CN115611656A - Foamed ceramic and preparation method thereof - Google Patents
Foamed ceramic and preparation method thereof Download PDFInfo
- Publication number
- CN115611656A CN115611656A CN202211635966.3A CN202211635966A CN115611656A CN 115611656 A CN115611656 A CN 115611656A CN 202211635966 A CN202211635966 A CN 202211635966A CN 115611656 A CN115611656 A CN 115611656A
- Authority
- CN
- China
- Prior art keywords
- parts
- ceramic
- zirconia
- photocuring
- photosensitive resin
- 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.)
- Pending
Links
- 239000000919 ceramic Substances 0.000 title claims abstract description 186
- 238000002360 preparation method Methods 0.000 title abstract description 15
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims abstract description 203
- 238000000016 photochemical curing Methods 0.000 claims abstract description 69
- 239000002002 slurry Substances 0.000 claims abstract description 69
- 229920005989 resin Polymers 0.000 claims abstract description 61
- 239000011347 resin Substances 0.000 claims abstract description 61
- 238000000034 method Methods 0.000 claims abstract description 38
- 238000010146 3D printing Methods 0.000 claims abstract description 35
- 238000005245 sintering Methods 0.000 claims abstract description 33
- 239000003085 diluting agent Substances 0.000 claims abstract description 27
- HMBNQNDUEFFFNZ-UHFFFAOYSA-N 4-ethenoxybutan-1-ol Chemical compound OCCCCOC=C HMBNQNDUEFFFNZ-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000000463 material Substances 0.000 claims abstract description 23
- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical compound C=CC(=O)OOOC(=O)C=C KCTAWXVAICEBSD-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000004844 aliphatic epoxy resin Substances 0.000 claims abstract description 22
- 239000012952 cationic photoinitiator Substances 0.000 claims abstract description 20
- 239000012949 free radical photoinitiator Substances 0.000 claims abstract description 20
- 239000002994 raw material Substances 0.000 claims abstract description 15
- 230000008569 process Effects 0.000 claims abstract description 14
- 238000004519 manufacturing process Methods 0.000 claims abstract description 11
- 238000002791 soaking Methods 0.000 claims abstract description 9
- 239000000843 powder Substances 0.000 claims description 43
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 36
- 238000007639 printing Methods 0.000 claims description 35
- 239000006260 foam Substances 0.000 claims description 24
- 238000001035 drying Methods 0.000 claims description 23
- 239000000395 magnesium oxide Substances 0.000 claims description 23
- 230000035939 shock Effects 0.000 claims description 20
- 238000007598 dipping method Methods 0.000 claims description 17
- 238000002156 mixing Methods 0.000 claims description 15
- 230000003287 optical effect Effects 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 13
- 238000005096 rolling process Methods 0.000 claims description 12
- FIHBHSQYSYVZQE-UHFFFAOYSA-N 6-prop-2-enoyloxyhexyl prop-2-enoate Chemical group C=CC(=O)OCCCCCCOC(=O)C=C FIHBHSQYSYVZQE-UHFFFAOYSA-N 0.000 claims description 10
- 238000000498 ball milling Methods 0.000 claims description 10
- 239000002245 particle Substances 0.000 claims description 10
- 238000005507 spraying Methods 0.000 claims description 10
- 125000005520 diaryliodonium group Chemical group 0.000 claims description 9
- VFHVQBAGLAREND-UHFFFAOYSA-N diphenylphosphoryl-(2,4,6-trimethylphenyl)methanone Chemical group CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 VFHVQBAGLAREND-UHFFFAOYSA-N 0.000 claims description 9
- 239000011230 binding agent Substances 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 230000008901 benefit Effects 0.000 abstract description 10
- 238000012797 qualification Methods 0.000 abstract description 8
- 230000009467 reduction Effects 0.000 abstract description 5
- 238000004134 energy conservation Methods 0.000 abstract description 2
- 238000004513 sizing Methods 0.000 description 21
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 12
- 238000004321 preservation Methods 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 11
- 239000000243 solution Substances 0.000 description 11
- 238000005516 engineering process Methods 0.000 description 10
- 239000004814 polyurethane Substances 0.000 description 10
- 229920002635 polyurethane Polymers 0.000 description 10
- 230000006872 improvement Effects 0.000 description 9
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 7
- 239000011148 porous material Substances 0.000 description 7
- 229910001928 zirconium oxide Inorganic materials 0.000 description 7
- 150000003254 radicals Chemical class 0.000 description 6
- 238000005266 casting Methods 0.000 description 5
- 238000005187 foaming Methods 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- 230000009286 beneficial effect Effects 0.000 description 4
- 229910010293 ceramic material Inorganic materials 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 4
- 230000007797 corrosion Effects 0.000 description 4
- 238000005260 corrosion Methods 0.000 description 4
- 238000013461 design Methods 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000005457 optimization Methods 0.000 description 4
- 238000001272 pressureless sintering Methods 0.000 description 4
- 239000003381 stabilizer Substances 0.000 description 4
- 230000002195 synergetic effect Effects 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 3
- 125000002091 cationic group Chemical group 0.000 description 3
- 150000001768 cations Chemical class 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000006835 compression Effects 0.000 description 3
- 238000007906 compression Methods 0.000 description 3
- 238000001723 curing Methods 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 230000000977 initiatory effect Effects 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 150000005839 radical cations Chemical class 0.000 description 3
- 230000000630 rising effect Effects 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 230000007704 transition Effects 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 238000005238 degreasing Methods 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 230000006698 induction Effects 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000011342 resin composition Substances 0.000 description 2
- 239000006104 solid solution Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- PSGCQDPCAWOCSH-UHFFFAOYSA-N (4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl) prop-2-enoate Chemical compound C1CC2(C)C(OC(=O)C=C)CC1C2(C)C PSGCQDPCAWOCSH-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
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 229910000505 Al2TiO5 Inorganic materials 0.000 description 1
- OWIKHYCFFJSOEH-UHFFFAOYSA-N Isocyanic acid Chemical compound N=C=O OWIKHYCFFJSOEH-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- BAECOWNUKCLBPZ-HIUWNOOHSA-N Triolein Natural products O([C@H](OCC(=O)CCCCCCC/C=C\CCCCCCCC)COC(=O)CCCCCCC/C=C\CCCCCCCC)C(=O)CCCCCCC/C=C\CCCCCCCC BAECOWNUKCLBPZ-HIUWNOOHSA-N 0.000 description 1
- PHYFQTYBJUILEZ-UHFFFAOYSA-N Trioleoylglycerol Natural products CCCCCCCCC=CCCCCCCCC(=O)OCC(OC(=O)CCCCCCCC=CCCCCCCCC)COC(=O)CCCCCCCC=CCCCCCCCC PHYFQTYBJUILEZ-UHFFFAOYSA-N 0.000 description 1
- MPIAGWXWVAHQBB-UHFFFAOYSA-N [3-prop-2-enoyloxy-2-[[3-prop-2-enoyloxy-2,2-bis(prop-2-enoyloxymethyl)propoxy]methyl]-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(COC(=O)C=C)(COC(=O)C=C)COCC(COC(=O)C=C)(COC(=O)C=C)COC(=O)C=C MPIAGWXWVAHQBB-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- XLJMAIOERFSOGZ-UHFFFAOYSA-N anhydrous cyanic acid Natural products OC#N XLJMAIOERFSOGZ-UHFFFAOYSA-N 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 239000004359 castor oil Substances 0.000 description 1
- 235000019438 castor oil Nutrition 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000013530 defoamer Substances 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 1
- 238000009775 high-speed stirring Methods 0.000 description 1
- 125000001165 hydrophobic group Chemical group 0.000 description 1
- 230000005661 hydrophobic surface Effects 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- PBOSTUDLECTMNL-UHFFFAOYSA-N lauryl acrylate Chemical compound CCCCCCCCCCCCOC(=O)C=C PBOSTUDLECTMNL-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910001338 liquidmetal Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 1
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920005906 polyester polyol Polymers 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- AABBHSMFGKYLKE-SNAWJCMRSA-N propan-2-yl (e)-but-2-enoate Chemical compound C\C=C\C(=O)OC(C)C AABBHSMFGKYLKE-SNAWJCMRSA-N 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 230000007847 structural defect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- PHYFQTYBJUILEZ-IUPFWZBJSA-N triolein Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OCC(OC(=O)CCCCCCC\C=C/CCCCCCCC)COC(=O)CCCCCCC\C=C/CCCCCCCC PHYFQTYBJUILEZ-IUPFWZBJSA-N 0.000 description 1
Images
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
- C04B38/00—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof
- C04B38/06—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof by burning-out added substances by burning natural expanding materials or by sublimating or melting out added substances
- C04B38/063—Preparing or treating the raw materials individually or as batches
- C04B38/0635—Compounding ingredients
- C04B38/0645—Burnable, meltable, sublimable materials
- C04B38/067—Macromolecular compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C64/00—Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
- B29C64/10—Processes of additive manufacturing
- B29C64/165—Processes of additive manufacturing using a combination of solid and fluid materials, e.g. a powder selectively bound by a liquid binder, catalyst, inhibitor or energy absorber
-
- 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
- B33Y10/00—Processes of additive manufacturing
-
- 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
-
- 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
- C04B35/48—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 zirconium or hafnium oxides, zirconates, zircon or hafnates
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/10—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers containing more than one epoxy radical per molecule
-
- 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
- C04B2235/50—Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
- C04B2235/54—Particle size related information
- C04B2235/5418—Particle size related information expressed by the size of the particles or aggregates thereof
- C04B2235/5436—Particle size related information expressed by the size of the particles or aggregates thereof micrometer sized, i.e. from 1 to 100 micron
-
- 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
- C04B2235/60—Aspects relating to the preparation, properties or mechanical treatment of green bodies or pre-forms
- C04B2235/602—Making the green bodies or pre-forms by moulding
-
- 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
- C04B2235/60—Aspects relating to the preparation, properties or mechanical treatment of green bodies or pre-forms
- C04B2235/606—Drying
-
- 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
- C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
- C04B2235/656—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes characterised by specific heating conditions during heat treatment
-
- 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
- C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
- C04B2235/656—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes characterised by specific heating conditions during heat treatment
- C04B2235/6562—Heating rate
-
- 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
- C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
- C04B2235/656—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes characterised by specific heating conditions during heat treatment
- C04B2235/6567—Treatment time
-
- 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
- C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
- C04B2235/658—Atmosphere during thermal treatment
- C04B2235/6583—Oxygen containing atmosphere, e.g. with changing oxygen pressures
-
- 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
- C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
- C04B2235/94—Products characterised by their shape
-
- 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
- C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
- C04B2235/96—Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance
-
- 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
- C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
- C04B2235/96—Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance
- C04B2235/9607—Thermal properties, e.g. thermal expansion coefficient
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Ceramic Engineering (AREA)
- Organic Chemistry (AREA)
- Structural Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Mechanical Engineering (AREA)
- Optics & Photonics (AREA)
- Composite Materials (AREA)
- Compositions Of Oxide Ceramics (AREA)
Abstract
The invention relates to the field of advanced ceramic manufacturing, and particularly discloses a foamed ceramic and a preparation method thereof, wherein the foamed ceramic is formed by soaking a sponge support body in zirconia ceramic slurry and then sintering at a high temperature, wherein the sponge support body is prepared by photocuring 3D printing a mixed photosensitive material, the mixed photosensitive material comprises mixed photosensitive resin, and the mixed photosensitive resin comprises the following raw materials in parts by weight: 30-60 parts of epoxy acrylate; 40-70 parts of reactive diluent; 1-5 parts of a free radical photoinitiator; 50-70 parts of aliphatic epoxy resin; 30-50 parts of hydroxybutyl vinyl ether; 1-5 parts of cationic photoinitiator. Correspondingly, the invention also discloses a preparation method of the foamed ceramic. By adopting the invention, the foamed ceramic has the advantages of high porosity, high mechanical property and the like, and the product has good stability and high qualification rate. Moreover, the method has the advantages of simple process, cost reduction, high efficiency, high speed, energy conservation, consumption reduction and industrialized application.
Description
Technical Field
The invention relates to the technical field of advanced ceramic manufacturing, in particular to foamed ceramic and a preparation method thereof.
Background
In the casting production process, the foamed ceramic can effectively reduce or eliminate inclusions in liquid metal, obviously improve the quality and yield of castings, and improve the quality level and economic benefit of cast products. Among them, zirconia ceramic foam has the characteristics of high strength, high temperature stability and corrosion resistance, is widely applied to the filtration of molten steel and high temperature melt, has the use temperature of about 1600 to 1650 ℃, and is favored by the casting industry. The preparation method of the foamed ceramics comprises a pore-forming method, a foaming method, an organic precursor impregnation method and the like, and a polyurethane sponge impregnation method is mostly adopted at present.
In recent years, ceramic additive manufacturing based on rapid prototyping can shorten the manufacturing period and reduce the manufacturing cost, and becomes a hot research point for ceramic material forming. The free radical photocuring system is high in speed, easy to adjust in performance, severe in curing shrinkage and low in forming precision when used alone; the cation curing system has high viscosity and low speed, but has small volume shrinkage, and can meet the requirement of forming precision. The free radical-cation hybrid photocuring system can form a cross-linked interpenetrating network, has the advantages of initiating synergistic effect, performance complementation and the like, and has a great application prospect in the field of additive manufacturing due to the fact that the forming process is simple, the speed is high, and the precision is high.
The traditional high-pressure foaming method is adopted to prepare the polyurethane sponge, the uniformity of the mesh size is poor, the consistency of the thickness and the fineness of the mesh is poor, and the final foamed ceramic product is easy to cause poor stability and low qualified rate, and the method specifically comprises the following steps: (1) Pores are generated due to gas generated by chemical reaction, and the pore diameter and the distribution of the sponge are difficult to control; (2) Due to the distribution and the dosage of the foaming agent and the difference of foaming speed, the size and the shape of pores in the sponge are greatly different and the distribution is uneven. The specific defects of the pore structure in the polyurethane sponge are as follows: (1) the diameter of the pore canal is large or small; (2) the inside of the pore canal may have larger spherical holes; and (3) holes which do not break the polyurethane wall exist in the sponge. The foamed ceramics produced by adopting the polyurethane sponge with defects have low mechanical strength and poor thermal shock resistance, and are easy to generate the phenomenon of product breakage in the pouring process.
And the photo-curing 3D printing technology is adopted to prepare ceramic products, and the photo-curing 3D printing method is difficult to carry out industrial production due to the high price of photosensitive ceramic slurry, low qualified rate of ceramic green bodies and large degreasing sintering shrinkage rate.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a foamed ceramic which has the advantages of high porosity, high mechanical property and the like, and the product has good stability and high qualification rate.
The technical problem to be solved by the invention is to provide a preparation method of the foamed ceramic, which has the advantages of simple process, cost reduction, high efficiency, rapidness, energy conservation, consumption reduction and industrial application.
In order to achieve the technical effects, the invention provides a foamed ceramic which is formed by soaking a sponge support body in zirconia ceramic slurry and then sintering at a high temperature, wherein the sponge support body is prepared by photocuring 3D printing a mixed photosensitive material, the mixed photosensitive material comprises a mixed photosensitive resin, and the mixed photosensitive resin comprises the following raw materials in parts by weight:
30-60 parts of epoxy acrylate;
40-70 parts of reactive diluent;
1-5 parts of a free radical photoinitiator;
50-70 parts of aliphatic epoxy resin;
30-50 parts of hydroxybutyl vinyl ether;
1-5 parts of cationic photoinitiator.
As an improvement of the scheme, the viscosity of the epoxy acrylate is less than or equal to 60000 mPas;
the active diluent is 1, 6-hexanediol diacrylate, and the viscosity of the active diluent is less than or equal to 10mPa & s;
the free radical photoinitiator is 2,4, 6-trimethylbenzoyl-diphenyl phosphorus oxide, and the component content is more than or equal to 99.0 percent;
the viscosity of the aliphatic epoxy resin is less than or equal to 300mPa & s;
the content of the hydroxybutyl vinyl ether is more than or equal to 98.0 percent;
the cationic photoinitiator is diaryl iodonium salt with the component content of more than or equal to 99.5 percent.
In the improvement of the scheme, the viscosity of the epoxy acrylate is 30000 to 60000mPa & s;
the active diluent is 1, 6-hexanediol diacrylate, and the viscosity of the active diluent is 5 to 10mPa & s;
the free radical photoinitiator is 2,4, 6-trimethylbenzoyl-diphenyl phosphorus oxide, and the content of the components is 99.0 to 99.5 percent;
the viscosity of the aliphatic epoxy resin is 200 to 300mPas;
the content of the hydroxybutyl vinyl ether is 98.0-99.5%;
the cationic photoinitiator is diaryl iodonium salt, and the content of the components is 99.5 to 99.8 percent.
As an improvement of the scheme, the mixed photosensitive material comprises mixed photosensitive resin and ceramic powder, the adding amount of the ceramic powder is 1-3 wt% of the mixed photosensitive resin, and the ceramic powder is zirconia powder.
As an improvement of the scheme, the zirconia ceramic slurry is prepared by mixing zirconia powder, magnesia and a binder and performing ball milling;
the particle size of the zirconium oxide powder is 5-30 mu m;
the viscosity of the zirconia ceramic slurry is 12000 mPas-15000 mPas.
As an improvement of the scheme, the through hole rate of the foamed ceramic is more than 85%, the normal-temperature compressive strength is more than 8.5MPa, and the residual strength after primary air thermal shock at 1400 ℃ is more than 3.5MPa.
Correspondingly, the invention also provides a preparation method of the foamed ceramic, which comprises the following steps:
(1) Uniformly stirring 30-60 parts by weight of epoxy acrylate, 40-70 parts by weight of reactive diluent, 2-5 parts by weight of free radical photoinitiator, 50-70 parts by weight of aliphatic epoxy resin, 30-50 parts by weight of hydroxybutyl vinyl ether and 1-5 parts by weight of cationic photoinitiator to obtain mixed photosensitive resin;
(2) Carrying out photocuring 3D printing on the mixed photosensitive resin to obtain a sponge support;
(3) Carrying out ceramic slurry dipping treatment on the sponge supporting body so as to enable zirconia ceramic slurry to be attached to the sponge supporting body, and obtaining a foamed ceramic blank;
(4) And drying the foamed ceramic blank, and then sintering at high temperature to obtain a foamed ceramic finished product.
As an improvement of the above scheme, the step (2) comprises:
uniformly mixing the raw materials of the mixed photosensitive resin;
setting the printing thickness, the printing speed, the optical power density and the photocuring time of the photocuring 3D printer;
and 3D printing the mixed photosensitive resin through a photocuring 3D printer to obtain the sponge support.
Alternatively, the step (2) comprises:
uniformly mixing the raw materials for mixing the photosensitive resin, and adding ceramic powder;
setting the printing layer thickness, printing speed, optical power density and photocuring time of the photocuring 3D printer;
and 3D printing the mixed photosensitive resin through a photocuring 3D printer to obtain the sponge support.
As an improvement of the scheme, the thickness of the printing layer is 0.01 to 0.1mm, the printing speed is 10 to 50mm/s, and the optical power density is 5 to 25mW/cm 2 And the photocuring time is 2 to 5s.
As a modification of the above, the step (3) comprises the steps of:
soaking the sponge supporting body in zirconia ceramic slurry, and rolling to form a first blank;
dipping the first green body in the zirconia ceramic slurry again, and rolling to form a second green body;
drying the second blank;
and after the second green body is dried, spraying the zirconia ceramic slurry on the surface of the second green body to obtain a foamed ceramic green body.
As an improvement of the above scheme, in the step (4): the drying treatment process parameters are as follows: the drying temperature is 35-45 ℃, and the drying time is 8-12h;
the conditions of the high-temperature sintering are as follows:
raising the temperature to 600-620 ℃ at a heating rate of 0.3-0.5 ℃/min, and keeping the temperature for 0.5-1h;
raising the temperature to 1680-1720 ℃ at the heating rate of 0.5-1.5 ℃/min, and keeping the temperature for 4-6 h;
the sintering atmosphere is air.
The implementation of the invention has the following beneficial effects:
the foamed ceramic is prepared by firstly preparing a sponge supporting body by photocuring 3D printing of mixed photosensitive resin, then soaking the sponge supporting body in zirconia ceramic slurry, and drying and sintering.
Firstly, the mixed photosensitive resin comprises epoxy acrylate, a reactive diluent, a free radical photoinitiator, aliphatic epoxy resin, hydroxybutyl vinyl ether and a cationic photoinitiator in a specific ratio, the raw materials form a free radical-cationic mixed photocuring system, a cross-linked interpenetrating network can be formed, the advantages of initiating synergistic effect, performance complementation and the like are achieved, and the structural design, printing rate, mechanical property and qualification rate of the photocuring 3D printing method formed sponge support can be remarkably improved. The obtained sponge supporting body has uniform mesh size, consistent mesh wire thickness and excellent mechanical property. In addition, the mixed photosensitive resin instead of the photosensitive zirconia ceramic slurry is adopted, so that the process difficulty is reduced, the cost is reduced, the sintering shrinkage rate is effectively controlled, the qualification rate of green bodies and the stability of product quality are improved, and the industrial production is realized.
Secondly, the sponge supporting body is placed into zirconia ceramic slurry, the zirconia ceramic slurry can be effectively attached to the sponge supporting body of photocuring 3D printing, magnesia is used as a stabilizer of the zirconia ceramic slurry, the zirconia foamed ceramic can be effectively enabled to have good room temperature strength and thermal shock residual strength after being sintered at high temperature, the unification of structure optimization and performance optimization is realized, meanwhile, the magnesia forms a weak alkaline environment in the ceramic slurry, and the corrosion of the ceramic slurry to equipment can be effectively reduced.
Finally, the zirconia foamed ceramic with high porosity and high mechanical strength can be prepared by printing the sponge support body in a photocuring 3D manner and performing slurry dipping, the zirconia foamed ceramic has good room temperature strength and thermal shock residual strength, the porosity is as high as 85 to 87 percent, the normal temperature compressive strength is as high as 14 to 16900 MPa, the residual strength after one-time air thermal shock at 1400 ℃ is as high as 6 to 8MPa, and the requirements of casting and pouring are met.
Drawings
FIG. 1 shows the phase compositions of zirconia ceramic foams obtained in examples 1 to 3 of the present invention;
FIG. 2 is a scanning electron micrograph of the zirconia ceramic foam obtained in example 1 of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below.
Term(s) for
Unless otherwise stated or contradicted, terms or phrases used herein have the following meanings:
in the present invention, the terms "combination thereof", "any combination thereof", and the like include all suitable combinations of any two or more of the listed items.
In the present invention, "preferred" is only an embodiment or an example for better description, and it should be understood that the scope of the present invention is not limited thereto.
In the present invention, the technical features described in the open type include a closed technical solution composed of the listed features, and also include an open technical solution including the listed features.
In the present invention, the numerical range is defined to include both endpoints of the numerical range unless otherwise specified.
Regarding the preparation of the foamed ceramics, the prior art can not consider the industrialized production, the cost reduction and the product quality. Therefore, the invention provides foamed ceramic which is formed by soaking a sponge supporting body in zirconia ceramic slurry and then sintering at high temperature. The sponge support body is prepared by carrying out photocuring 3D printing on a mixed photosensitive material, wherein the mixed photosensitive material comprises mixed photosensitive resin, and the mixed photosensitive resin comprises the following raw materials in parts by weight:
30-60 parts of epoxy acrylate;
40-70 parts of reactive diluent;
1-5 parts of a free radical photoinitiator;
50-70 parts of aliphatic epoxy resin;
30-50 parts of hydroxybutyl vinyl ether;
1-5 parts of cationic photoinitiator.
Preferably, the mixed photosensitive resin comprises the following raw materials in parts by weight:
35-55 parts of epoxy acrylate;
45-65 parts of a reactive diluent;
2-5 parts of a free radical photoinitiator;
55-65 parts of aliphatic epoxy resin;
35-45 parts of hydroxybutyl vinyl ether;
3-5 parts of cationic photoinitiator.
More preferably, the mixed photosensitive resin comprises the following raw materials in parts by weight:
40-50 parts of epoxy acrylate;
50-60 parts of a reactive diluent;
2-5 parts of a free radical photoinitiator;
57-63 parts of aliphatic epoxy resin;
37-43 parts of hydroxybutyl vinyl ether;
3-5 parts of cationic photoinitiator.
The sponge support body is prepared by photo-curing 3D printing of a mixed photosensitive material, the mixed photosensitive material comprises mixed photosensitive resin, the photo-curing 3D printing technology is based on the photo-curing principle of liquid photosensitive resin, and the main components of the photo-curing 3D printing technology are oligomer, reactive diluent, photoinitiator and the like. The free radical-cation hybrid system composed of the free radical type resin and the cation type resin can promote the hybrid photocuring system to have synergistic effects in the aspects of photo initiation, volume change complementation and performance regulation, and is beneficial to the optimization of the precision of a formed part and the improvement of the performance of the photocuring resin. The viscosity of the epoxy acrylate and the aliphatic epoxy resin will affect the printing rate and the mechanical strength of the photosensitive resin system. Preferably, the epoxy acrylate has a viscosity of 60000 mPas (25 ℃) and the aliphatic epoxy resin has a viscosity of 300 mPas (25 ℃). More preferably, the viscosity of the epoxy acrylate is 30000 to 60000mPa.s (at 25 ℃), and the viscosity of the aliphatic epoxy resin is 200 to 300mPa.s (at 25 ℃).
The viscosity of the epoxy acrylate and the viscosity of the aliphatic epoxy resin are measured at 25 ℃.
The invention selects free radical photosensitive resin, cationic photosensitive resin, and matched reactive diluent and photoinitiator in specific proportion. The free radical type photocuring material has the advantages of short induction period, low viscosity, good toughness, low cost, large volume shrinkage and poor adhesion; the cationic photocuring has longer induction period, long service life of the active intermediate, small volume shrinkage and good adhesive force, and can still continue the curing reaction after the illumination is stopped. The free radical type and the cationic photosensitive resin system can obviously accelerate the photo-printing speed, enhance the strength of the sponge support body and improve the qualification rate of the sponge support body under the synergistic action.
Preferably, the reactive diluent is 1, 6-hexanediol diacrylate with a viscosity of less than or equal to 10 mPa.s (25 ℃); the free radical photoinitiator is 2,4, 6-trimethylbenzoyl-diphenyl phosphorus oxide, and the component content is more than or equal to 99.0 percent; the content of the hydroxybutyl vinyl ether is more than or equal to 98.0 percent; the cationic photoinitiator is diaryl iodonium salt with the component content of more than or equal to 99.5 percent.
More preferably, the reactive diluent is 1, 6-hexanediol diacrylate, and the viscosity of the reactive diluent is 5 to 10mPa.s (at 25 ℃); the free radical photoinitiator is 2,4, 6-trimethylbenzoyl-diphenyl phosphorus oxide, and the content of the components is 99.0 to 99.5 percent; the content of the hydroxybutyl vinyl ether is 98.0-99.5%; the cationic photoinitiator is diaryl iodonium salt, and the content of the components is 99.5 to 99.8 percent.
The viscosity of 1, 6-hexanediol diacrylate is measured at 25 ℃.
The mixed photosensitive resin comprises epoxy acrylate, a reactive diluent, a free radical photoinitiator, aliphatic epoxy resin, hydroxybutyl vinyl ether and a cationic photoinitiator in a specific proportion, and the raw materials form a free radical-cationic hybrid photocuring system, so that the printing precision, the mechanical strength and the qualification rate of the sponge support formed by the photocuring 3D printing method can be remarkably improved. The obtained sponge support has uniform mesh size, consistent mesh thickness and excellent mechanical property. In addition, the invention adopts the mixed photosensitive resin instead of the photosensitive ceramic slurry, thereby reducing the process difficulty, reducing the cost, effectively controlling the sintering shrinkage rate, improving the qualification rate of green bodies and the stability of product quality, and realizing industrialized production.
Preferably, the mixed photosensitive material comprises mixed photosensitive resin and ceramic powder, the addition amount of the ceramic powder is 1-3 wt% of the mixed photosensitive resin, the strength of the printed photosensitive resin can be improved, and the surface of the printed sponge support is roughened, so that the adsorption effect of the ceramic slurry in slurry dipping is facilitated. Preferably, the addition amount of the ceramic powder is 1 to 2.5wt% of the mixed photosensitive resin.
The ceramic powder added in the mixed photosensitive material is single ceramic powder, and zirconia powder is preferably selected.
In one embodiment, the sponge support is rapidly molded by setting the printing thickness, the printing speed, the optical power density and the photocuring time. Preferably, the printing layer has the thickness of 0.01 to 0.1mm, the printing speed of 10 to 50mm/s and the optical power density of 5 to 25mW/cm 2 And the photocuring time is 2 to 5s.
According to the invention, the sponge supporting body is prepared by adopting a 3D printing and forming method, and the foamed ceramic is prepared by soaking the ceramic slurry by taking the sponge supporting body as a template, rather than directly preparing the foamed ceramic by adopting the 3D printing ceramic slurry. The density of the 3D printing sponge support body prepared by the invention is 25 to 30kg/m 3 (ii) a The tensile strength is more than or equal to 280kPa; the elongation at break is more than or equal to 80 percent; the compression set force (40%) was 5.5. + -. 1.5N.
The invention adopts the photocuring 3D printing forming method of the free radical-cation hybrid photocuring system, can obviously improve the structural design, printing speed, mechanical property and qualification rate of the sponge supporting body, and the obtained sponge supporting body has uniform mesh size and uniform mesh silk thickness. The 3D printing and forming method is beneficial to designing the mesh structure of the sponge supporting body, and the mesh structure can be determined according to the application requirements of the product. The foamed ceramic product prepared by using the template has good mesh consistency, can reduce the product defects caused by the structural defects of pore channels in polyurethane sponge prepared by the traditional method, and can reduce the problems that the foamed ceramic product does not meet the requirements and the like due to different mesh sizes.
Further, the zirconia ceramic slurry is prepared by mixing zirconia powder, magnesia and a binder and performing ball milling. Preferably, the addition amount of the magnesium oxide is 3-10 mol% of zirconium oxide content; the binder is PVA solution, the addition amount of the binder is 5-20 wt% of zirconia powder, and the viscosity of the zirconia ceramic slurry is 12000-15000 mPa.
The zirconia-zirconia ceramic slurry consists of zirconia powder, magnesia powder and PVA solution, wherein the sintering activity and the mechanical strength of the product are influenced by the overlarge particle size of the zirconia, and preferably, the particle size of the zirconia powder is less than or equal to 30 mu m. Preferably, the particle size of the zirconia powder is 5-30 mu m.
The magnesia is used as a stabilizer, has a cation radius similar to that of zirconia, can enter a crystal structure of the zirconia in a solid solution manner in a high-temperature sintering process, and can effectively regulate and control the proportion of monoclinic phase and tetragonal phase in the zirconia ceramic. Compared with other stabilizers such as yttrium oxide, cerium oxide and the like, the zirconia ceramic stabilized by magnesium oxide has more outstanding thermal shock resistance. Meanwhile, microcracks generated by phase change can better resist crack expansion caused by thermal shock, so that the energy required by crack expansion is improved, and the material has higher thermal shock resistance macroscopically. In addition, the alkaline environment formed by the magnesium oxide in the ceramic slurry can effectively reduce the corrosion of the slurry to equipment.
Therefore, the magnesium oxide fully utilizes the volume change caused by the phase change of monoclinic phase and tetragonal phase in the sintering process by adjusting and controlling the phase composition and the content of the zirconia ceramic, can optimize the thermal expansion performance of the material, and improve the thermal shock resistance of the material. Preferably, when the weight part of the zirconia is 100 parts, the weight part of the magnesia powder is 3.7 to 7.4 parts. Illustratively, the weight part of zirconia is 100 parts, and the weight part of magnesia may be 3.7 parts, 4.0 parts, 5.0 parts, 6.0 parts, 7.0 parts, 7.4 parts, etc., but is not limited thereto. In addition, the grain diameter of the magnesium oxide powder is less than or equal to 2.0 mu m; more preferably, the particle size of the magnesium oxide powder is 1.0 μm to 2.0 μm.
The PVA solution is used as a binder, can be effectively attached to a sponge support body for photocuring 3D printing, and can effectively regulate and control sizing weight and slurry hanging uniformity. Preferably, the PVA solution accounts for 6 to 10 parts by weight, and the polymerization degree is 5000 to 7000; the concentration of the PVA solution is 10% -15%.
According to the invention, the zirconia ceramic slurry is attached to the sponge supporting body by soaking the sponge supporting body in the zirconia ceramic slurry, so that the zirconia foamed ceramic has good room temperature strength and thermal shock residual strength after being sintered at high temperature, the unification of structure optimization and excellent performance is realized, and meanwhile, magnesia forms a weak alkaline environment in the ceramic slurry, so that the corrosion of the ceramic slurry to equipment can be effectively reduced.
In conclusion, the zirconia ceramic provided by the invention has the performances of high strength, high hardness, low density, good chemical stability and the like, and the traditional process cannot efficiently form or process a complex hollow structure and the like, so that the application of the advanced ceramic material in the high and new technical fields is severely restricted. The 3D printing technology adopted by the invention is a die-free forming technology and has remarkable advantages in the aspect of solving the problem of precision forming of ceramic parts with complex structures. The photocuring 3D printing technology can realize the design of the structure of the sponge supporting body, and the sponge supporting body based on the structural design can be used for preparing zirconia ceramic materials with different structures through slurry dipping. By utilizing the phase transition mechanism of monoclinic phase and tetragonal phase of zirconia, the zirconia ceramic product has good thermal shock resistance and can be applied to extreme high-temperature thermal shock environments.
The through hole rate of the foamed ceramic prepared by the invention is more than 85%, the normal-temperature compressive strength is more than 8.5MPa, and the residual strength after primary air thermal shock at 1400 ℃ is more than 3.5MPa. Preferably, the porosity of the prepared porous ceramic material is as high as 85 to 87 percent, the normal-temperature compressive strength is as high as 14 to 1699 MPa, and the residual strength after primary air thermal shock at 1400 ℃ is as high as 6 to 8MPa.
Correspondingly, the invention also provides a preparation method of the foamed ceramic, which comprises the following steps:
(1) Uniformly stirring 30-60 parts by weight of epoxy acrylate, 40-70 parts by weight of reactive diluent, 2-5 parts by weight of free radical photoinitiator, 50-70 parts by weight of aliphatic epoxy resin, 30-50 parts by weight of hydroxybutyl vinyl ether and 1-5 parts by weight of cationic photoinitiator to obtain mixed photosensitive resin;
in the step (1), the raw material of the mixed photosensitive resin is selected, and the technical details thereof are the same as those described above and are not described herein again.
(2) Carrying out photocuring 3D printing on the mixed photosensitive resin to obtain a sponge support;
preferably, step (2) comprises:
uniformly mixing the raw materials of the mixed photosensitive resin;
setting the printing thickness, the printing speed, the optical power density and the photocuring time of the photocuring 3D printer;
and 3D printing the mixed photosensitive resin through a photocuring 3D printer to obtain the sponge support.
Alternatively, the step (2) comprises:
uniformly mixing the raw materials for mixing the photosensitive resin, and adding ceramic powder;
setting the printing layer thickness, printing speed, optical power density and photocuring time of the photocuring 3D printer;
and 3D printing the mixed photosensitive resin through a photocuring 3D printer to obtain the sponge support.
More preferably, the print layer has a thickness of 0.01 to 0.1mm, a printing rate of 10 to 50mm/s, and an optical power density of 5 to 25mW/cm 2 And the photocuring time is 2 to 5s.
According to the invention, the precision forming problem of the ceramic part with a complex structure is solved by photocuring 3D printing and a die-free forming technology according to actual needs, and the manufacturing requirements of sponge supporting bodies with different structures are met.
(3) Carrying out ceramic slurry dipping treatment on the sponge supporting body so as to enable zirconia ceramic slurry to be attached to the sponge supporting body, and obtaining a foamed ceramic blank;
preferably, step (3) comprises the steps of:
dipping the sponge supporting body in zirconia ceramic slurry, and rolling to form a first blank body;
dipping the first blank body in the zirconia ceramic slurry again, and rolling to form a second blank body;
drying the second blank;
and after the second blank body is dried, spraying the zirconia ceramic slurry on the surface of the second blank body to obtain a foamed ceramic blank body.
Preferably, the sizing amount of the first blank is 15-20wt%; the sizing amount of the second blank is 80 to 70wt%; and the sizing amount of the surface spraying of the second blank is 5-10wt%.
Three sizing layers are respectively formed by adopting a mode of sizing for three times, wherein the first sizing is to improve the hydrophobic surface of the sponge body and form a transition layer which is beneficial to the attachment of zirconia sizing; the second sizing is carried out on the basis of the transition layer to carry out mass sizing to form a zirconia foamed ceramic main body; and the third sizing is to modify the surface of the foamed ceramic to ensure that the lines are more round and sturdy.
(4) And drying the foamed ceramic blank, and then sintering at high temperature to obtain a foamed ceramic finished product.
In one embodiment, the process parameters of the drying treatment are: the drying temperature is 35-45 ℃, and the drying time is 10h-12h. Preferably, the water content after the drying treatment is not higher than 2wt%.
In one embodiment, the sintering conditions are:
raising the temperature to 600-620 ℃ at a heating rate of 0.3-0.5 ℃/min and keeping the temperature for 0.5-1h;
raising the temperature to 1680-1720 ℃ at the heating rate of 0.5-1.5 ℃/min, and keeping the temperature for 4-6 h;
the sintering atmosphere is air.
Preferably, the sintering conditions are: carrying out pressureless sintering by adopting a pushed slab kiln, wherein the heating rate is 0.3 ℃/min, the sintering temperature is up to 600 ℃, and the heat preservation time is 1h; the temperature rising rate is 1.5 ℃/min, the sintering temperature is 1720 ℃ for heat preservation treatment, the heat preservation time is 4h, and the sintering atmosphere is air, so that the zirconia foamed ceramic is obtained.
According to the invention, the temperature is increased to 600-620 ℃ at a slow heating rate and is kept for 0.5-1h, so that the component degreasing of the sponge support body is facilitated, and then the temperature is increased to 1680-1720 ℃ at a fast heating rate and is sintered for 4-6h, so that the solid solution effect of magnesium element can be performed to the maximum extent, the densification of the zirconia ceramic is improved, and the mechanical strength and the thermal shock resistance of the zirconia ceramic are enhanced.
The invention is further illustrated by the following specific examples
Example 1
The embodiment provides a preparation method of zirconia foamed ceramic, which comprises the following steps:
s1, uniformly stirring 60 parts of epoxy acrylate, 40 parts of active diluent 1, 6-hexanediol diacrylate (HDDA), 5 parts of free radical photoinitiator 2,4, 6-trimethylbenzoyl-diphenyl phosphorus oxide (TPO), 70 parts of aliphatic epoxy resin, 30 parts of hydroxybutyl vinyl ether (HBVE) and 5 parts of cationic photoinitiator diaryl iodonium salt in parts by weight to obtain a mixed photosensitive resin system;
s2, preparing a sponge supporting body by adopting a photocuring 3D printing technology, and setting photocuring parameters: the thickness of the printing layer was set to 0.1mm, the printing rate was set to 20mm/s, and the optical power density was set to 24mW/cm 2 The photocuring time was set to 2s. And pouring mixed photosensitive resin into a scraper trough of the photocuring 3D printer, and starting to print to obtain a sponge support body, wherein the printing specification is that the diameter is 100mm, the thickness is 30mm, and the mesh is 10ppi.
And S3, the zirconia ceramic slurry consists of zirconia powder, magnesia powder and PVA solution. Wherein, the weight portion of the zirconium oxide is 100 portions, and the grain diameter of the zirconium powder is 30 μm; 7.4 parts of magnesium oxide and 1.0 micron of magnesium oxide powder particle size; the PVA accounts for 10 parts by weight, the polymerization degree is 7000, and the concentration is 15%. And grinding in a ball milling mode to obtain ceramic slurry, wherein the ball-to-material ratio of ball milling is 5, the mixing time is 4h, and the viscosity of the zirconia ceramic slurry is 12100mPa & s.
S4, dipping the sponge supporting body with ceramic slurry, and automatically rolling to form a first blank body, wherein the sizing amount of the first blank body is 15wt%; soaking the first blank body in the ceramic slurry again, and automatically rolling to form a second blank body, wherein the sizing amount of the second blank body is 80wt%; after the second green body is dried, spraying the ceramic slurry on the surface of the second green body, wherein the spraying sizing amount is 5wt%, so as to obtain a zirconium oxide foamed ceramic green body;
s5, drying the foamed ceramic blank for 12 hours by using a drying chamber at 35 ℃, wherein the water content of the dried zirconia foamed ceramic is lower than 2wt%;
carrying out pressureless sintering on the dried foamed ceramic blank by adopting a pushed slab kiln, wherein the heating rate is 0.3 ℃/min, the sintering temperature is 600 ℃, and the heat preservation time is 1h; the temperature rise rate is 1.5 ℃/min, the sintering temperature is 1720 ℃ for heat preservation, the heat preservation time is 4h, and the sintering atmosphere is air, so that the zirconia foamed ceramic is obtained.
FIG. 2 is a scanning electron micrograph of the zirconia ceramic foam obtained in example 1.
Example 2
The embodiment provides a preparation method of zirconia foamed ceramic, which comprises the following steps:
s1, uniformly stirring 30 parts of epoxy acrylate, 70 parts of 1, 6-hexanediol diacrylate (HDDA) serving as an active diluent, 2 parts of 2,4, 6-trimethylbenzoyl-diphenyl phosphorus oxide (TPO) serving as a free radical photoinitiator, 50 parts of aliphatic epoxy resin, 50 parts of hydroxybutyl vinyl ether (HBVE) and 3 parts of diaryliodonium salt serving as a cationic photoinitiator to obtain a mixed photosensitive resin system;
s2, preparing a sponge supporting body by adopting a photocuring 3D printing technology, and setting photocuring parameters: the print layer thickness was set to 0.1mm, the print rate was set to 20mm/s, and the optical power density was set to 24mW/cm 2 The photocuring time was set to 2s. And pouring mixed photosensitive resin into a scraper trough of the photocuring 3D printer, and starting printing to obtain a sponge support body, wherein the printing specification is that the diameter is 60mm, the thickness is 20mm, and the mesh is 20ppi.
And S3, the zirconia ceramic slurry consists of zirconia powder, magnesia powder and PVA solution. The weight part of the zirconium oxide is 100 parts, and the particle size of the zirconium powder is 5 mu m; 3.7 parts of magnesium oxide, and the particle size of the magnesium oxide powder is 1.0 mu m; the PVA accounts for 6 parts by weight, the polymerization degree is 7000, and the concentration is 15%. Grinding by combining a ball milling mode to obtain ceramic slurry, wherein the ball-to-material ratio of ball milling is 3, the mixing time is 8h, and the viscosity of the zirconia ceramic slurry is 14600mPa & s.
S4, dipping the sponge supporting body with ceramic slurry, and automatically rolling to form a first blank body, wherein the sizing amount of the first blank body is 20wt%; dipping the first green body in the ceramic slurry again, and automatically rolling to form a second green body, wherein the sizing amount of the second green body is 70wt%; and after the second green body is dried, spraying the ceramic slurry on the surface of the second green body, wherein the spraying sizing amount is 10wt%, so as to obtain the zirconia foamed ceramic green body.
S5, drying the foamed ceramic blank for 10 hours by using a 45 ℃ drying chamber, wherein the water content of the dried zirconia foamed ceramic is lower than 2wt%;
carrying out pressureless sintering on the dried foamed ceramic blank by adopting a pushed slab kiln, wherein the heating rate is 0.5 ℃/min, the sintering temperature is 620 ℃, and the heat preservation time is 0.5h; the temperature rising rate is 0.5 ℃/min, the sintering temperature is 1680 ℃, the heat preservation treatment is carried out, the heat preservation time is 6h, and the sintering atmosphere is air, so that the zirconia foamed ceramic is obtained.
Example 3
The embodiment provides a preparation method of zirconia foamed ceramic, which comprises the following steps:
s1, uniformly stirring 50 parts of epoxy acrylate, 50 parts of active diluent 1, 6-hexanediol diacrylate (HDDA), 3 parts of free radical photoinitiator 2,4, 6-trimethylbenzoyl-diphenyl phosphorus oxide (TPO), 60 parts of aliphatic epoxy resin, 40 parts of hydroxybutyl vinyl ether (HBVE) and 3 parts of cationic photoinitiator diaryl iodonium salt to obtain a mixed photosensitive resin system;
s2, preparing a sponge support body by adopting a photocuring 3D printing technology, and setting photocuring parameters: the print layer thickness was set to 0.1mm, the print rate was set to 20mm/s, and the optical power density was set to 24mW/cm 2 The photocuring time was set to 2s. And pouring mixed photosensitive resin into a scraper trough of the photocuring 3D printer, and starting printing to obtain the sponge support, wherein the printing specification is that the diameter is 30mm, the thickness is 10mm, and the mesh is 30ppi.
And S3, the zirconia ceramic slurry consists of zirconia powder, magnesia powder and PVA solution. Wherein, the weight portion of the zirconium oxide is 100 portions, and the grain diameter of the zirconium powder is 15 μm; 7.4 parts of magnesium oxide and 2.0 mu m of magnesium oxide powder particle size; 10 parts by weight of PVA, 7000 degrees of polymerization, and a concentration of 15%. And grinding in a ball milling mode to obtain ceramic slurry, wherein the ball-material ratio of ball milling is 4, the mixing time is 6h, and the viscosity of the zirconia ceramic slurry is 13300mPa & s.
S4, dipping the sponge supporting body with ceramic slurry, and automatically rolling to form a first blank body, wherein the sizing amount of the first blank body is 15wt%; dipping the first green body in the ceramic slurry again, and automatically rolling to form a second green body, wherein the sizing amount of the second green body is 70wt%; after the second green body is dried, spraying the ceramic slurry on the surface of the second green body, wherein the spraying sizing amount is 10wt%, so as to obtain a zirconium oxide foamed ceramic green body;
s5, drying the foamed ceramic blank for 12 hours by using a 45 ℃ drying chamber, wherein the water content of the dried zirconia foamed ceramic is lower than 2wt%;
carrying out pressureless sintering on the dried foamed ceramic blank by adopting a pushed slab kiln, wherein the heating rate is 0.3 ℃/min, the sintering temperature is 600 ℃, and the heat preservation time is 1h; the temperature rising rate is 1.0 ℃/min, the sintering temperature is 1700 ℃, the heat preservation treatment is carried out, the heat preservation time is 4h, and the sintering atmosphere is air, so that the zirconia foamed ceramic is obtained.
Example 4
This example provides a method for preparing a zirconia ceramic foam, which is different from example 3 in the step S2. Example 4 a mixed photosensitive resin and zirconia ceramic powder was poured into the doctor blade tank of a photo-curing 3D printer, the amount of zirconia ceramic powder added was 1wt% of the mixed photosensitive resin, and printing was started to obtain a sponge support.
Example 5
This example provides a method for preparing a zirconia ceramic foam, which is different from example 3 in the step S2. Example 5 a sponge support was obtained by pouring a mixed photosensitive resin and zirconia ceramic powder in an amount of 2.5wt% of the mixed photosensitive resin into a doctor blade tank of a photo-curing 3D printer and starting printing.
Comparative example 1
The embodiment provides a preparation method of zirconia foamed ceramic, which is different from the embodiment 3 in steps S1 to S2, and the comparative example 1 adopts polyurethane sponge prepared by a traditional high-pressure method as a sizing template, and the rest is the same as the embodiment 3.
The traditional high-pressure method for preparing the polyurethane sponge comprises the following steps:
the polyurethane sponge is prepared by taking 65-85 parts of polyester polyol as a main material, adding 15-35 parts of isocyanic acid, 0.5-2.5 parts of triethanolamine serving as a catalyst and 0.5-1.8 parts of organosilicon foam serving as a stabilizer, and performing chain extension reaction, foaming, communication and other processes on the polyurethane sponge by combining an automatic feeding system and a high-pressure polyester foaming machine under the conditions of constant temperature of 21 ℃ and high-speed stirring.
Comparative example 2
The embodiment provides a preparation method of zirconia foamed ceramics, which is different from embodiment 3 in step S1, and comparative example 2 adopts an existing photosensitive resin composition for 3D printing, wherein the photosensitive resin composition comprises 290 parts by mass of epoxy acrylate, 210 parts by mass of dipentaerythritol hexaacrylate, 140 parts by mass of lauryl acrylate and isobornyl acrylate (volume ratio 2/1), 300 parts by mass of one-component epoxy resin, 8 parts by mass of defoamer hydrophobic group stearate EL-2600, 6 parts by mass of polymerization inhibitor hydroquinone, 9 parts by mass of leveling agent karmet KMT-5510, 37 parts by mass of radical initiators Irgacure 819 and Irgacure 651 (weight ratio 3/1).
Comparative example 3
This example provides a method for preparing a ceramic foam, which is different from example 3 in step S3. Comparative example 3 the ceramic slurry selected was an aluminum titanate ceramic slurry consisting of calcined alpha-Al 2 O 3 3kg of anatase type titanium dioxide, 2kg of magnesium carbonate powder, 350g of silicon dioxide powder, 10g of ferric oxide, 16g of lanthanum oxide, 1.2 kg of phenolic resin, 20g of polyvinyl butyral, 15g of castor oil, 5g of glycerol trioleate, 1600g of ethanol and 400g of butanone, and the nano-composite material is obtained by mixing and ball milling for 5 hours.
The sponge supports prepared in examples 1 to 5 and comparative examples 1 to 3 were subjected to performance tests, and the results are shown in table 1:
table 1 shows the results of the tests on the performance of the sponge supports prepared in examples 1 to 5 and comparative examples 1 to 3
As can be seen from the data in Table 1, the sponge supporting bodies prepared in the examples of the invention have the density of 25 to 30kg/m 3 (ii) a The tensile strength is more than or equal to 280kPa; the elongation at break is more than or equal to 80 percent; the compression deformation force (40%) was 5.5. + -. 1.5N. The tensile strength and the compression deformation force of the alloy are better than those of a comparative example.
The performance tests were carried out on the zirconia ceramics foams prepared in examples 1 to 5 and comparative examples 1 to 3, and the test results are shown in Table 2.
Table 2 shows the results of the performance tests of the zirconia-based ceramic foams prepared in examples 1 to 5 and comparative examples 1 to 3
As can be seen from the data in Table 2, the zirconia foamed ceramic of the embodiment of the invention has the through hole rate of more than 85 percent, the normal-temperature compressive strength of more than 8.5MPa and the residual strength of more than 3.5MPa after primary air thermal shock at 1400 ℃, and meets the requirement of casting and pouring.
Wherein the through hole rate of the zirconia foamed ceramic is 85.2 to 89.1 percent;
the normal-temperature compressive strength of the zirconia foamed ceramic is 14.6 to 16.9MPa, the residual strength after primary air thermal shock at 1400 ℃ is 6.1 to 7.8 MPa, and the proportion is greatly improved;
FIG. 1 shows the phase compositions of zirconia ceramic foams obtained in examples 1 to 3 of the present invention. As can be seen from FIG. 1, the ceramic foam of the invention has monoclinic ZrO 2 (m-ZrO 2 ) Tetragonal zirconia (t-ZrO) 2 ) Two crystalline states, which have better thermal shock stability. FIG. 2 is a scanning electron micrograph of the zirconia ceramic foam obtained in example 1, and FIG. 2 shows the grain size, area and distribution of the zirconia ceramic foam. The zirconia foamed ceramic prepared by printing the sponge support body by photocuring 3D and performing slurry dipping can be obtained by combining the figure 1, the figure 2 and the table 1, and has high porosity, high mechanical strength and strong thermal shock residual strengthAnd (4) degree and the like.
While the foregoing is directed to the preferred embodiment of the present invention, it will be understood by those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of the invention.
Claims (12)
1. The foamed ceramic is characterized in that a sponge support body is formed by soaking in zirconia ceramic slurry and then sintering at high temperature, wherein the sponge support body is prepared by photocuring 3D printing of a mixed photosensitive material, the mixed photosensitive material comprises a mixed photosensitive resin, and the mixed photosensitive resin comprises the following raw materials in parts by weight:
30-60 parts of epoxy acrylate;
40-70 parts of reactive diluent;
1-5 parts of a free radical photoinitiator;
50-70 parts of aliphatic epoxy resin;
30-50 parts of hydroxybutyl vinyl ether;
1-5 parts of cationic photoinitiator.
2. The ceramic foam of claim 1, wherein the epoxy acrylate has a viscosity of 60000 mPa-s or less;
the active diluent is 1, 6-hexanediol diacrylate, and the viscosity of the active diluent is less than or equal to 10mPa & s;
the free radical photoinitiator is 2,4, 6-trimethylbenzoyl-diphenyl phosphorus oxide, and the component content is more than or equal to 99.0 percent;
the viscosity of the aliphatic epoxy resin is less than or equal to 300mPa & s;
the content of the hydroxybutyl vinyl ether is more than or equal to 98.0 percent;
the cationic photoinitiator is diaryl iodonium salt with the component content of more than or equal to 99.5 percent.
3. The ceramic foam according to claim 2, wherein the viscosity of the epoxy acrylate is 30000 to 60000mPa · s;
the active diluent is 1, 6-hexanediol diacrylate, and the viscosity of the active diluent is 5 to 10mPa & s;
the free radical photoinitiator is 2,4, 6-trimethylbenzoyl-diphenyl phosphorus oxide, and the content of the components is 99.0 to 99.5 percent;
the viscosity of the aliphatic epoxy resin is 200 to 300mPas;
the content of the hydroxybutyl vinyl ether is 98.0-99.5%;
the cationic photoinitiator is diaryl iodonium salt, and the content of the components is 99.5 to 99.8 percent.
4. The ceramic foam according to claim 1, wherein the mixed photosensitive material comprises a mixed photosensitive resin and a ceramic powder, the ceramic powder is added in an amount of 1 to 3wt% based on the mixed photosensitive resin, and the ceramic powder is a zirconia powder.
5. The ceramic foam according to claim 1, wherein the zirconia ceramic slurry is prepared by mixing zirconia powder, magnesia and a binder and performing ball milling;
the particle size of the zirconia powder is 5-30 mu m;
the viscosity of the zirconia ceramic slurry is 12000 mPas-15000 mPas.
6. The ceramic foam of claim 1 having a porosity of greater than 85%, a compressive strength at room temperature of greater than 8.5MPa, and a residual strength after primary air thermal shock at 1400 ℃ of greater than 3.5MPa.
7. A method for preparing a ceramic foam, comprising:
(1) Uniformly stirring 30-60 parts by weight of epoxy acrylate, 40-70 parts by weight of reactive diluent, 2-5 parts by weight of free radical photoinitiator, 50-70 parts by weight of aliphatic epoxy resin, 30-50 parts by weight of hydroxybutyl vinyl ether and 1-5 parts by weight of cationic photoinitiator to obtain mixed photosensitive resin;
(2) Carrying out photocuring 3D printing on the mixed photosensitive resin to obtain a sponge support body;
(3) Carrying out ceramic slurry dipping treatment on the sponge supporting body so as to enable zirconia ceramic slurry to be attached to the sponge supporting body, and obtaining a foamed ceramic blank;
(4) And drying the foamed ceramic blank, and then sintering at high temperature to obtain a foamed ceramic finished product.
8. The method of preparing a ceramic foam according to claim 7, wherein the step (2) comprises:
uniformly mixing the raw materials of the mixed photosensitive resin;
setting the printing layer thickness, the printing speed, the optical power density and the photocuring time of the photocuring 3D printer;
and 3D printing the mixed photosensitive resin through a photocuring 3D printer to obtain the sponge support.
9. The method of claim 7, wherein step (2) comprises:
uniformly mixing the raw materials mixed with the photosensitive resin, and adding ceramic powder;
setting the printing layer thickness, the printing speed, the optical power density and the photocuring time of the photocuring 3D printer;
and 3D printing the mixed photosensitive resin through a photocuring 3D printer to obtain the sponge support.
10. The method for producing a ceramic foam according to claim 8 or 9, wherein the print layer has a thickness of 0.01 to 0.1mm, a print rate of 10 to 50mm/s, and an optical power density of 5 to 25mW/cm 2 And the photocuring time is 2 to 5s.
11. The method of preparing ceramic foam according to claim 7, wherein the step (3) comprises the steps of:
dipping the sponge supporting body in zirconia ceramic slurry, and rolling to form a first blank body;
dipping the first green body in the zirconia ceramic slurry again, and rolling to form a second green body;
drying the second blank;
and after the second green body is dried, spraying the zirconia ceramic slurry on the surface of the second green body to obtain a foamed ceramic green body.
12. The method of preparing a ceramic foam according to claim 7, wherein in step (4): the drying treatment process parameters are as follows: the drying temperature is 35-45 ℃, and the drying time is 8-12h;
the conditions of the high-temperature sintering are as follows:
raising the temperature to 600-620 ℃ at a heating rate of 0.3-0.5 ℃/min, and keeping the temperature for 0.5-1h;
heating to 1680-1720 ℃ at the heating rate of 0.5-1.5 ℃/min, and keeping the temperature for 4-6 h;
the sintering atmosphere is air.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211635966.3A CN115611656A (en) | 2022-12-20 | 2022-12-20 | Foamed ceramic and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211635966.3A CN115611656A (en) | 2022-12-20 | 2022-12-20 | Foamed ceramic and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN115611656A true CN115611656A (en) | 2023-01-17 |
Family
ID=84880666
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211635966.3A Pending CN115611656A (en) | 2022-12-20 | 2022-12-20 | Foamed ceramic and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115611656A (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112759387A (en) * | 2020-12-31 | 2021-05-07 | 松山湖材料实验室 | Zirconia ceramic, preparation method thereof and ceramic filter |
| CN115286745A (en) * | 2022-08-26 | 2022-11-04 | 浙江浙创三维科技有限公司 | Flame-retardant SLA photosensitive resin for 3D printing and preparation method thereof |
-
2022
- 2022-12-20 CN CN202211635966.3A patent/CN115611656A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112759387A (en) * | 2020-12-31 | 2021-05-07 | 松山湖材料实验室 | Zirconia ceramic, preparation method thereof and ceramic filter |
| CN115286745A (en) * | 2022-08-26 | 2022-11-04 | 浙江浙创三维科技有限公司 | Flame-retardant SLA photosensitive resin for 3D printing and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 俞立英, 复旦大学出版社 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104258737B (en) | The preparation method of large size, thin walled hollow ceramic membrane | |
| CN113563103B (en) | Method for preparing gradient alumina porous ceramic by adopting tape casting forming method | |
| CN105254323B (en) | A kind of micropore corundum-mullite ceramics separation-membrane support and preparation method thereof | |
| CN107399989B (en) | Preparation method of reinforced silicon carbide-alumina composite foamed ceramic | |
| WO2018019201A1 (en) | Ceramic foam filter and manufacturing method thereof | |
| CN105272189A (en) | Microporous mullite ceramic separation membrane support and preparation method thereof | |
| CN109879661B (en) | Tundish coating material and preparation method thereof | |
| CN106083075B (en) | The restorative procedure of blast-furnace shaft upper inner liner wet spray material, its application and blast-furnace shaft upper inner liner | |
| CN113087534B (en) | High-temperature-resistant alkali-activated aluminosilicate binder and preparation method thereof | |
| CN114057467B (en) | High-strength ceramic tile and preparation method thereof | |
| CN111056858A (en) | Preparation method of flat ceramic membrane support and ceramic pug thereof | |
| CN106631068A (en) | Bauxite-based homogenous corundum environment-friendly steel ladle base brick and preparation method | |
| CN110040995B (en) | Preparation method of high-temperature light tough mullite aggregate | |
| CN111807812A (en) | Light high-strength ceramic decorative plate and preparation method thereof | |
| CN108997001B (en) | Preparation method of microporous ceramic rod for air brick | |
| CN110669975A (en) | High-strength ceramic material | |
| CN115611656A (en) | Foamed ceramic and preparation method thereof | |
| CN113443901A (en) | High-strength alumina foamed ceramic and preparation method thereof | |
| CN112745134A (en) | Air brick containing corundum ceramic balls and preparation method thereof | |
| CN109704722B (en) | Method for preparing foamed ceramic slurry by using aluminum ash | |
| CN102284677A (en) | Die shell for precisely casting titanium alloy | |
| CN116354729B (en) | SiC ceramic part and preparation method and application thereof | |
| CN113880563B (en) | High-temperature creep-resistant ceramic material and preparation method thereof | |
| CN114538938B (en) | Shell, preparation method thereof and electronic equipment | |
| CN101654359A (en) | Mullite combined alumina-carborundum high-temperature ceramic material and preparation method thereof |
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 | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20230117 |
|
| RJ01 | Rejection of invention patent application after publication |