CN108456456B - 3D direct-writing zirconia colloidal ink - Google Patents
3D direct-writing zirconia colloidal ink Download PDFInfo
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- CN108456456B CN108456456B CN201611141192.3A CN201611141192A CN108456456B CN 108456456 B CN108456456 B CN 108456456B CN 201611141192 A CN201611141192 A CN 201611141192A CN 108456456 B CN108456456 B CN 108456456B
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- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 title claims abstract description 142
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 59
- 239000002253 acid Substances 0.000 claims abstract description 43
- 239000002245 particle Substances 0.000 claims abstract description 35
- 239000003513 alkali Substances 0.000 claims abstract description 31
- 239000000843 powder Substances 0.000 claims abstract description 15
- 239000002904 solvent Substances 0.000 claims abstract description 15
- 239000002270 dispersing agent Substances 0.000 claims abstract description 13
- 229920002125 Sokalan® Polymers 0.000 claims abstract description 10
- 239000011230 binding agent Substances 0.000 claims abstract description 10
- 239000004584 polyacrylic acid Substances 0.000 claims abstract description 10
- 239000007787 solid Substances 0.000 claims abstract description 10
- 229920000058 polyacrylate Polymers 0.000 claims abstract description 7
- 239000002994 raw material Substances 0.000 claims abstract description 6
- 229920002873 Polyethylenimine Polymers 0.000 claims abstract description 3
- 229920005646 polycarboxylate Polymers 0.000 claims abstract description 3
- 239000000919 ceramic Substances 0.000 claims description 41
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 36
- -1 hydrogen ions Chemical class 0.000 claims description 20
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 18
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 18
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 239000008367 deionised water Substances 0.000 claims description 12
- 229910021641 deionized water Inorganic materials 0.000 claims description 12
- 229910052739 hydrogen Inorganic materials 0.000 claims description 9
- 239000001257 hydrogen Substances 0.000 claims description 9
- 239000007790 solid phase Substances 0.000 claims description 9
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 6
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 6
- 239000001913 cellulose Substances 0.000 claims description 6
- 229920002678 cellulose Polymers 0.000 claims description 6
- 239000003822 epoxy resin Substances 0.000 claims description 6
- 229920000647 polyepoxide Polymers 0.000 claims description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 5
- 229910017604 nitric acid Inorganic materials 0.000 claims description 5
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 4
- 229920001817 Agar Polymers 0.000 claims description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 4
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 claims description 4
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 claims description 4
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 4
- 108010010803 Gelatin Proteins 0.000 claims description 4
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 4
- 239000008272 agar Substances 0.000 claims description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 4
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 4
- 239000008273 gelatin Substances 0.000 claims description 4
- 229920000159 gelatin Polymers 0.000 claims description 4
- 235000019322 gelatine Nutrition 0.000 claims description 4
- 235000011852 gelatine desserts Nutrition 0.000 claims description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 4
- 150000007522 mineralic acids Chemical class 0.000 claims description 4
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 claims description 4
- 150000007524 organic acids Chemical group 0.000 claims description 4
- 239000001814 pectin Substances 0.000 claims description 4
- 235000010987 pectin Nutrition 0.000 claims description 4
- 229920001277 pectin Polymers 0.000 claims description 4
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims description 4
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 claims description 4
- 239000004202 carbamide Substances 0.000 claims description 3
- 150000007529 inorganic bases Chemical class 0.000 claims description 3
- 150000007530 organic bases Chemical group 0.000 claims description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 2
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 2
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 2
- 239000005711 Benzoic acid Substances 0.000 claims description 2
- 239000005635 Caprylic acid (CAS 124-07-2) Substances 0.000 claims description 2
- 229920001661 Chitosan Polymers 0.000 claims description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 2
- 229920000084 Gum arabic Polymers 0.000 claims description 2
- IOVCWXUNBOPUCH-UHFFFAOYSA-N Nitrous acid Chemical compound ON=O IOVCWXUNBOPUCH-UHFFFAOYSA-N 0.000 claims description 2
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims description 2
- 241000978776 Senegalia senegal Species 0.000 claims description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 2
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 claims description 2
- 239000000205 acacia gum Substances 0.000 claims description 2
- 235000010489 acacia gum Nutrition 0.000 claims description 2
- 239000001361 adipic acid Substances 0.000 claims description 2
- 235000011037 adipic acid Nutrition 0.000 claims description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 2
- 239000001099 ammonium carbonate Substances 0.000 claims description 2
- QZPSXPBJTPJTSZ-UHFFFAOYSA-N aqua regia Chemical compound Cl.O[N+]([O-])=O QZPSXPBJTPJTSZ-UHFFFAOYSA-N 0.000 claims description 2
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 claims description 2
- 229910001863 barium hydroxide Inorganic materials 0.000 claims description 2
- 235000010233 benzoic acid Nutrition 0.000 claims description 2
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 2
- 239000004327 boric acid Substances 0.000 claims description 2
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 claims description 2
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 2
- 239000000920 calcium hydroxide Substances 0.000 claims description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims description 2
- XTEGARKTQYYJKE-UHFFFAOYSA-N chloric acid Chemical compound OCl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-N 0.000 claims description 2
- 229940005991 chloric acid Drugs 0.000 claims description 2
- QBWCMBCROVPCKQ-UHFFFAOYSA-N chlorous acid Chemical compound OCl=O QBWCMBCROVPCKQ-UHFFFAOYSA-N 0.000 claims description 2
- 229940077239 chlorous acid Drugs 0.000 claims description 2
- 235000019253 formic acid Nutrition 0.000 claims description 2
- 150000001261 hydroxy acids Chemical class 0.000 claims description 2
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 2
- 239000000347 magnesium hydroxide Substances 0.000 claims description 2
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 2
- CVMIVKAWUQZOBP-UHFFFAOYSA-L manganic acid Chemical compound O[Mn](O)(=O)=O CVMIVKAWUQZOBP-UHFFFAOYSA-L 0.000 claims description 2
- 229960002446 octanoic acid Drugs 0.000 claims description 2
- 235000006408 oxalic acid Nutrition 0.000 claims description 2
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 claims description 2
- 150000004965 peroxy acids Chemical class 0.000 claims description 2
- 235000019260 propionic acid Nutrition 0.000 claims description 2
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims description 2
- 229960004889 salicylic acid Drugs 0.000 claims description 2
- 229920002554 vinyl polymer Polymers 0.000 abstract description 9
- 150000003839 salts Chemical class 0.000 abstract description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 abstract 2
- 229910021529 ammonia Inorganic materials 0.000 abstract 1
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 abstract 1
- 239000000976 ink Substances 0.000 description 77
- 238000000034 method Methods 0.000 description 22
- 238000007639 printing Methods 0.000 description 19
- 239000000463 material Substances 0.000 description 17
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 17
- 229910001928 zirconium oxide Inorganic materials 0.000 description 17
- 238000001035 drying Methods 0.000 description 15
- 238000005245 sintering Methods 0.000 description 15
- 239000007921 spray Substances 0.000 description 15
- 239000000725 suspension Substances 0.000 description 15
- 238000005516 engineering process Methods 0.000 description 14
- 238000010438 heat treatment Methods 0.000 description 11
- 238000000465 moulding Methods 0.000 description 11
- 230000008569 process Effects 0.000 description 8
- 238000010146 3D printing Methods 0.000 description 7
- 229910010293 ceramic material Inorganic materials 0.000 description 7
- 239000002002 slurry Substances 0.000 description 7
- 238000002156 mixing Methods 0.000 description 6
- 239000012530 fluid Substances 0.000 description 5
- 230000014759 maintenance of location Effects 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 238000012545 processing Methods 0.000 description 5
- 238000010008 shearing Methods 0.000 description 5
- WJRBRSLFGCUECM-UHFFFAOYSA-N hydantoin Chemical compound O=C1CNC(=O)N1 WJRBRSLFGCUECM-UHFFFAOYSA-N 0.000 description 4
- 229940091173 hydantoin Drugs 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000011224 oxide ceramic Substances 0.000 description 4
- 238000004321 preservation Methods 0.000 description 4
- 230000009471 action Effects 0.000 description 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 3
- 230000001276 controlling effect Effects 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 230000010355 oscillation Effects 0.000 description 3
- 230000000737 periodic effect Effects 0.000 description 3
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 229920000142 Sodium polycarboxylate Polymers 0.000 description 2
- 238000000498 ball milling Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000000903 blocking effect Effects 0.000 description 2
- 235000013877 carbamide Nutrition 0.000 description 2
- 238000001723 curing Methods 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 239000000499 gel Substances 0.000 description 2
- 150000002466 imines Chemical class 0.000 description 2
- 238000007641 inkjet printing Methods 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 238000003754 machining Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000005459 micromachining Methods 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229920001169 thermoplastic Polymers 0.000 description 2
- 239000004416 thermosoftening plastic Substances 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- LDDQLRUQCUTJBB-UHFFFAOYSA-N ammonium fluoride Chemical compound [NH4+].[F-] LDDQLRUQCUTJBB-UHFFFAOYSA-N 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 235000011116 calcium hydroxide Nutrition 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000011960 computer-aided design Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 239000000495 cryogel Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000007943 implant Substances 0.000 description 1
- 238000000608 laser ablation Methods 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 238000009768 microwave sintering Methods 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 238000000016 photochemical curing Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 235000011118 potassium hydroxide Nutrition 0.000 description 1
- 238000011085 pressure filtration Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000000110 selective laser sintering Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 238000002174 soft lithography Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
Images
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/30—Inkjet printing inks
-
- 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
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/30—Inkjet printing inks
- C09D11/38—Inkjet printing inks characterised by non-macromolecular additives other than solvents, pigments or dyes
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Ceramic Engineering (AREA)
- Compositions Of Oxide Ceramics (AREA)
- Composite Materials (AREA)
- Manufacturing & Machinery (AREA)
- Structural Engineering (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
Abstract
3D直写的氧化锆胶体墨水，原料包括氧化锆颗粒，溶剂，粘结剂，酸剂，碱剂以及分散剂；所述的氧化锆颗粒粒径范围为0.05‑2μm，其在墨水中的固相含量范围为40‑56vol％；所述的分散剂为聚丙烯酸、聚乙烯酸、聚丙烯酸氨、聚乙烯亚胺、聚丙烯酸盐、聚乙烯酸盐、聚羧酸盐中的一种或几种，所述的分散剂为氧化锆颗粒干粉质量的0.1‑4wt％；所述的酸剂的量为不超过墨水质量的0.1％,所述的碱剂的量为不超过墨水质量的0.1％，所述的酸剂和碱剂中的氢离子与氢氧根离子的摩尔比为(0.01‑4)∶1。本发明在室温下打印，具有较高的固含量的同时仍可以从精细的喷嘴中流出而不发生堵塞，并且可以迅速固化成具有一定强度的细丝用于各种造型，具有良好流变性能。The zirconia colloidal ink for 3D direct writing, the raw materials include zirconia particles, a solvent, a binder, an acid agent, an alkali agent and a dispersant; the zirconia particles have a particle size range of 0.05-2 μm, and their solidity in the ink is 0.05-2 μm. The phase content range is 40-56vol%; the dispersant is one or more of polyacrylic acid, polyvinyl acid, polyacrylic acid ammonia, polyethylene imine, polyacrylate, polyvinyl acid salt, and polycarboxylate. The amount of the dispersant is 0.1-4wt% of the dry powder quality of the zirconia particles; the amount of the acid agent is no more than 0.1% of the ink mass, and the amount of the alkali agent is no more than 0.1% of the ink mass , the mol ratio of hydrogen ion and hydroxide ion in described acid agent and alkali agent is (0.01-4): 1. The invention prints at room temperature, has high solid content and can still flow out from fine nozzles without clogging, and can be quickly solidified into filaments with a certain strength for various shapes, and has good rheological properties .
Description
Technical Field
The invention relates to zirconia colloidal ink for 3D direct writing, and belongs to the technical field of 3D printing material design.
Background
Modern micromachining technology has incomparable advantages of traditional machining methods on the micro-nano scale. The micromachining technology includes a soft lithography technology, a laser ablation technology, a stereolithography technology, a two-photon polymerization technology, an electrostatic discharge technology, a 3D direct writing technology, and the like. Among them, the 3D Direct-writing (also called Direct-writing Assembly) is a branch of the 3D printing technology. Typical examples of 3D printing manufacturing techniques include photocuring molding, selective laser sintering molding, and layered solid molding, but the methods have the disadvantages of low molding precision, complex subsequent processing, and low molding strength, and are not suitable for preparing small and fine parts. In recent years, the 3D Direct write molding (DIW) based on rapid prototyping has attracted much attention of researchers because it can produce complex and fine three-dimensional periodic structures having a large aspect ratio and containing span features.
3D direct writing refers broadly to a technique for precision molding of materials of specific composition according to a structure set by computer software using a molding machine mounted on a computer-controlled platform. Generally, ink materials (ink) are stored in a temperature-controllable charging barrel, a nozzle is connected with the charging barrel and is installed on a three-axis CNC positioning table, the materials are sprayed out by a pressure-controlled feeding micro-nozzle (microzyme), and different curing processes are selected according to the curing modes of the materials to cure and form the sprayed ink materials. As long as the ink has proper rheological property and certain shape retention, various materials can be designed into printing ink for the modeling mode, the diameter of the printed filament ranges from hundreds of nanometers to millimeters, and the filament can span a larger gap and even can be freely formed in space to complete processing tasks which are difficult to complete by other processing technologies.
The 3D direct-writing forming technology is a novel model-free forming technology, accurately controls the deposition of suspension by means of computer aided design and precision machinery, and prepares simple three-dimensional periodic structures and complex three-dimensional structures containing spans (without supports) or having large height-width ratios in a layer-by-layer overlapping mode. Compared with other rapid forming methods, the direct-writing forming technology has the following remarkable advantages: 1) the forming process does not need a die, the production period is short, the efficiency is high, and the cost is low; 2) the shape and the size of the sample can be conveniently changed according to the requirement, the production is flexible, and the control is accurate; 3) the raw materials are diversified, and inorganic nonmetal, metal, organic polymer and the like exist; 4) can be used for preparing functional materials in the fields of biology, optics, electronics and the like, even living cells.
The method is completely different from the traditional material processing technology, and the 3D direct writing has the advantages of strong simulation, high speed, low price, high usability and the like, and is a subversive change to the traditional manufacturing industry. However, as an immature technique, the scientific and technical research of 3D direct writing is still in the beginning stage, and there are few researches and literature reports on this stage, and no literature reports are found in China. Moreover, 3D direct-writing printing ink needs to flow out of a fine nozzle without blockage, and can be quickly solidified into a filament with certain strength for various modeling; therefore, 3D direct write printing inks must possess both shear thinning and viscoelasticity, such as elastic modulus over loss modulus. In general, inks for ultra-fine scale printing have a shear strain rate of 20-200S-1The viscosity is about 10 to 100Pa · S.
The ceramic material is one of 3D printing materials, and due to the structure and the bonding property of the ceramic material, the ceramic material has few slippage systems, and dislocation generation and movement are difficult, on the other hand, the ceramic material has a tendency of separation along a grain boundary, and the series of conditions make the ceramic material essentially a brittle material; thermoplastic processability and flowability of brittle materials are difficult to control, so 3D printing of ceramic materials is more difficult to control than metallic materials. Chinese patent publication No. CN104108131A discloses a 3D printing molding method for ceramic materials, which mixes sol with low-temperature freezing characteristics with ceramic or metal powder to prepare slurry with cryogel properties, and the slurry is sprayed on a low-temperature printing platform by a printing head to be frozen and gel-cured, and then is printed layer by layer to obtain various materials and products. The method has the characteristics of simple raw material preparation process, rapidness and convenience, but the method needs a frozen state in the 3D printing process and has high cost. In addition, publication No. 104877463 discloses a zirconia ceramic ink for 3D inkjet printing and a preparation method thereof; however, the ink is used for 3D ink-jet printing, the requirement on solid content is not high, and the ink cannot be effectively cured and formed in a 3D direct-writing state, so that the ink obtained according to the scheme does not meet the requirement of the 3D direct-writing ink at all. Therefore, for those skilled in the art, how to obtain a ceramic ink which is low in preparation cost and suitable for 3D direct-write printing is still a technical problem to be solved.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides the zirconia colloidal ceramic ink for 3D direct writing, which is printed at room temperature, has higher solid content, can still flow out from a fine nozzle without blockage, can be quickly solidified into filaments with certain strength for various shapes, and has good rheological property. The invention provides 3D direct-writing zirconia colloidal ceramic ink which comprises zirconia particles, a solvent, a binder, an acid agent, an alkali agent and a dispersing agent; the particle size range of the zirconia particles is 0.05-2 mu m, and the solid phase content of the zirconia particles in the ink is 40-56 vol%; the dispersing agent is one or more of polyacrylic acid, polyvinyl acid, ammonium polyacrylate, polyethyleneimine, polyacrylate, polyvinyl acid salt and polycarboxylate, and the dispersing agent accounts for 0.1-4 wt% of the dry powder of the zirconia particles; the amount of the acid agent is not more than 0.1 percent of the mass of the ink, the amount of the alkali agent is not more than 0.1 percent of the mass of the ink, and the molar ratio of hydrogen ions to hydroxide ions in the acid agent and the alkali agent is (0.01-4) to 1.
The solvent is preferably one or more of deionized water, absolute ethyl alcohol, ethylene glycol, propylene glycol and glycerol.
The binder is preferably one or more of acrylamide, gelatin, agar, epoxy resin, cellulose, chitosan, gum arabic and pectin.
The binder is preferably 0.01 to 25 wt% of the mass of the solvent.
The inventors of the present invention have conducted intensive studies on 3D direct-write zirconia ink, and surprisingly found that by controlling the amount of the dispersant to be 0.1-4 wt% of the dry powder mass of zirconia particles, controlling the amount of the acid and alkali agents to be not more than 0.1% of the mass of the ink, and controlling the molar ratio of hydrogen ions to hydroxyl ions to be (0.01-4): 1, the synergistic effect of these conditions can ensure that the viscosity of the ink suspension is still low in the range of the solid content in the zirconia ink up to 40-58 vol% and under the high shear action, the ink suspension can smoothly pass through the nozzle without clogging, and can be rapidly cured into filaments having a certain strength for various molding, and still have good rheological properties. In addition, the inventors found through experiments that serious agglomeration phenomenon occurs if the amount of the acid or alkali agent exceeds 0.1% by mass of the ink. This solution is not achieved as the skilled person is not aware. The proposal of the invention well solves the problem of nozzle blockage with high solid content and ensures the high solid content of the zirconia ceramic powder, thereby effectively avoiding the cracking or deformation of the forming structure caused by shrinkage in the drying and sintering processes in the forming process of the ink.
In the present invention, the molar ratio of hydrogen ions to hydroxide ions of the acid agent to the alkali agent is preferably (0.1-3) to 1.
The elastic modulus of the zirconia ceramic ink obtained by the scheme of the invention is 102-106Pa, viscosity of 0.1-100 pas.
The acid agent is organic acid or inorganic acid.
The organic acid is one or more of formic acid, acetic acid, carboxylic acid, hydroxy acid, glycolic acid, oxalic acid, adipic acid, succinic acid, benzoic acid, salicylic acid, propionic acid, butyric acid, caprylic acid and acrylic acid.
The inorganic acid is one or more of hydrochloric acid, nitric acid, sulfuric acid, perchloric acid, hydrofluoric acid, boric acid, phosphoric acid, carbonic acid, chloric acid, manganic acid, chlorous acid, nitrous acid, peroxyacid, superoxide acid, ozone acid, peroxywater and aqua regia.
The alkaline agent is organic alkali or inorganic alkali.
The inorganic base is one or more of potassium hydroxide, calcium hydroxide, sodium hydroxide, ammonium bicarbonate, ammonia water, ammonium hydrofluoride, aluminum hydroxide, magnesium hydroxide and barium hydroxide.
The organic base is one or more of methylamine, urea (carbamide), ethylamine, ethanolamine and ethylenediamine.
Uniformly mixing raw material zirconium oxide particles, a binder, a solvent, an acid agent, an alkali agent and a dispersant to form slurry, adding zirconium oxide grinding balls and a defoaming agent, performing ball milling, and performing ultrasonic oscillation to prepare the zirconium oxide ceramic ink.
In the scheme, the preferable solid content range of the zirconium oxide is 40-56 vol%, the solvent is water, the dispersing agent is polyethylene acid, polyacrylic acid or ammonium polyacrylate and is 0.2-2.0% of the mass of the zirconium oxide particle dry powder, and the binder is 0.01-15% of the mass of the solvent; the acid agent is hydrochloric acid, sulfuric acid or nitric acid, and accounts for 0.001-0.1% of the mass of the ink, the alkali agent is sodium hydroxide, potassium hydroxide or ammonia water and accounts for 0.001-0.1% of the mass of the ink, and the molar ratio of hydrogen ions to hydroxide ions of the acid agent to the alkali agent is (0.1-3): 1.
the first further preferable technical scheme of the invention is as follows: mixing zirconia particles with the particle size of 0.1-1 mu m, deionized water, cellulose, an acid agent, an alkali agent and polyethylene acid to form slurry; in the slurry: the solid phase content of the zirconia is 40-56 vol%, the content of the cellulose in the deionized water is 0.002-0.008g/ml, and the polyvinyl carboxylic acid accounts for 0.4-1.2% of the mass content of the zirconia particle dry powder; the acid agent is hydrochloric acid, the alkali agent is sodium hydroxide, and the molar ratio of hydrogen ions to hydroxide ions of the acid agent to the alkali agent is (1.5-2): 1.
a further preferred embodiment of the present invention is: mixing 0.05-1 mu m zirconium oxide particles, solvent deionized water, acid agent, alkali agent, adhesive hydantoin epoxy resin, polyvinyl acid or polyacrylic acid, wherein the solid phase content of zirconium oxide is 40-56 vol%, the content of hydantoin epoxy resin in deionized water is 5-25 wt%, the content of polyvinyl acid polyacrylic acid is 0.4-1.2% of dry powder content, the acid agent is sulfuric acid, the alkali agent is sodium hydroxide, and the molar ratio of hydrogen ions to hydroxide ions of the acid agent to the alkali agent is (0.5-2): 1.
the raw materials are mixed and then are placed on a ball mill to be ball milled for 12-24h at the rotating speed of 100-.
The specific application of the 3D direct-writing zirconia ceramic ink is as follows: the method comprises the steps of loading 3D direct-writing zirconia ceramic ink into a spray cylinder of 3D direct-writing equipment, setting the diameter of a spray nozzle to be 0.5-400 mu m, starting a program of the 3D direct-writing equipment, printing in the air in a layer-by-layer overlapping mode to obtain a three-dimensional structure, drying the obtained three-dimensional structure at room temperature for 6-12h, then drying at 60 ℃ for 12-24h, then drying at 80 ℃ for 12-24h to obtain a green compact of the three-dimensional structure, and then placing the green compact in a common sintering furnace, heating to 1300-1700 ℃ by the program, and sintering to obtain the zirconia ceramic product with the three-dimensional structure.
The 3D direct-writing forming method of the zirconia ceramic ink comprises the following steps:
loading the prepared zirconia ceramic ink into a spray cylinder of 3D direct writing equipment, wherein the temperature of the spray cylinder is room temperature, inputting programming and parameter setting of related programs on a computer, starting printing to obtain a green body structure in a layer-by-layer superposition mode, drying the green body at room temperature, then drying at 60 ℃, then drying at 80 ℃, and after drying is finished, placing the obtained green body in a sintering furnace, and heating to 1300-1700 ℃ by a program to sinter to obtain the 3D structure zirconia ceramic product.
Preferably, the sintering method can be common sintering and microwave sintering, the sintering procedure preferably comprises the steps of heating to 500 ℃ at 1 ℃/min, keeping the temperature for 4h, heating to 1000 ℃ at 10 ℃/min, keeping the temperature for 1h, and then heating to 1550 ℃ at the same speed for heat-preservation sintering.
The scheme of the invention can prepare a complex and fine micro-scale three-dimensional structure. In the forming process, the suspension ink can smoothly pass through the micro-nano-scale fine cylindrical nozzle to form characteristic linear fluid, and is quickly cured to keep the shape, and even the shape of the suspension ink is kept without collapse or fracture when a structure containing span or a suspended beam (without support) is formed. The suspension ink of the present invention has the following distinct 3 advantages: 1) under the action of high shear, the viscosity of the suspension is very low, so that the suspension can smoothly pass through the nozzle without blockage; 2) the linear fluid is rapidly solidified without shearing action, and the solidified linear fluid has better elastic property and strength and can keep the original shape even under the condition of no support; 3) the suspension has a high solid volume fraction which prevents the formation of cracks or deformations caused by shrinkage during drying and sintering
In the suspension ink of the present invention, the radial shear stress applied to the filament inside the nozzle increases linearly from the center to the edge during the formation process. The center of the suspension ink filament of the present invention is substantially unaffected by shear stress and is in a rigid gel state. And the edge part of the filament has larger friction with the inner wall of the nozzle to generate shear stress, and when the shear stress is larger than tau y, the surface viscosity of the filament is sharply reduced and is in a flowing state. Thus, the filaments of the suspension ink of the present invention in the nozzle have a rigid (gel) core-shear fluid shell structure that functions well to maintain the molded shape. In addition, the suspension ink can be smoothly output from the nozzle, the blockage of the micro-nano-scale nozzle caused by the pressure filtration phenomenon of the suspension is avoided, and the inventor finds that the shear stress acting on the filiform linear fluid required by the ink forming of the 3D direct writing forming is in accordance with the relation that the yield shear stress is greater than the yield shear stress tau y and is smaller than the compressive yield stress py of the suspension.
The ink of the invention is printed in 20-100S-1The viscosity is less than 10 Pa.S under the shearing speed, and the ink has good rheological property under the direct writing state. The ink printing of the invention does not need thermoplastic processing, and can be directly formed without subsequent machining process because of near net size forming. The green structure produced by the ink printing of the invention is a scaffold structure with three-dimensional periodic directional arrangement. In addition, the ink printing of the invention can also be suitable for the spray head with the nozzle diameter of 50nm-1mm, and the application range is very wide.
The application of the 3D direct-writing formed zirconia ceramic can be used for preparing various special-shaped parts, structural parts and customized products of zirconia ceramic, and comprises the step of preparing the zirconia ceramic ink into medical implants and tissue engineering scaffolds through 3D direct writing.
The zirconia ceramic ink developed by the invention can be directly used for 3D direct writing printing, the zirconia ceramic support printed by the 3D direct writing printing has high strength, the porosity and the support width can be randomly regulated, the preparation method is simple and easy to operate, the preparation condition is mild and has no special requirements, and the large-scale industrial application is easy.
Drawings
Fig. 1 is a 16-layer zirconia ceramic scaffold 3D direct-written from the zirconia colloidal ceramic ink of example 1.
Fig. 2 is a schematic process diagram of 3D direct writing molding of zirconia colloidal ceramic ink in example 1.
FIG. 3 is a graph of viscosity data for the zirconia colloidal ceramic ink of example 1, shear rate on the abscissa and viscosity on the ordinate, at 10s-1The viscosity at shear rate was 2 pas.
FIG. 4 shows the elastic modulus of the zirconia colloidal ceramic ink of example 1, with the abscissa representing the oscillating stress and the ordinate representing the elastic modulus, which is still as high as 10 at a pressure of 10Pa4Pa。
Fig. 5 is a special-shaped zirconia ceramic structural member prepared by 3D direct writing zirconia colloidal ceramic ink in example 2.
FIG. 6 is a graph of viscosity data for the zirconia colloidal ceramic ink of example 2, shear rate on the abscissa and viscosity on the ordinate, at 10s-1The viscosity at shear rate was 4 pas.
FIG. 7 shows the elastic modulus of the zirconia colloidal ceramic ink of example 2, the abscissa represents the oscillation stress, and the ordinate represents the elastic modulus, and the elastic modulus of the ceramic ink is still as high as 10 under a pressure of 10Pa3Pa。
FIG. 8 is a graph of viscosity data for the zirconia colloidal ceramic ink of example 3, shear rate on the abscissa and viscosity on the ordinate, at 10s-1The viscosity at shear rate was 10 pas.
FIG. 9 shows the elastic modulus of the zirconia colloidal ceramic ink of example 3, the abscissa shows the oscillating stress and the ordinate shows the elastic modulus, and the elastic modulus of the ceramic ink is still as high as 10 under a pressure of 10Pa5Pa
Fig. 10 is a comparison of the dispersion of zirconia particles in a conventional slurry and a 3D direct writing ink, in which a shows the dispersion of zirconia particles in a conventional slurry, the zirconia particles being dispersed independently of each other in a solvent, and b shows the dispersion of particles in an ink according to the present invention, the particles being connected to each other to form a network structure and being dispersed in a solvent.
Detailed Description
The following examples are intended to illustrate the invention without further limiting it.
Example 1
Zirconium oxide particles (preferably particle diameter D)500.8um), deionized water, sulfuric acid, sodium hydroxide, cellulose and polyvinyl acid, wherein the solid phase content of zirconium oxide is 45 percent, the cellulose content is 0.002g/ml, the content of polyvinyl carboxylic acid is 0.6 percent of the dry powder content, the sulfuric acid content is 0.05 percent, and the sodium hydroxide content is 0.05 percent, the materials are mixed in proportion and then placed on a ball mill to be ball milled for 12 hours at the rotating speed of 90rmp, and the zirconium oxide ceramic ink is obtained and has very good shearing thinning propertyProperty, it is in 10s-1A viscosity at shear rate of 2 pas and very good viscoelasticity, with an elastic modulus of up to 10Pa at 10Pa4Pa, good shape retention, being capable of smoothly blocking through a needle nozzle and keeping a three-dimensional shape, then filling the ink into a spray cylinder of 3D direct writing equipment, setting the diameter of the spray nozzle to be 100um, setting the program of the 3D direct writing equipment, starting printing in the air in a layer-by-layer superposition mode to obtain a three-dimensional structure, drying the obtained three-dimensional structure at room temperature for 6h, then drying at 60 ℃ for 12h, then drying at 80 ℃ for 12h to obtain a green body of the three-dimensional structure, then placing the green body in a common sintering furnace, heating to 500 ℃ at a speed of 1 ℃/min, keeping the temperature for 4h, then heating to 1000 ℃ at a speed of 10 ℃/min, keeping the temperature for 1h, and then heating to 1550 ℃ at the same speed to obtain the zirconia ceramic product with the three-dimensional structure. (see FIGS. 1-4).
Example 2
Mixing 1 micron zirconia particles, deionized water, an acid agent, an alkali agent, hydantoin epoxy resin and polyacrylic acid, wherein the solid phase content of the zirconia is 40 vol%, the hydantoin epoxy resin with the content of 15 wt%, the polyacrylic acid is 0.8% of the dry powder content, the sulfuric acid is 0.1% of the mass of the ink, the alkali agent is sodium hydroxide with the amount of 0.05% of the mass of the ink, mixing the materials in proportion, placing the mixture on a ball mill, performing ball milling for 12-24h at the rotation speed of 100 rmp 140, taking down, and performing ultrasonic oscillation for 1-12h to obtain the 3D direct-written zirconia ceramic ink. It is in 10s-1A viscosity at shear rate of 4 pas and very good viscoelasticity, with an elastic modulus of up to 10 at 10Pa3Pa, good shape retention, and can smoothly pass through the needle nozzle to block and maintain the three-dimensional shape.
The 3D direct-writing zirconia ceramic ink is filled into a spray cylinder of 3D direct-writing equipment, the diameter of a spray nozzle is 2 microns, the program of the 3D direct-writing equipment is set, the three-dimensional structure can be obtained by printing in the air in a layer-by-layer overlapping mode, the obtained three-dimensional structure is dried at room temperature for 6-12 hours and then dried at 60 ℃ for 12-24 hours, then dried at 80 ℃ for 12-24 hours to obtain a green body of the three-dimensional structure, and then the green body is placed into a common sintering furnace to be sintered at 1400 ℃ by program heating to obtain the zirconia ceramic product of the three-dimensional structure. (see FIGS. 5-7).
Example 3
Mixing 0.5 mu m zirconium oxide particles, deionized water, pectin, an acid agent, an alkali agent and a sodium polycarboxylate, wherein the solid phase content of the zirconium oxide is 55 vol%, the pectin content is 0.1g/ml, the sodium polycarboxylate is 0.8% of the dry powder content, the acid agent is sulfuric acid, the acid agent is 0.05%, the alkali agent is sodium hydroxide, the alkali agent is 0.05%, the materials are mixed in proportion and then placed on a ball mill to be ball-milled for 12-24h at the rotating speed of 100 plus 140rmp, and then the mixture is taken down and ultrasonically oscillated for 1-12h to obtain the 3D direct-written zirconium oxide ceramic ink. It is in 10s-1Viscosity at shear rate of 10 pas and very good viscoelasticity with an elastic modulus of up to 10Pa at 10Pa5Pa, good shape retention, and can smoothly pass through the needle nozzle to block and maintain the three-dimensional shape.
The 3D direct-writing zirconia ceramic ink is filled into a spray cylinder of 3D direct-writing equipment, the diameter of a spray nozzle is 10 microns, a program of the 3D direct-writing equipment is set, the three-dimensional structure can be obtained by printing in the air in a layer-by-layer overlapping mode, the obtained three-dimensional structure is dried at room temperature for 6-12 hours and then dried at 60 ℃ for 12-24 hours, then dried at 80 ℃ for 12-24 hours to obtain a green body of the three-dimensional structure, and then the green body is placed into a common sintering furnace to be sintered at 1500 ℃ by the program heating to obtain the zirconia ceramic product of the three-dimensional structure. (see FIGS. 8 and 9)
Example 4
Zirconium oxide particles (preferably particle diameter D)500.7um), deionized water, hydrochloric acid, sodium hydroxide, gelatin and polyacetyl imine are mixed, the solid phase content of zirconium oxide is 40 percent, the content of gelatin is 0.03g/ml, the content of polyacetyl imine is 1.0 percent of the dry powder content, the content of hydrochloric acid is 0.01 percent, the content of sodium hydroxide is 0.1 percent, the materials are mixed according to a certain proportion and then placed on a ball mill to be ball milled for 14 hours at a rotating speed of 80rmp, and the zirconium oxide ceramic ink is obtained and has very good shearing thinning property, and the shearing thinning property is 10s-1A viscosity at shear rate of 2 pas and very good viscoelasticity, with an elastic modulus of up to 10Pa at 10Pa3Pa, good shape retentionThe ink can be smoothly blocked by a needle nozzle and keeps a three-dimensional shape, then the ink is filled into a spray cylinder of 3D direct writing equipment, the diameter of the spray nozzle is 100 micrometers, a program of the 3D direct writing equipment is set, the three-dimensional structure can be obtained by printing in the air in a layer-by-layer superposition mode, the obtained three-dimensional structure is dried at room temperature for 6 hours and then dried at 60 ℃ for 12 hours, then dried at 80 ℃ for 12 hours to obtain a green body of the three-dimensional structure, then the green body is placed in a common sintering furnace to be heated to 500 ℃ at a speed of 1 ℃/min for heat preservation for 4 hours, then the green body is heated to 1000 ℃ at a speed of 10 ℃/min for heat preservation for 1 hour, and then the temperature is heated to 1550 ℃ at the same speed for heat preservation and sintering.
Example 5
Zirconium oxide particles (preferably particle diameter D)500.6um), deionized water, nitric acid, potassium hydroxide, agar and ammonium polyacrylate are mixed, the content of zirconia solid phase is 42 percent, the content of agar is 0.05g/ml, the content of ammonium polyacrylate is 1.20 percent of the content of dry powder, the content of hydrochloric acid is 0.1 percent, and the content of potassium hydroxide is 0.09 percent, the materials are mixed according to a certain proportion and then placed on a ball mill to be ball milled for 14 hours at a rotating speed of 80rmp, and the zirconia ceramic ink is obtained and has very good shear thinning property, and the shear thinning property is 10s-1A viscosity at shear rate of 2 pas and very good viscoelasticity, with an elastic modulus of up to 10Pa at 10Pa4Pa, good shape retention, being capable of smoothly blocking through a needle nozzle and keeping a three-dimensional shape, then filling the ink into a spray cylinder of 3D direct writing equipment, setting the diameter of the spray nozzle to be 100um, setting the program of the 3D direct writing equipment, starting printing in the air in a layer-by-layer superposition mode to obtain a three-dimensional structure, drying the obtained three-dimensional structure at room temperature for 6h, then drying at 60 ℃ for 12h, then drying at 80 ℃ for 12h to obtain a green body of the three-dimensional structure, then placing the green body in a common sintering furnace, heating to 500 ℃ at a speed of 1 ℃/min, keeping the temperature for 4h, then heating to 1000 ℃ at a speed of 10 ℃/min, keeping the temperature for 1h, and then heating to 1550 ℃ at the same speed to obtain the zirconia ceramic product with the three-dimensional structure.
Claims (7)
1. The 3D direct-writing zirconia colloidal ink is characterized in that raw materials comprise zirconia particles, a solvent, a binder, an acid agent, an alkali agent and a dispersant; the particle size range of the zirconia particles is 0.05-2 mu m, and the solid phase content of the zirconia particles in the ink is 40-56 vol%; the dispersant is one or more of polyacrylic acid, polyethyleneimine and polycarboxylate, and the dispersant accounts for 0.1-4 wt% of the mass of the zirconia particle dry powder; the binder is one or more of acrylamide, gelatin, agar, epoxy resin, cellulose, chitosan, gum arabic and pectin; the amount of the acid agent is not more than 0.1 percent of the mass of the ink, the amount of the alkali agent is not more than 0.1 percent of the mass of the ink, and the molar ratio of hydrogen ions to hydroxide ions in the acid agent and the alkali agent is (0.01-4) to 1.
2. The 3D direct-written zirconia colloidal ink according to claim 1, wherein the solvent is one or more of deionized water, absolute ethyl alcohol, ethylene glycol, propylene glycol, and glycerol.
3. A 3D direct-write zirconia colloidal ink according to claim 1 wherein the binder is 0.01 to 25 wt% of the solvent mass.
4. The 3D direct-written zirconia colloidal ink according to claim 1, wherein the molar ratio of hydrogen ions to hydroxide ions of the acid agent to the alkali agent is (0.1-3) to 1.
5. The 3D direct-written zirconia colloidal ceramic ink according to claim 1, wherein the acid agent is an organic acid or an inorganic acid; the organic acid is one or more of formic acid, acetic acid, hydroxy acid, oxalic acid, adipic acid, succinic acid, benzoic acid, salicylic acid, propionic acid, butyric acid, caprylic acid and acrylic acid;
the inorganic acid is one or more of hydrochloric acid, nitric acid, sulfuric acid, perchloric acid, hydrofluoric acid, boric acid, phosphoric acid, carbonic acid, chloric acid, manganic acid, chlorous acid, nitrous acid, peroxyacid, superoxide acid, ozone acid, peroxywater and aqua regia.
6. The 3D direct-write zirconia colloidal ceramic ink according to claim 1, wherein the alkaline agent is an organic or inorganic base; the inorganic base is one or more of potassium hydroxide, calcium hydroxide, sodium hydroxide, ammonium bicarbonate, ammonia water, aluminum hydroxide, magnesium hydroxide and barium hydroxide; the organic base is one or more of methylamine, urea, ethylamine, ethanolamine and ethylenediamine.
7. The 3D direct-write zirconia colloidal ink according to claim 1, wherein the zirconia solid content is in the range of 40-56 vol%, the solvent is deionized water, the dispersant is polyacrylic acid or ammonium polyacrylate and is 0.2-2.0% by mass of the zirconia particle dry powder, and the binder is 0.01-15% by mass of the solvent; the acid agent is hydrochloric acid, sulfuric acid or nitric acid, and accounts for 0.001-0.1% of the mass of the ink, the alkali agent is sodium hydroxide, potassium hydroxide or ammonia water and accounts for 0.001-0.1% of the mass of the ink, and the molar ratio of hydrogen ions to hydroxide ions of the acid agent to the alkali agent is (0.1-3): 1.
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| CN113604098B (en) * | 2021-07-29 | 2024-02-06 | 西湖未来智造(杭州)科技发展有限公司 | 3D printing ink and preparation method and application thereof |
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