CN111592274A - Oxide ceramic reinforced light-cured material for making three-dimensional objects - Google Patents
Oxide ceramic reinforced light-cured material for making three-dimensional objects Download PDFInfo
- Publication number
- CN111592274A CN111592274A CN202010483088.2A CN202010483088A CN111592274A CN 111592274 A CN111592274 A CN 111592274A CN 202010483088 A CN202010483088 A CN 202010483088A CN 111592274 A CN111592274 A CN 111592274A
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- CN
- China
- Prior art keywords
- oxide ceramic
- light
- accelerant
- parts
- acrylate
- 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
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- 239000011224 oxide ceramic Substances 0.000 title claims abstract description 61
- 229910052574 oxide ceramic Inorganic materials 0.000 title claims abstract description 59
- 239000000463 material Substances 0.000 title claims abstract description 47
- 239000000843 powder Substances 0.000 claims abstract description 65
- 238000001723 curing Methods 0.000 claims abstract description 22
- 230000009974 thixotropic effect Effects 0.000 claims abstract description 18
- 238000000016 photochemical curing Methods 0.000 claims abstract description 15
- 239000003085 diluting agent Substances 0.000 claims abstract description 12
- 239000005416 organic matter Substances 0.000 claims abstract description 12
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 11
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 11
- 238000004519 manufacturing process Methods 0.000 claims abstract description 10
- 239000000654 additive Substances 0.000 claims abstract description 8
- 230000000996 additive effect Effects 0.000 claims abstract description 8
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 8
- 230000031700 light absorption Effects 0.000 claims abstract description 8
- 239000002994 raw material Substances 0.000 claims abstract description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 24
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 20
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 18
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 18
- 238000000498 ball milling Methods 0.000 claims description 18
- 238000002156 mixing Methods 0.000 claims description 18
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 9
- 239000002202 Polyethylene glycol Substances 0.000 claims description 8
- 229920001223 polyethylene glycol Polymers 0.000 claims description 8
- 239000000377 silicon dioxide Substances 0.000 claims description 7
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- -1 polyepoxyacrylate Polymers 0.000 claims description 6
- 238000001291 vacuum drying Methods 0.000 claims description 6
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 5
- HVVWZTWDBSEWIH-UHFFFAOYSA-N [2-(hydroxymethyl)-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(COC(=O)C=C)COC(=O)C=C HVVWZTWDBSEWIH-UHFFFAOYSA-N 0.000 claims description 5
- 239000006096 absorbing agent Substances 0.000 claims description 5
- PCLLJCFJFOBGDE-UHFFFAOYSA-N (5-bromo-2-chlorophenyl)methanamine Chemical compound NCC1=CC(Br)=CC=C1Cl PCLLJCFJFOBGDE-UHFFFAOYSA-N 0.000 claims description 4
- 229920000058 polyacrylate Polymers 0.000 claims description 4
- 229920000909 polytetrahydrofuran Polymers 0.000 claims description 4
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 claims description 3
- HWSSEYVMGDIFMH-UHFFFAOYSA-N 2-[2-[2-(2-methylprop-2-enoyloxy)ethoxy]ethoxy]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOCCOCCOC(=O)C(C)=C HWSSEYVMGDIFMH-UHFFFAOYSA-N 0.000 claims description 3
- FZSHSWCZYDDOCK-UHFFFAOYSA-N 2-methylprop-2-enoic acid;oxolane Chemical compound C1CCOC1.CC(=C)C(O)=O FZSHSWCZYDDOCK-UHFFFAOYSA-N 0.000 claims description 3
- 239000004593 Epoxy Substances 0.000 claims description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 claims description 3
- RZLXRFDFCORTQM-UHFFFAOYSA-N OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OCCn1c(=O)n(CCO)c(=O)n(CCO)c1=O Chemical compound OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OCCn1c(=O)n(CCO)c(=O)n(CCO)c1=O RZLXRFDFCORTQM-UHFFFAOYSA-N 0.000 claims description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 3
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 3
- IAXXETNIOYFMLW-COPLHBTASA-N [(1s,3s,4s)-4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl] 2-methylprop-2-enoate Chemical compound C1C[C@]2(C)[C@@H](OC(=O)C(=C)C)C[C@H]1C2(C)C IAXXETNIOYFMLW-COPLHBTASA-N 0.000 claims description 3
- VEBCLRKUSAGCDF-UHFFFAOYSA-N ac1mi23b Chemical compound C1C2C3C(COC(=O)C=C)CCC3C1C(COC(=O)C=C)C2 VEBCLRKUSAGCDF-UHFFFAOYSA-N 0.000 claims description 3
- 150000001412 amines Chemical class 0.000 claims description 3
- QUZSUMLPWDHKCJ-UHFFFAOYSA-N bisphenol A dimethacrylate Chemical class C1=CC(OC(=O)C(=C)C)=CC=C1C(C)(C)C1=CC=C(OC(=O)C(C)=C)C=C1 QUZSUMLPWDHKCJ-UHFFFAOYSA-N 0.000 claims description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 3
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 claims description 3
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Chemical compound CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 claims description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 3
- 229940119545 isobornyl methacrylate Drugs 0.000 claims description 3
- 239000000395 magnesium oxide Substances 0.000 claims description 3
- RZFODFPMOHAYIR-UHFFFAOYSA-N oxepan-2-one;prop-2-enoic acid Chemical compound OC(=O)C=C.O=C1CCCCCO1 RZFODFPMOHAYIR-UHFFFAOYSA-N 0.000 claims description 3
- 229920000728 polyester Polymers 0.000 claims description 3
- 229920000570 polyether Polymers 0.000 claims description 3
- 229920001451 polypropylene glycol Polymers 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 claims description 3
- 229940124543 ultraviolet light absorber Drugs 0.000 claims description 3
- 239000006097 ultraviolet radiation absorber Substances 0.000 claims description 3
- 239000011787 zinc oxide Substances 0.000 claims description 3
- ZRFJGMIABGDKBZ-UHFFFAOYSA-N C(C(=C)C)(=O)OC(C(C)(COC(C(=C)C)=O)C)OCCC Chemical compound C(C(=C)C)(=O)OC(C(C)(COC(C(=C)C)=O)C)OCCC ZRFJGMIABGDKBZ-UHFFFAOYSA-N 0.000 claims 1
- 238000010146 3D printing Methods 0.000 abstract description 7
- 238000000034 method Methods 0.000 abstract description 7
- 229920005989 resin Polymers 0.000 description 15
- 239000011347 resin Substances 0.000 description 15
- 239000000919 ceramic Substances 0.000 description 10
- 239000011259 mixed solution Substances 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- 235000019441 ethanol Nutrition 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- NJWGQARXZDRHCD-UHFFFAOYSA-N 2-methylanthraquinone Chemical compound C1=CC=C2C(=O)C3=CC(C)=CC=C3C(=O)C2=C1 NJWGQARXZDRHCD-UHFFFAOYSA-N 0.000 description 4
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 4
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 4
- 239000012965 benzophenone Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 235000012239 silicon dioxide Nutrition 0.000 description 4
- LNBMZFHIYRDKNS-UHFFFAOYSA-N 2,2-dimethoxy-1-phenylethanone Chemical compound COC(OC)C(=O)C1=CC=CC=C1 LNBMZFHIYRDKNS-UHFFFAOYSA-N 0.000 description 3
- NLGDWWCZQDIASO-UHFFFAOYSA-N 2-hydroxy-1-(7-oxabicyclo[4.1.0]hepta-1,3,5-trien-2-yl)-2-phenylethanone Chemical compound OC(C(=O)c1cccc2Oc12)c1ccccc1 NLGDWWCZQDIASO-UHFFFAOYSA-N 0.000 description 3
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- HJIAMFHSAAEUKR-UHFFFAOYSA-N (2-hydroxyphenyl)-phenylmethanone Chemical class OC1=CC=CC=C1C(=O)C1=CC=CC=C1 HJIAMFHSAAEUKR-UHFFFAOYSA-N 0.000 description 2
- QZPSOSOOLFHYRR-UHFFFAOYSA-N 3-hydroxypropyl prop-2-enoate Chemical compound OCCCOC(=O)C=C QZPSOSOOLFHYRR-UHFFFAOYSA-N 0.000 description 2
- ZCILGMFPJBRCNO-UHFFFAOYSA-N 4-phenyl-2H-benzotriazol-5-ol Chemical class OC1=CC=C2NN=NC2=C1C1=CC=CC=C1 ZCILGMFPJBRCNO-UHFFFAOYSA-N 0.000 description 2
- VMRIVYANZGSGRV-UHFFFAOYSA-N 4-phenyl-2h-triazin-5-one Chemical class OC1=CN=NN=C1C1=CC=CC=C1 VMRIVYANZGSGRV-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N N-phenyl amine Natural products NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- HLJYBXJFKDDIBI-UHFFFAOYSA-N O=[PH2]C(=O)C1=CC=CC=C1 Chemical compound O=[PH2]C(=O)C1=CC=CC=C1 HLJYBXJFKDDIBI-UHFFFAOYSA-N 0.000 description 2
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- 235000008411 Sumatra benzointree Nutrition 0.000 description 2
- ULQMPOIOSDXIGC-UHFFFAOYSA-N [2,2-dimethyl-3-(2-methylprop-2-enoyloxy)propyl] 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(C)(C)COC(=O)C(C)=C ULQMPOIOSDXIGC-UHFFFAOYSA-N 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 description 2
- 150000004056 anthraquinones Chemical class 0.000 description 2
- WURBFLDFSFBTLW-UHFFFAOYSA-N benzil Chemical compound C=1C=CC=CC=1C(=O)C(=O)C1=CC=CC=C1 WURBFLDFSFBTLW-UHFFFAOYSA-N 0.000 description 2
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- 229910052809 inorganic oxide Inorganic materials 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 229960003742 phenol Drugs 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 229910052814 silicon oxide Inorganic materials 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 229920001187 thermosetting polymer Polymers 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- JNELGWHKGNBSMD-UHFFFAOYSA-N xanthone Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3OC2=C1 JNELGWHKGNBSMD-UHFFFAOYSA-N 0.000 description 2
- PDGQDNBBPDKZRE-UHFFFAOYSA-N (1-aminocyclohexa-2,4-dien-1-yl)-phenylmethanone Chemical compound C=1C=CC=CC=1C(=O)C1(N)CC=CC=C1 PDGQDNBBPDKZRE-UHFFFAOYSA-N 0.000 description 1
- VVKZEEWRYIIUOF-UHFFFAOYSA-N (1-hydroxycyclohexa-2,4-dien-1-yl)-phenylmethanone Chemical compound C=1C=CC=CC=1C(=O)C1(O)CC=CC=C1 VVKZEEWRYIIUOF-UHFFFAOYSA-N 0.000 description 1
- LPGGIATUXYOFDU-UHFFFAOYSA-N (2-hydroxy-3-propan-2-ylphenyl)-phenylmethanone Chemical compound CC(C)C1=CC=CC(C(=O)C=2C=CC=CC=2)=C1O LPGGIATUXYOFDU-UHFFFAOYSA-N 0.000 description 1
- QRWAIZJYJNLOPG-UHFFFAOYSA-N (2-oxo-1,2-diphenylethyl) acetate Chemical compound C=1C=CC=CC=1C(OC(=O)C)C(=O)C1=CC=CC=C1 QRWAIZJYJNLOPG-UHFFFAOYSA-N 0.000 description 1
- MSAHTMIQULFMRG-UHFFFAOYSA-N 1,2-diphenyl-2-propan-2-yloxyethanone Chemical compound C=1C=CC=CC=1C(OC(C)C)C(=O)C1=CC=CC=C1 MSAHTMIQULFMRG-UHFFFAOYSA-N 0.000 description 1
- ZANRHLGMHYOWQU-UHFFFAOYSA-N 1,5-bis[4-(2-hydroxyethoxy)phenyl]-2,4-dimethylpentan-3-one Chemical compound C=1C=C(OCCO)C=CC=1CC(C)C(=O)C(C)CC1=CC=C(OCCO)C=C1 ZANRHLGMHYOWQU-UHFFFAOYSA-N 0.000 description 1
- PWMWNFMRSKOCEY-UHFFFAOYSA-N 1-Phenyl-1,2-ethanediol Chemical compound OCC(O)C1=CC=CC=C1 PWMWNFMRSKOCEY-UHFFFAOYSA-N 0.000 description 1
- BOCJQSFSGAZAPQ-UHFFFAOYSA-N 1-chloroanthracene-9,10-dione Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C=CC=C2Cl BOCJQSFSGAZAPQ-UHFFFAOYSA-N 0.000 description 1
- CERJZAHSUZVMCH-UHFFFAOYSA-N 2,2-dichloro-1-phenylethanone Chemical compound ClC(Cl)C(=O)C1=CC=CC=C1 CERJZAHSUZVMCH-UHFFFAOYSA-N 0.000 description 1
- KWVGIHKZDCUPEU-UHFFFAOYSA-N 2,2-dimethoxy-2-phenylacetophenone Chemical compound C=1C=CC=CC=1C(OC)(OC)C(=O)C1=CC=CC=C1 KWVGIHKZDCUPEU-UHFFFAOYSA-N 0.000 description 1
- KMNCBSZOIQAUFX-UHFFFAOYSA-N 2-ethoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OCC)C(=O)C1=CC=CC=C1 KMNCBSZOIQAUFX-UHFFFAOYSA-N 0.000 description 1
- SJEBAWHUJDUKQK-UHFFFAOYSA-N 2-ethylanthraquinone Chemical compound C1=CC=C2C(=O)C3=CC(CC)=CC=C3C(=O)C2=C1 SJEBAWHUJDUKQK-UHFFFAOYSA-N 0.000 description 1
- QPXVRLXJHPTCPW-UHFFFAOYSA-N 2-hydroxy-2-methyl-1-(4-propan-2-ylphenyl)propan-1-one Chemical compound CC(C)C1=CC=C(C(=O)C(C)(C)O)C=C1 QPXVRLXJHPTCPW-UHFFFAOYSA-N 0.000 description 1
- XMLYCEVDHLAQEL-UHFFFAOYSA-N 2-hydroxy-2-methyl-1-phenylpropan-1-one Chemical compound CC(C)(O)C(=O)C1=CC=CC=C1 XMLYCEVDHLAQEL-UHFFFAOYSA-N 0.000 description 1
- BQZJOQXSCSZQPS-UHFFFAOYSA-N 2-methoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OC)C(=O)C1=CC=CC=C1 BQZJOQXSCSZQPS-UHFFFAOYSA-N 0.000 description 1
- UMWZLYTVXQBTTE-UHFFFAOYSA-N 2-pentylanthracene-9,10-dione Chemical compound C1=CC=C2C(=O)C3=CC(CCCCC)=CC=C3C(=O)C2=C1 UMWZLYTVXQBTTE-UHFFFAOYSA-N 0.000 description 1
- AXYQEGMSGMXGGK-UHFFFAOYSA-N 2-phenoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(=O)C(C=1C=CC=CC=1)OC1=CC=CC=C1 AXYQEGMSGMXGGK-UHFFFAOYSA-N 0.000 description 1
- YTPSFXZMJKMUJE-UHFFFAOYSA-N 2-tert-butylanthracene-9,10-dione Chemical compound C1=CC=C2C(=O)C3=CC(C(C)(C)C)=CC=C3C(=O)C2=C1 YTPSFXZMJKMUJE-UHFFFAOYSA-N 0.000 description 1
- SXNICUVVDOTUPD-UHFFFAOYSA-N CC1=CC(C)=CC(C)=C1C(=O)P(=O)C1=CC=CC=C1 Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)C1=CC=CC=C1 SXNICUVVDOTUPD-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- BDAHDQGVJHDLHQ-UHFFFAOYSA-N [2-(1-hydroxycyclohexyl)phenyl]-phenylmethanone Chemical compound C=1C=CC=C(C(=O)C=2C=CC=CC=2)C=1C1(O)CCCCC1 BDAHDQGVJHDLHQ-UHFFFAOYSA-N 0.000 description 1
- RVWADWOERKNWRY-UHFFFAOYSA-N [2-(dimethylamino)phenyl]-phenylmethanone Chemical compound CN(C)C1=CC=CC=C1C(=O)C1=CC=CC=C1 RVWADWOERKNWRY-UHFFFAOYSA-N 0.000 description 1
- 150000001251 acridines Chemical class 0.000 description 1
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- 238000005452 bending Methods 0.000 description 1
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- 150000008366 benzophenones Chemical class 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
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- 239000000945 filler Substances 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
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- YRHRIQCWCFGUEQ-UHFFFAOYSA-N thioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3SC2=C1 YRHRIQCWCFGUEQ-UHFFFAOYSA-N 0.000 description 1
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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
- C04B26/00—Compositions of mortars, concrete or artificial stone, containing only organic binders, e.g. polymer or resin concrete
- C04B26/02—Macromolecular compounds
- C04B26/04—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C04B26/06—Acrylates
-
- 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
- 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
- C04B20/00—Use of materials as fillers for mortars, concrete or artificial stone according to more than one of groups C04B14/00 - C04B18/00 and characterised by shape or grain distribution; Treatment of materials according to more than one of the groups C04B14/00 - C04B18/00 specially adapted to enhance their filling properties in mortars, concrete or artificial stone; Expanding or defibrillating materials
- C04B20/02—Treatment
- C04B20/023—Chemical treatment
-
- C—CHEMISTRY; METALLURGY
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Abstract
The invention provides an oxide ceramic reinforced light curing material for manufacturing a three-dimensional object, which comprises the following raw materials in parts by mass: 100 parts of photocuring organic matter, 20-400 parts of accelerant modified oxide ceramic powder and 0.12-30 parts of additive; the light-cured organic matter comprises a light-cured oligomer and a reactive diluent, and the mass ratio of the light-cured oligomer to the reactive diluent is 20-90: 10-80; the accelerant comprises a thixotropic accelerant and a strength accelerant, and the mass ratio of the thixotropic accelerant to the strength accelerant to the oxide ceramic powder is 0.5-10: 100; the additive comprises a photoinitiator, a light absorption agent and an antioxidant, wherein the mass ratio of the photoinitiator to the light absorption agent to the antioxidant to the photocuring organic matter is 0.1-10: 0.01-10: 100. The light-cured material has specific thixotropy, and has the characteristic suitable for a 3D printing process.
Description
Technical Field
The invention relates to the field of 3D printing, in particular to an oxide ceramic reinforced photocuring material for manufacturing a three-dimensional object.
Background
3D printing is a molding process for manufacturing solid three-dimensional objects by layering liquid (powder) materials with computer aided design and control, which has been developed to date with the best molding precision in Stereolithography (SLA) and Digital Light Processing (DLP). The SLA/DLP 3d forming technology uses liquid light-cured resin, and the liquid light-cured resin is cured by radiation under light energy with specific wavelength, and becomes a solid cross-linked structure, and the material essentially belongs to thermosetting plastic materials, has higher cross-linking density than the traditional thermosetting cross-linked structure materials, has hard and brittle natural defects, poor fatigue resistance and poor ageing resistance, and cannot be applied to terminal products. The traditional dental prosthesis material is prepared by adding 70-90 wt% of ceramic reinforced material into photosensitive resin, and has the properties of toughness, wear resistance and the like. However, the dental photosensitive resin has a high viscosity and is difficult to use for 3D printing.
Disclosure of Invention
In view of the problems in the background art, an object of the present invention is to provide an oxide ceramic reinforced photocurable material for fabricating a three-dimensional object, which has a characteristic thixotropy that imparts characteristics suitable for a 3D printing process, has an extremely small shrinkage rate after photocuring molding, and has high toughness and high wear resistance similar to those of dental photosensitive resins, and a three-dimensional object fabricated therefrom can be used as an end product.
In order to achieve the purpose, the invention provides an oxide ceramic reinforced light-cured material for manufacturing a three-dimensional object, which comprises the following raw materials in parts by mass: 100 parts of photocuring organic matter, 20-400 parts of accelerant modified oxide ceramic powder and 0.12-30 parts of additive; the light-cured organic matter comprises a light-cured oligomer and a reactive diluent, and the mass ratio of the light-cured oligomer to the reactive diluent is 20-90: 10-80; the accelerant comprises a thixotropic accelerant and a strength accelerant, wherein the mass ratio of the thixotropic accelerant to the strength accelerant to the oxide ceramic powder is 0.5-10: 100; the additive comprises a photoinitiator, a light absorption agent and an antioxidant, wherein the mass ratio of the photoinitiator to the light absorption agent to the antioxidant to the photocuring organic matter is 0.1-10: 0.01-10: 100.
Further, the light-cured oligomer comprises one or more of polyacrylate, polyepoxy acrylate, polyester acrylate, polyether acrylate and polyurethane acrylate.
Further, the reactive diluent comprises one or more of dicyclopentadiene methacrylate, tetrahydrofuran methacrylate, diphenoxyethyl acrylate, isobornyl methacrylate, caprolactone acrylate, trimethylolpropane formal acrylate, cyclohexane dimethanol diacrylate, ethoxylated bisphenol A dimethacrylate, triethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, (propylene oxide) neopentyl glycol dimethacrylate, tricyclodecane dimethanol diacrylate, tris (2-hydroxyethyl) isocyanuric acid triacrylate and pentaerythritol triacrylate.
Further, the oxide ceramic powder comprises at least one of silicon dioxide, aluminum oxide, zirconium oxide, magnesium oxide and zinc oxide.
Further, the thixotropic accelerator is one or more of polyethylene glycol, polypropylene glycol and polytetrahydrofuran.
Further, the strength promoter comprises one or more of hydroxyl functional group acrylate, carboxyl functional group acrylate and epoxy functional group acrylate.
Further, the photoinitiator is a free radical photoinitiator.
Further, the light absorber is an organic ultraviolet light absorber.
Further, the antioxidant comprises one or more of hindered amine and hindered phenol.
Further, the preparation method of the accelerant modified oxide ceramic powder comprises the following steps: (1) mixing oxide ceramic powder and a thixotropic accelerant according to a mass ratio, carrying out ball milling for 0.5-1h, and carrying out vacuum drying at 100-110 ℃ after ball milling to obtain pretreated oxide ceramic powder; (2) dissolving a strength promoter according to the mass ratio of 10-30: 100 to ethanol, mixing the strength promoter and the pretreated oxide ceramic powder in a ball mill, continuously ball-milling at 120-150 ℃ to obtain dry dispersed powder, and naturally cooling to obtain promoter-modified oxide ceramic powder.
The invention has the following beneficial technical effects:
it is known to those skilled in the art that it is not difficult to add a large amount of inorganic oxide ceramic powder to the photosensitive resin, but in general, a large amount of inorganic inert powder is added because of poor dispersibility, which not only greatly deteriorates the viscosity uniformity of the photosensitive resin, but also causes poor thixotropy, which is not conducive to processing, but also greatly reduces the strength of the photosensitive resin after curing. According to the invention, the oxide ceramic powder is modified by a unique process through a functional thixotropic accelerant and a strength accelerant creatively, so that the liquid photosensitive resin still has good thixotropy-shear thinning after a large amount of modified oxide ceramic powder is added, the force applied to the photocuring material when the 3D printing platform falls is used for promoting the viscosity of the material to be reduced, and the 3D printing process can be smoothly carried out; meanwhile, the strength promoter and the thixotropic promoter can react to a certain degree, and oxide ceramic powder is attached and wrapped in sequence, so that a certain active functional group is endowed to the surface of the inorganic ceramic oxide powder, and the inorganic ceramic oxide powder can participate in the reaction during the curing of the photosensitive resin, thereby greatly improving the mechanical strength of the product.
Therefore, the modified inorganic oxide ceramic powder material is added into the photosensitive resin in a large scale, so that the dispersibility, the compatibility with the photosensitive resin and the binding property of the photosensitive resin are improved, and the inert oxide ceramic material is successfully added in a large scale, so that the photosensitive resin is endowed with low shrinkage, high dimensional stability, high modulus, high hardness, high wear resistance and excellent ageing resistance. Through tests, the three-dimensional object manufactured by the invention has the low volume shrinkage rate of 0.1-1% (the general volume shrinkage rate of the general photosensitive resin is 1-10%), strong and tough mechanical performance characteristics, the tensile strength is 30-90 MPa, the bending strength is 60-150 MPa, the elongation at break is 2-10%, and the mechanical performance index is kept at 70-100% after six months of outdoor weather resistance tests, so that the requirement of the performance index used as a terminal product material is met.
Detailed Description
The present invention will be described in detail with reference to the following embodiments in order to make the aforementioned objects, features and advantages of the invention more comprehensible.
In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention, but the present invention may be practiced in other ways than those specifically described and will be readily apparent to those of ordinary skill in the art without departing from the spirit of the present invention, and therefore the present invention is not limited to the specific embodiments disclosed below.
The oxide ceramic reinforced light-cured material for manufacturing the three-dimensional object comprises the following raw materials in parts by mass: 100 parts of photocuring organic matter, 20-400 parts of accelerant modified oxide ceramic powder and 0.12-30 parts of additive. The light-cured organic matter can comprise a light-cured oligomer and a reactive diluent, and the mass ratio of the light-cured oligomer to the reactive diluent can be 20-90: 10-80; the accelerant can comprise a thixotropic accelerant and a strength accelerant, wherein the mass ratio of the thixotropic accelerant to the strength accelerant to the oxide ceramic powder can be 0.5-10: 100; the additive can comprise a photoinitiator, a light absorption agent and an antioxidant, wherein the mass ratio of the photoinitiator to the light absorption agent to the antioxidant to the photocuring organic matter can be 0.1-10: 0.01-10: 100.
In the oxide ceramic reinforced light-curing material for fabricating a three-dimensional object according to the present invention, the light-curing oligomer may include one or more of polyacrylate, polyepoxyacrylate, polyester acrylate, polyether acrylate and urethane acrylate.
In the oxide ceramic reinforced photocurable material for fabricating a three-dimensional object according to the present invention, the reactive diluent may include one or more of dicyclopentadiene methacrylate, tetrahydrofuran methacrylate, diphenoxyethyl acrylate, isobornyl methacrylate, caprolactone acrylate, trimethylolpropane formal acrylate, cyclohexane dimethanol diacrylate, ethoxylated bisphenol a dimethacrylate, triethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, (propoxylated) neopentyl glycol dimethacrylate, tricyclodecane dimethanol diacrylate, tris (2-hydroxyethyl) isocyanuric acid triacrylate, pentaerythritol triacrylate.
In the oxide ceramic reinforced light-curing material for fabricating a three-dimensional object according to the present invention, the oxide ceramic powder may include at least one of silica, alumina, zirconia, magnesia, and zinc oxide. Wherein the grain diameter of the oxide ceramic powder filler can be 20 nm-5 mu m.
In the oxide ceramic reinforced light-curing material for fabricating a three-dimensional object according to the present invention, the thixotropic accelerator may be one or more of polyethylene glycol, polypropylene glycol, and polytetrahydrofuran. Wherein the molecular weight of the thixotropic accelerator can be 300-1000.
In the oxide ceramic reinforced photocurable material for fabricating a three-dimensional object according to the present invention, the strength promoter may include one or more of a hydroxyl functional acrylate, a carboxyl functional acrylate, and an epoxy functional acrylate.
In the oxide ceramic enhanced photocurable material for fabricating a three-dimensional object according to the present invention, the photoinitiator may be a radical photoinitiator. Wherein, the free radical photoinitiator can comprise one or more of benzoin, acetophenone, benzil ketal, anthraquinone, triphenylphosphine, benzoylphosphine oxide, bisacylphosphine oxide, benzophenone, thioxanthone, xanthone, acridine derivative, phenazine derivative, quinoxaline derivative, 1-phenyl-1, 2-propanedione-2-O-benzoyl oxime, 4- (2-hydroxyethoxy) phenyl- (2-propyl) ketone, 1-aminobenzene and 1-hydroxybenzene ketone. Preferably, the benzoin comprises benzoin ether, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin phenyl ether and benzoin acetate; the acetophenone includes 2, 2-dimethoxyacetophenone and 1, 1-dichloroacetophenone; the benzil ketals include benzil dimethyl ketal and benzil diethyl ketal; the anthraquinone includes 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 1-chloroanthraquinone and 2-amylanthraquinone; the benzoylphosphine oxides include 2,4, 6-trimethylbenzoylphenylphosphine oxide (Luzirin TPO); the benzophenone comprises benzophenone, 4-bis (N, N' -dimethylamino) benzophenone; the 1-aminobenzophenone or 1-hydroxybenzophenone includes 1-hydroxycyclohexyl benzophenone, 2-hydroxyisopropyl benzophenone, phenyl 1-hydroxyisopropyl ketone and 4-isopropyl phenyl 1-hydroxyisopropyl ketone.
In the oxide ceramic enhanced light-curing material for fabricating a three-dimensional object according to the present invention, the light absorber may be an organic ultraviolet light absorber. Wherein the organic UV absorber may comprise one or more of hydroxybenzophenones, hydroxyphenyl benzotriazoles, oxanilides, benzophenones, hydroxyphenyl triazines and/or benzotriazole UV absorbers.
In the oxide ceramic reinforced light-curing material for fabricating three-dimensional objects according to the present invention, the antioxidant may include one or more of hindered amine, hindered phenol.
In the oxide ceramic reinforced photocurable material for fabricating a three-dimensional object according to the present invention, the method for preparing the accelerator-modified oxide ceramic powder may include the steps of: (1) mixing oxide ceramic powder and a thixotropic accelerant according to a mass ratio, carrying out ball milling for 0.5-1h, and carrying out vacuum drying at 100-110 ℃ after ball milling to obtain pretreated oxide ceramic powder; (2) dissolving a strength promoter according to the mass ratio of 10-30: 100 to ethanol, mixing the strength promoter and the pretreated oxide ceramic powder in a ball mill, continuously ball-milling at 120-150 ℃ to obtain dry dispersed powder, and naturally cooling to obtain promoter-modified oxide ceramic powder.
Hereinafter, the oxide ceramic reinforced light-curing material for producing a three-dimensional object according to the present invention will be described in detail with reference to specific examples.
Example one
1. Preparing the silicon dioxide ceramic powder modified by the accelerant: (1) mixing 100 parts of silicon dioxide and 0.5 part of polyethylene glycol according to the parts by weight, adding 10 parts of absolute ethyl alcohol for ball milling for 0.5-1h, and carrying out vacuum drying at 110 ℃ after ball milling to obtain pretreated oxide ceramic powder; (2) mixing and dissolving 0.5 part of hydroxypropyl acrylate with 30 parts of ethanol in parts by weight, mixing the mixture with pretreated silicon oxide powder in a ball mill, continuously ball-milling at the temperature of 120-150 ℃ to obtain dry dispersed powder, and naturally cooling to obtain the accelerator modified silicon dioxide powder.
2. Preparing a silicon dioxide reinforced light curing material: (1) adding 0.1 part of benzoin ether into 50 parts of pentaerythritol triacrylate according to the parts by mass, stirring to completely mix the benzoin ether and the pentaerythritol triacrylate, and then adding 50 parts of urethane acrylate to obtain a primary mixed solution; (2) dividing 20 parts of accelerator-modified silicon dioxide ceramic powder into 5 equal parts by mass, adding the powder one by one under the stirring condition at intervals of 0.5 hours, and stirring the powder for 0.5 hour after all the powder is added to obtain a mixed solution; (3) and finally, sequentially adding 0.01 part of hydroxybenzophenone and 0.01 part of benzoic acid (2, 2, 6, 6-tetramethyl-4-hydroxypiperidine) ester into the mixed solution according to the parts by mass, and uniformly mixing to obtain the silicon oxide ceramic reinforced light curing material for manufacturing the three-dimensional object.
Example two
1. Preparing the promoter modified alumina ceramic powder: (1) mixing 100 parts of alumina and 10 parts of polyethylene glycol according to parts by weight, adding 20 parts of absolute ethyl alcohol for ball milling for 0.5-1h, and carrying out vacuum drying at 110 ℃ after ball milling to obtain pretreated alumina ceramic powder; (2) mixing and dissolving 10 parts by mass of hydroxypropyl acrylate with 50 parts by mass of ethanol, mixing the mixture with pretreated aluminum oxide powder in a ball mill, continuously ball-milling at 150 ℃ to obtain dry dispersed powder, and naturally cooling to obtain the accelerator modified aluminum oxide powder.
2. Preparing an alumina reinforced photocuring material: (1) adding 10 parts by mass of 2, 2-dimethoxyacetophenone into 80 parts by mass of cyclohexane dimethanol diacrylate, stirring to completely mix the 2, 2-dimethoxyacetophenone, and then adding 20 parts by mass of polyepoxy acrylate to obtain a primary mixed solution; (2) dividing 400 parts of accelerator modified alumina powder into 20 equal parts by weight, adding the powder one by one under the stirring condition, wherein the interval time is 0.5 hour, and stirring the powder for 0.5 hour after all the powder is added to obtain a mixed solution; (3) and finally, sequentially adding 10 parts of hydroxyphenyl triazine and 10 parts of 2, 8-di-tert-butyl-4-methylphenol into the mixed solution in parts by mass, and uniformly mixing to obtain the alumina ceramic reinforced light curing material for manufacturing the three-dimensional object.
EXAMPLE III
1. Preparing promoter modified zirconium ceramic powder: (1) mixing 100 parts of zirconia and 5 parts of polytetrahydrofuran according to parts by weight, adding 10 parts of absolute ethyl alcohol for ball milling for 0.8h, and carrying out vacuum drying at 105 ℃ after ball milling to obtain pretreated zirconia ceramic powder; (2) mixing 5 parts by weight of methacrylic acid with 25 parts by weight of ethanol for dissolving, mixing with the pretreated zirconia ceramic powder in a ball mill, continuously ball-milling at 130 ℃ to obtain dry dispersed powder, and naturally cooling to obtain the promoter-modified zirconia powder.
2. Preparation of the zirconia-reinforced photocuring material: (1) adding 5 parts by weight of 2-methylanthraquinone into 10 parts by weight of acrylic caprolactone, stirring to completely mix the two, and then adding 90 parts by weight of polyacrylate to obtain a primary mixed solution; (2) dividing 200 parts of promoter modified zirconia ceramic powder into 10 equal parts by weight, adding the powder one by one under the stirring condition, wherein the interval time is 0.5 hour, and stirring the powder for 0.5 hour after all the powder is added to obtain a mixed solution; (3) and finally, sequentially adding 5 parts of hydroxyphenyl benzotriazole and 5 parts of benzoic acid (2, 2, 6, 6-tetramethyl-4-hydroxypiperidine) ester into the mixed solution according to the parts by mass, and uniformly mixing to obtain the zirconia ceramic reinforced light curing material for manufacturing the three-dimensional object.
Example four
The procedure was as in example 1 except that zirconia was used instead of silica.
Comparative example 1
The photo-curing oligomer, the reactive diluent, the photoinitiator, the zirconia, the thixotropic accelerant, the strength accelerant and other materials are directly mixed and ball-milled for 10 hours at normal temperature, and the specific material types and the proportion are the same as those in the embodiment 3.
Performance testing
Using the photo-curing materials prepared in the above examples and comparative examples, sheet-like test strips 2mm thick, 100mm long and 10mm wide were 3D-printed and subjected to various property tests and evaluations, the results of which are shown in the following table:
as can be seen from the table, the examples have a better combination of properties than the comparative examples, because of better mechanical properties, less shrinkage and weather resistance.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (10)
1. An oxide ceramic reinforced light-cured material for manufacturing a three-dimensional object is characterized by comprising the following raw materials in parts by mass: 100 parts of photocuring organic matter, 20-400 parts of accelerant modified oxide ceramic powder and 0.12-30 parts of additive;
the light-cured organic matter comprises a light-cured oligomer and a reactive diluent, and the mass ratio of the light-cured oligomer to the reactive diluent is 20-90: 10-80;
the accelerant comprises a thixotropic accelerant and a strength accelerant, wherein the mass ratio of the thixotropic accelerant to the strength accelerant to the oxide ceramic powder is 0.5-10: 100;
the additive comprises a photoinitiator, a light absorption agent and an antioxidant, wherein the mass ratio of the photoinitiator to the light absorption agent to the antioxidant to the photocuring organic matter is 0.1-10: 0.01-10: 100.
2. The oxide ceramic reinforced light-curing material for making three-dimensional objects according to claim 1, wherein the light-curing oligomer comprises one or more of polyacrylate, polyepoxyacrylate, polyester acrylate, polyether acrylate and urethane acrylate.
3. The oxide ceramic reinforced light-curing material for fabricating three-dimensional objects as claimed in claim 1, wherein the reactive diluent comprises one or more of dicyclopentadiene methacrylate, tetrahydrofuran methacrylate, diphenoxyethyl acrylate, isobornyl methacrylate, caprolactone acrylate, trimethylolpropane formal acrylate, cyclohexane dimethanol diacrylate, ethoxylated bisphenol a dimethacrylate, triethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, (propyloxy) neopentyl glycol dimethacrylate, tricyclodecane dimethanol diacrylate, tris (2-hydroxyethyl) isocyanuric acid triacrylate, pentaerythritol triacrylate.
4. The oxide ceramic reinforced light-curing material for fabricating three-dimensional objects according to claim 1, wherein the oxide ceramic powder comprises at least one of silica, alumina, zirconia, magnesia and zinc oxide.
5. The oxide ceramic reinforced light-curing material for fabricating three-dimensional objects as claimed in claim 1, wherein the thixotropic promoter is one or more of polyethylene glycol, polypropylene glycol and polytetrahydrofuran.
6. The oxide ceramic reinforced light-curing material for making three-dimensional objects according to claim 1, wherein the strength promoter comprises one or more of hydroxyl functional acrylate, carboxyl functional acrylate and epoxy functional acrylate.
7. The oxide ceramic reinforced photocurable material for producing three-dimensional objects according to claim 1, wherein said photoinitiator is a radical photoinitiator.
8. The oxide ceramic reinforced light-curing material for fabricating three-dimensional objects according to claim 1, wherein the light absorber is an organic ultraviolet light absorber.
9. The oxide ceramic reinforced light-cured material for manufacturing three-dimensional objects as claimed in claim 1, wherein the antioxidant comprises one or more of hindered amine and hindered phenol.
10. The oxide ceramic reinforced light-curing material for fabricating three-dimensional objects as claimed in claim 1, wherein the preparation method of the promoter-modified oxide ceramic powder comprises the following steps:
(1) mixing oxide ceramic powder and a thixotropic accelerant according to a mass ratio, carrying out ball milling for 0.5-1h, and carrying out vacuum drying at 100-110 ℃ after ball milling to obtain pretreated oxide ceramic powder;
(2) dissolving a strength promoter according to the mass ratio of 10-30: 100 to ethanol, mixing the strength promoter and the pretreated oxide ceramic powder in a ball mill, continuously ball-milling at 120-150 ℃ to obtain dry dispersed powder, and naturally cooling to obtain promoter-modified oxide ceramic powder.
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