-dimensional product made of the bioactive glass, wherein the bioactive glass three-dimensional product has good structural strength because of the reduced amount of the binder without residual excess holes. In the present embodiment, the heat treatment is performed on the blank at 1050-1150 ℃ for 1-3 hours, and the duration of the heat treatment can be selected according to the size of the blank, so as to remove the excess binder. In this case, the bioactive glass three-dimensional product may include 1 to 10% by weight of a colored metal oxide, and may further include 35 to 40% by weight of silica, 5 to 10% by weight of sodium oxide, 39 to 43% by weight of calcium oxide, and 10 to 15% by weight of phosphorus pentoxide.
To prove that the bioactive glass can be formed into the bioactive glass three-dimensional product by the selective laser sintering method, and the bioactive glass three-dimensional product has good biocompatibility and structural strength, the following tests are carried out:
(A) adjustment of laser parameters
This test is carried out with a composition comprising 5% by weight of iron oxide (Fe)2O3) Is tested at 1, 1.5, 2, 2.5 or 3cal/cm, respectively2The laser sintering is performed with power of 3, 4, 5W, and the result is shown in FIG. 2. although the change of power has no obvious influence on the laser sintering result, the forming effect is improved with the increase of the radiation energy density, wherein the radiation energy density is 2.5cal/cm2The effect of (2) is good.
(B) Effect of Heat treatment temperature on structural Strength
The test is also carried out so as to contain 5% by weight of iron oxide (Fe)2O3) The bioactive glass of (1) was tested, after the formation of the crude blank, the crude blank was heat-treated at 1050 ℃ (group B1), 1100 ℃ (group B2), 1150 ℃ (group B3) for 1 hour, and then the compressive strength (compressive strength) of the bioactive glass three-dimensional product finally obtained was tested, and as a result, as shown in fig. 3, the compressive strength of the bioactive glass three-dimensional product obtained by heat-treating at 1100 ℃ was the best, and the compressive strength of the bioactive glass three-dimensional product obtained by heat-treating at 1050 ℃ was the worst, only about 10MPa, but still satisfied the compressive strength (4-12 MPa) of human cancellous bone.
In addition, as shown in fig. 4a to 4c, the bioactive glass three-dimensional products of group B1 have more pores, and the bioactive glass three-dimensional products of group B3 have larger crystal grains (crystal grains), respectively, as a result of analyzing the bioactive glass three-dimensional products of groups B1 to B3 by Scanning Electron Microscope (SEM).
(C) Effect of three-dimensional articles of bioactive glass containing iron on cell viability
The test is also carried out so as to contain 5% by weight of iron oxide (Fe)2O3) After the crude embryo is formed, the crude embryo is respectively treated with heat for 1 hour at the temperature of 1050 ℃ (group C3), 1100 ℃ (group C4) and 1150 ℃ (group C5) so as to obtain bioactive glass three-dimensional products of groups C3-C5; in addition, a bioactive glass three-dimensional product made of Zinc Dithiocarbamate (ZDEC) and High Density Polyethylene (HDPE) is used as a positive and negative control group, Zinc dithiocarbamate is a material known to be cytotoxic to cells, and high density polyethylene is a material known to be non-cytotoxic to cells, the bioactive glass three-dimensional product of groups C1-C5 is immersed in a cell culture solution, and after a reaction in a 37 ℃ water bath for 72 hours, the cells are cultured for 24 hours with the cell culture solution, and finally, an MTT test (3- (4, 5-dimethylthiozol-2-yl) -2,5-diphenyltetrazolium bromide, MTay)To test the cell viability of each group of cells; the C0 group cells were also used as a comparison, without any bioactive glass three-dimensional preparations added.
Referring to fig. 5, the bioactive glass three-dimensional products of groups C4 and C5 obtained by heat-treating the crude embryo at 1100-1150 ℃ do not affect the survival of cells, indicating that the bioactive glass three-dimensional products should have good biocompatibility.
(D) Influence of iron content
The test is carried out with iron oxide (Fe) in a proportion of 1%, 5% or 10% by weight2O3) The bioactive glass of (1) was tested, and color change, integrity (integrity), and structural strength of the resulting three-dimensional product of the bioactive glass were observed as evaluation criteria, and the results are shown in table 1.
TABLE 1 evaluation chart of three-dimensional bioactive glass products of each group in the test
1: 0 score means no or burnt (burn out); score 1 indicates slightly; score 2 indicates light; score 3 indicates medium; score 4 indicates severity.
2: 0 to 5 points of no moldability; 6 to 9 points represent weak formability; and (3) a sufficient moldability of 10 to 15 points.
As shown in Table 1, the three-dimensional bioactive glass products of group D3, in which the amount of iron oxide added was 5%, were excellent in moldability.
(E) Influence of copper content
The test was conducted using a bioactive glass containing 0.5%, 1% or 2% by weight of copper oxide (CuO), and the resulting bioactive glass three-dimensional article was observed for color change, integrity, structural strength as evaluation criteria, and the results are shown in table 2.
TABLE 2 evaluation chart of bioactive glass three-dimensional products of each group in the test
1: 0 score means no or burnt (burn out); score 1 indicates slightly; score 2 indicates light; score 3 indicates medium; score 4 indicates severity.
2: 0 to 5 points of no moldability; 6 to 9 points represent weak formability; and (3) a sufficient moldability of 10 to 15 points.
As shown in Table 2, the formability of the bioactive glass three-dimensional product of groups E3 and E4 was preferably such that the amount of copper oxide added was 1-2%.
(F) Effect of three-dimensional articles of copper-containing bioactive glass on cell viability
The test was also carried out with a bioactive glass comprising, in weight percent, 0.5% (group F3), 1% (group F4) or 2% (group F5) copper oxide (CuO), after forming the raw blank, the raw blank was heat-treated at 1050 ℃ for 1 hour to obtain bioactive glass three-dimensional articles of groups F3 to F5; in addition, a bioactive glass three-dimensional product made of Zinc dithiocarbamate (ZDEC for short) and High Density Polyethylene (HDPE) is used as a positive control group and a negative control group, Zinc dithiocarbamate is a material known to have cytotoxicity to cells, and high density polyvinyl chloride is a material known to have no cytotoxicity to cells, the bioactive glass three-dimensional product of groups F1-F5 is soaked in a cell culture solution, reacts in a water bath at 37 ℃ for 72 hours, then the cells are cultured for 24 hours by the cell culture solution, and finally, an MTT test is carried out to test the cell survival rate of each group of cells; in addition, the cells of group F0, to which no three-dimensional preparation of bioactive glass had been added, were used as a comparison.
Referring to fig. 6, the bioactive glass three-dimensional product of groups F3 and F4 containing 0.5-1 wt% of copper oxide does not affect the survival of cells, indicating that the bioactive glass three-dimensional product should have good biocompatibility.
In summary, the amount of the binder is reduced to 10-30% by adding the non-ferrous metal oxide, so that when the bioactive glass is used as the material powder for the selective laser sintering method, the pores on the formed bioactive glass three-dimensional product after degreasing and sintering can be reduced, the structural strength of the formed bioactive glass three-dimensional product is improved, and the bioactive glass has the effects of the invention.
Furthermore, according to the manufacturing method of the bioactive glass three-dimensional product, the bioactive glass is used as the material powder, the radiation energy released by the laser with the wavelength between 400 nm and 1200nm can be effectively absorbed by the bioactive glass, the adhesion forming effect of the bioactive glass is improved, the generation of holes after high-temperature degreasing and sintering is reduced, and the bioactive glass three-dimensional product formed by the bioactive glass has good biocompatibility and good structural strength, so that the effect of the invention is achieved.
Although the present invention has been described with reference to the above preferred embodiments, it should be understood that various changes and modifications can be made without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (9)
1. A bioactive glass, comprising: 60-80% of a substrate, 10-30% of a binder and 1-10% of a non-ferrous metal oxide by weight percentage, wherein the non-ferrous metal oxide contains a metal element.
2. The bioactive glass of claim 1 wherein the metallic element is a transition metal element.
3. The bioactive glass of claim 2 wherein the transition metal element is selected from the group consisting of one or more of vanadium, chromium, iron, cobalt, nickel and copper.
4. The bioactive glass of any of claims 1 to 3 wherein the substrate comprises a silicon oxide, a sodium oxide, a calcium oxide and a phosphorus oxide.
5. The bioactive glass of claim 4 wherein the matrix comprises, by weight, 35-40% silica, 5-10% sodium oxide, 39-43% calcium oxide and 10-15% phosphorus pentoxide.
6. A method of making a three-dimensional article of bioactive glass comprising:
providing a bioactive glass as claimed in any of claims 1 to 5;
performing laser sintering on the bioactive glass by using a laser with a wavelength of 400-1200 nm to form a rough blank; and
and carrying out heat treatment on the rough blank, and removing the binder in the rough blank to obtain a bioactive glass three-dimensional product.
7. The method of claim 6, wherein the heat treatment is performed on the blank at 1050-1150 ℃ for 1-3 hours.
8. The method for producing a three-dimensional bioactive glass product according to claim 6, wherein the amount of the bioactive glass is 1 to 3cal/cm2The laser sintering is performed at the radiation energy density.
9. The method of claim 6, wherein the laser used to laser sinter the bioactive glass is a neodymium-doped yttrium aluminum garnet laser.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000007349A (en) * | 1998-06-18 | 2000-01-11 | Asahi Glass Co Ltd | Synthetic silica glass optical member and its production |
| CN1562834A (en) * | 2004-03-26 | 2005-01-12 | 中国科学院上海硅酸盐研究所 | Degradable porous glass rack having bioactivity and preparation method |
| CN101108769A (en) * | 2006-07-19 | 2008-01-23 | 联合大学 | Method for improving fluorescent strength of oxide compound glass |
| US20100133242A1 (en) * | 2007-05-07 | 2010-06-03 | Chemische Fabrik Budenheim Kg | Laser pigments for ceramics |
| WO2010071176A1 (en) * | 2008-12-19 | 2010-06-24 | 旭硝子株式会社 | Glass member with seal-bonding material layer and method for producing same, and electronic device and method for manufacturing same |
| US20100304513A1 (en) * | 2009-05-28 | 2010-12-02 | Kelvin Nguyen | Method for forming an organic light emitting diode device |
-
2020
- 2020-11-18 CN CN202011295270.1A patent/CN114516720A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000007349A (en) * | 1998-06-18 | 2000-01-11 | Asahi Glass Co Ltd | Synthetic silica glass optical member and its production |
| CN1562834A (en) * | 2004-03-26 | 2005-01-12 | 中国科学院上海硅酸盐研究所 | Degradable porous glass rack having bioactivity and preparation method |
| CN101108769A (en) * | 2006-07-19 | 2008-01-23 | 联合大学 | Method for improving fluorescent strength of oxide compound glass |
| US20100133242A1 (en) * | 2007-05-07 | 2010-06-03 | Chemische Fabrik Budenheim Kg | Laser pigments for ceramics |
| WO2010071176A1 (en) * | 2008-12-19 | 2010-06-24 | 旭硝子株式会社 | Glass member with seal-bonding material layer and method for producing same, and electronic device and method for manufacturing same |
| US20100304513A1 (en) * | 2009-05-28 | 2010-12-02 | Kelvin Nguyen | Method for forming an organic light emitting diode device |
Non-Patent Citations (1)
| Title |
|---|
| KRISHNA C.R. KOLAN 等: "Effect of materrial, process parameters, and simulated body fluids on mechanical properties of 13-93 bioactive glass porous constructs made by selective laser sintering", 《SCIVERSE SCIENCEDIRECT》, pages 14 - 23 * |
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