CN116553926A - Lead-free piezoelectric ceramic slurry for DLP photocuring 3D printing and preparation method thereof - Google Patents
Lead-free piezoelectric ceramic slurry for DLP photocuring 3D printing and preparation method thereof Download PDFInfo
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- CN116553926A CN116553926A CN202310823564.4A CN202310823564A CN116553926A CN 116553926 A CN116553926 A CN 116553926A CN 202310823564 A CN202310823564 A CN 202310823564A CN 116553926 A CN116553926 A CN 116553926A
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- potassium sodium
- niobate powder
- coupling agent
- printing
- lead
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- 239000002002 slurry Substances 0.000 title claims abstract description 67
- 239000000919 ceramic Substances 0.000 title claims abstract description 49
- 238000000016 photochemical curing Methods 0.000 title claims abstract description 49
- 238000010146 3D printing Methods 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000000843 powder Substances 0.000 claims abstract description 93
- BITYAPCSNKJESK-UHFFFAOYSA-N potassiosodium Chemical class [Na].[K] BITYAPCSNKJESK-UHFFFAOYSA-N 0.000 claims abstract description 69
- 239000011347 resin Substances 0.000 claims abstract description 52
- 229920005989 resin Polymers 0.000 claims abstract description 52
- 150000003254 radicals Chemical class 0.000 claims abstract description 49
- 239000007822 coupling agent Substances 0.000 claims abstract description 37
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 31
- 125000001931 aliphatic group Chemical group 0.000 claims abstract description 28
- 239000003085 diluting agent Substances 0.000 claims abstract description 26
- 239000002318 adhesion promoter Substances 0.000 claims abstract description 24
- 239000002270 dispersing agent Substances 0.000 claims abstract description 23
- 229920002635 polyurethane Polymers 0.000 claims abstract description 23
- 239000004814 polyurethane Substances 0.000 claims abstract description 23
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 20
- 239000002518 antifoaming agent Substances 0.000 claims abstract description 11
- 239000003999 initiator Substances 0.000 claims abstract description 10
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 30
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 12
- 238000000498 ball milling Methods 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 9
- -1 ethyl 2,4, 6-trimethylbenzoyl phenyl Chemical group 0.000 claims description 8
- 239000011259 mixed solution Substances 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- 239000013530 defoamer Substances 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- 239000002245 particle Substances 0.000 claims description 7
- 239000000725 suspension Substances 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 6
- 239000000049 pigment Substances 0.000 claims description 6
- 238000009210 therapy by ultrasound Methods 0.000 claims description 6
- 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 claims description 5
- ZDQNWDNMNKSMHI-UHFFFAOYSA-N 1-[2-(2-prop-2-enoyloxypropoxy)propoxy]propan-2-yl prop-2-enoate Chemical compound C=CC(=O)OC(C)COC(C)COCC(C)OC(=O)C=C ZDQNWDNMNKSMHI-UHFFFAOYSA-N 0.000 claims description 5
- MYWOJODOMFBVCB-UHFFFAOYSA-N 1,2,6-trimethylphenanthrene Chemical compound CC1=CC=C2C3=CC(C)=CC=C3C=CC2=C1C MYWOJODOMFBVCB-UHFFFAOYSA-N 0.000 claims description 4
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 4
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 claims description 4
- FSDNTQSJGHSJBG-UHFFFAOYSA-N piperidine-4-carbonitrile Chemical compound N#CC1CCNCC1 FSDNTQSJGHSJBG-UHFFFAOYSA-N 0.000 claims description 4
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 claims description 3
- VOBUAPTXJKMNCT-UHFFFAOYSA-N 1-prop-2-enoyloxyhexyl prop-2-enoate Chemical compound CCCCCC(OC(=O)C=C)OC(=O)C=C VOBUAPTXJKMNCT-UHFFFAOYSA-N 0.000 claims description 3
- POLZHVHESHDZRD-UHFFFAOYSA-N 2-hydroxyethyl 2-methylprop-2-enoate;phosphoric acid Chemical compound OP(O)(O)=O.CC(=C)C(=O)OCCO POLZHVHESHDZRD-UHFFFAOYSA-N 0.000 claims description 3
- 229910019142 PO4 Inorganic materials 0.000 claims description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- 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 claims description 3
- PHYFQTYBJUILEZ-UHFFFAOYSA-N Trioleoylglycerol Natural products CCCCCCCCC=CCCCCCCCC(=O)OCC(OC(=O)CCCCCCCC=CCCCCCCCC)COC(=O)CCCCCCCC=CCCCCCCCC PHYFQTYBJUILEZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000013504 Triton X-100 Substances 0.000 claims description 3
- 229920004890 Triton X-100 Polymers 0.000 claims description 3
- GUCYFKSBFREPBC-UHFFFAOYSA-N [phenyl-(2,4,6-trimethylbenzoyl)phosphoryl]-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C(=O)C1=C(C)C=C(C)C=C1C GUCYFKSBFREPBC-UHFFFAOYSA-N 0.000 claims description 3
- MQDJYUACMFCOFT-UHFFFAOYSA-N bis[2-(1-hydroxycyclohexyl)phenyl]methanone Chemical compound C=1C=CC=C(C(=O)C=2C(=CC=CC=2)C2(O)CCCCC2)C=1C1(O)CCCCC1 MQDJYUACMFCOFT-UHFFFAOYSA-N 0.000 claims description 3
- VFHVQBAGLAREND-UHFFFAOYSA-N diphenylphosphoryl-(2,4,6-trimethylphenyl)methanone Chemical compound 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 3
- 239000010452 phosphate Substances 0.000 claims description 3
- 239000004094 surface-active agent Substances 0.000 claims description 3
- 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 claims description 3
- 229940117972 triolein Drugs 0.000 claims description 3
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 2
- 238000005119 centrifugation Methods 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 claims description 2
- 229920001296 polysiloxane Polymers 0.000 claims description 2
- GJKGAPPUXSSCFI-UHFFFAOYSA-N 2-Hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone Chemical compound CC(C)(O)C(=O)C1=CC=C(OCCO)C=C1 GJKGAPPUXSSCFI-UHFFFAOYSA-N 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims 1
- 238000007639 printing Methods 0.000 abstract description 18
- 238000001723 curing Methods 0.000 abstract description 17
- 239000000463 material Substances 0.000 abstract description 17
- 239000007787 solid Substances 0.000 abstract description 5
- 230000036632 reaction speed Effects 0.000 abstract description 4
- 230000002035 prolonged effect Effects 0.000 abstract description 3
- 239000011248 coating agent Substances 0.000 abstract description 2
- 238000000576 coating method Methods 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 25
- 239000000126 substance Substances 0.000 description 9
- 229910010293 ceramic material Inorganic materials 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 238000004062 sedimentation Methods 0.000 description 6
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 description 5
- 230000001105 regulatory effect Effects 0.000 description 5
- 238000002835 absorbance Methods 0.000 description 4
- 230000002411 adverse Effects 0.000 description 4
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 description 3
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 238000007873 sieving Methods 0.000 description 3
- 238000004513 sizing Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 229910000838 Al alloy Inorganic materials 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N acetone Substances CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 229910021485 fumed silica Inorganic materials 0.000 description 2
- 230000031700 light absorption Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- FIHBHSQYSYVZQE-UHFFFAOYSA-N 6-prop-2-enoyloxyhexyl prop-2-enoate Chemical compound C=CC(=O)OCCCCCCOC(=O)C=C FIHBHSQYSYVZQE-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052451 lead zirconate titanate Inorganic materials 0.000 description 1
- HFGPZNIAWCZYJU-UHFFFAOYSA-N lead zirconate titanate Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ti+4].[Zr+4].[Pb+2] HFGPZNIAWCZYJU-UHFFFAOYSA-N 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
Classifications
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- 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
- C04B35/495—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 vanadium, niobium, tantalum, molybdenum or tungsten oxides or solid solutions thereof with other oxides, e.g. vanadates, niobates, tantalates, molybdates or tungstates
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y70/00—Materials specially adapted for additive manufacturing
- B33Y70/10—Composites of different types of material, e.g. mixtures of ceramics and polymers or mixtures of metals and biomaterials
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
- C04B35/63—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B using additives specially adapted for forming the products, e.g.. binder binders
- C04B35/632—Organic additives
- C04B35/634—Polymers
- C04B35/63404—Polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C04B35/63424—Polyacrylates; Polymethacrylates
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
- C04B35/63—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B using additives specially adapted for forming the products, e.g.. binder binders
- C04B35/632—Organic additives
- C04B35/634—Polymers
- C04B35/63448—Polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C04B35/63456—Polyurethanes; Polyisocyanates
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- 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
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Abstract
The invention relates to the field of 3D printing materials, and discloses a lead-free piezoelectric ceramic slurry for DLP photo-curing 3D printing and a preparation method thereof, wherein the components comprise: the coating comprises coupling agent modified potassium sodium niobate powder, free radical type photosensitive resin, a diluent, a free radical type initiator, a dispersing agent, an anti-settling agent, a defoaming agent, an adhesion promoter and a toner; the free radical type photosensitive resin comprises difunctional, trifunctional and hexafunctional aliphatic polyurethane acrylate. The invention selects the combination of the specific free radical type photosensitive resin and the diluent, so that the slurry has high solid volume, low viscosity, good fluidity and high curing reaction speed, and meets the requirement of rapid printing; the coupling agent is used for modifying potassium sodium niobate powder, and is matched with the dispersing agent and the anti-settling agent for use, so that the settling rate of the powder is obviously reduced, and the quality guarantee period of the slurry is prolonged; meanwhile, the adhesion promoter and the toner are added, so that the printing precision is improved, and the sintered product has high density and good piezoelectric performance.
Description
Technical Field
The invention relates to the technical field of 3D printing materials, in particular to a lead-free piezoelectric ceramic slurry for DLP photo-curing 3D printing and a preparation method thereof.
Background
Lead-based piezoelectric ceramics are gradually limited by legislation in various countries because of the high concentration of lead and the great damage to the environment and human body. Therefore, environment-friendly lead-free piezoelectric ceramics, especially potassium sodium niobate (KNN) -based ceramics, are favored because of their large piezoelectric coefficient, high curie temperature, and even properties comparable to lead zirconate titanate.
At present, the manufacture and development of high-performance piezoelectric ceramic parts with complex shapes have become the focus of attention in various fields, but the traditional process method is difficult to form once when manufacturing the complex shapes, and the secondary processing material reduction manufacture is easy to cause defects on the piezoelectric ceramics with high strength, high hardness and brittleness, thereby influencing the use. While 3D printing is an emerging technology for additive manufacturing, piezoelectric materials are brought into a new development stage. The light-cured 3D printing technology mainly comprising DLP (Digital Light Processing) can realize high-precision, customized and personalized design, a better technical means is provided for the finish machining of ceramic materials, and the problems of die dependence, complex shape, difficult manufacturing of various functional parts and the like can be solved by introducing the technology into KNN piezoelectric ceramic manufacturing.
Currently, some researches on KNN-based ceramic slurries that can be used for 3D printing have been conducted, for example, chinese patent document publication No. CN109650887a discloses "a method for preparing a photo-cured potassium-sodium niobate-based leadless piezoelectric ceramic"; chinese patent publication No. CN112608150a discloses "a potassium sodium niobate based leadless piezoelectric ceramic powder and slurry and a preparation process thereof"; the preparation method comprises the steps of mixing potassium sodium niobate ceramic powder with a photoinitiator, photosensitive resin, a dispersing agent and a defoaming agent to prepare ceramic slurry, and then adopting 3D printing light curing molding.
However, the ceramic slurry prepared by mixing potassium sodium niobate ceramic powder, a photoinitiator, a photosensitive resin, a dispersing agent and a defoaming agent in the prior art generally has the problems of low curing speed and poor adhesion between the slurry and a forming table in the printing process, and the KNN powder has high absorbance, so that the photo-curing of the resin can be adversely affected, and the piezoelectric performance of the 3D printed product is poor; in addition, the KNN-based 3D printing paste in the prior art is easy to settle in the storage process, and is unfavorable for storage.
Disclosure of Invention
The invention aims to overcome the problems of the KNN-based 3D printing ceramic slurry in the prior art, and provides a lead-free piezoelectric ceramic slurry for DLP photo-curing 3D printing and a preparation method thereof, wherein the combination of free radical photosensitive resin and diluent is selected to ensure that the slurry has high solid volume, low viscosity, good fluidity and high curing reaction speed, and meets the requirement of rapid printing; the coupling agent is used for modifying potassium sodium niobate powder, and is matched with the dispersing agent and the anti-settling agent for use, so that the settling rate of the powder is obviously reduced, and the quality guarantee period of the slurry is prolonged; meanwhile, the adhesion promoter and the toner are added, so that the printing precision is improved while the viscosity of the slurry is not influenced, and the sintered product has high density and good piezoelectric performance.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
the lead-free piezoelectric ceramic slurry for DLP photocuring 3D printing comprises the following components in parts by weight: 50-75 parts of coupling agent modified potassium sodium niobate powder, 20-36.5 parts of free radical type photosensitive resin, 10-15 parts of diluent, 1-2 parts of free radical type initiator, 1-2 parts of dispersing agent, 0.5-1.5 parts of anti-settling agent, 0.3-1 part of defoamer, 0.1-1 part of adhesion promoter and 0.1-1 part of toner;
the free radical type photosensitive resin comprises difunctional aliphatic polyurethane acrylate, trifunctional aliphatic polyurethane acrylate and hexafunctional aliphatic polyurethane acrylate in a mass ratio of 3-5:1-3:1;
the diluent is at least one selected from hexanediol diacrylate, hydroxyethyl acrylate, isobornyl acrylate, tripropylene glycol diacrylate, dipropylene glycol diacrylate, pentaerythritol tetraacrylate and trimethylolpropane triacrylate;
the anti-settling agent is at least one of titanate coupling agent and BYK-410;
the adhesion promoter is at least one of 2-methyl-2-acrylic acid-2-hydroxyethyl phosphate, hydroxyethyl methacrylate phosphate and CD 9051;
the toner is liquid nano white UV pigment.
The types and the functionalities of the free radical type photosensitive resin and the diluent have obvious influence on the 3D printing performance of the sizing agent, the higher the functionality of the resin is, the faster the curing speed of the sizing agent is, and the forming strength is further increased, but the rapid improvement of the shrinkage rate after curing is the consequences, namely the excessive reduction of the precision and the generation of overexposure are brought about; in order to improve the printing performance of the sizing agent, the invention selects the aliphatic polyurethane acrylic ester with specific proportion of di-functional, tri-functional and hexafunctional degrees to be matched with the free radical photosensitive resin, and selects the low-functional diluent to adjust the viscosity of the free radical photosensitive resin, and the low-functional diluent is favorable for shrinkage control in the curing process; in the system composed of the free radical photosensitive resin and the diluent, a certain kind of anti-settling agent, an adhesion promoter, a toner and other auxiliary agents are added for matching use, and the obtained slurry has high solid volume, low viscosity, good fluidity, high curing reaction speed and low shrinkage rate after curing, and meets the requirement of rapid printing.
Because the slurry is suspension and the powder is easy to settle, the invention uses the coupling agent to carry out surface modification treatment on the potassium sodium niobate powder, so that the potassium sodium niobate powder has larger steric hindrance, and is matched with a dispersing agent and a certain anti-settling agent for use, thereby effectively reducing the settling rate of the powder, and greatly prolonging the shelf life of the slurry, wherein the settling rate of the powder is less than 5% in 30 days. The invention can avoid the influence of the introduction of the anti-settling agent on the viscosity of the slurry by selecting the type of the anti-settling agent.
Because KNN powder is gray and has large absorbance, the light curing of the resin can be adversely affected, the invention adds the toner, and adjusts the color of the slurry to be nearly white so as to increase the light absorption during 3D printing; meanwhile, the adhesion promoter is added, so that parts can be better adhered to a forming table of an aluminum alloy material in the printing process, and the success rate of sample printing is increased; therefore, the slurry has high printing precision, high density of sintered products and good piezoelectric performance. Under the action of a system formed by the components together, the invention can obtain the light-cured KNN-based ceramic slurry which has high solid load, low shrinkage, less agglomeration, low viscosity, slow sedimentation and stability.
Preferably, the free radical initiator is at least one selected from 1-hydroxycyclohexyl phenyl ketone, phenyl bis (2, 4, 6-trimethylbenzoyl) phosphine oxide, 2,4, 6-trimethylbenzoyl-diphenyl phosphine oxide, ethyl 2,4, 6-trimethylbenzoyl phenyl phosphonate and 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl ] -1-acetone.
Preferably, the dispersing agent is at least one selected from BYK-111, BYK-142, triton X-100, PM1590 and triolein.
Preferably, the defoaming agent is at least one selected from the group consisting of silicones, surfactants and paraffins.
Preferably, the preparation method of the coupling agent modified potassium sodium niobate powder comprises the following steps: a) Adding sanded potassium sodium niobate powder into a mixed solution of hydrogen peroxide and absolute ethyl alcohol, and reacting to obtain hydroxylated potassium sodium niobate powder; b) And (3) reacting the potassium sodium hydroxyl niobate powder with a silane coupling agent to obtain the coupling agent modified potassium sodium niobate powder. The invention firstly uses hydrogen peroxide to activate the surface of potassium sodium niobate powder to obtain hydroxylated potassium sodium niobate powder, then reacts with silane coupling agent to obtain coupling agent modified potassium sodium niobate powder, reduces the specific surface area of potassium sodium niobate powder, and can obviously reduce the sedimentation of potassium sodium niobate powder by the combined action of dispersing agent and anti-sedimentation agent.
Preferably, in the step A), potassium sodium niobate powder is sanded and then added into a mixed solution of hydrogen peroxide and absolute ethyl alcohol, the pH of the system is regulated to 5.5-6.5, and after stirring reaction is carried out for 8-10 hours, the obtained suspension is centrifuged and washed to obtain hydroxylated potassium sodium niobate powder; the mass ratio of the potassium sodium niobate powder after sanding to the hydrogen peroxide and the absolute ethyl alcohol is 200-300:30-40:500.
Preferably, the particle size of the potassium sodium niobate powder in the step A) is 400-600 nm; the rotating speed during sanding is 300-500 r/min, and the sanding time is 1-2 h.
Preferably, in the step B), a silane coupling agent is added into the potassium sodium hydroxyl niobate powder, the ultrasonic treatment is carried out for 30-40 min, the mixture is heated to 95-105 ℃ and kept for 1-2 h, and the potassium sodium niobate powder modified by the coupling agent is obtained after centrifugation, washing and drying; the mass ratio of the potassium sodium hydroxyl niobate powder to the silane coupling agent is 200-300:2.
The invention also provides a preparation method of the lead-free piezoelectric ceramic slurry for DLP photocuring 3D printing, which comprises the following steps:
(1) Preparing coupling agent modified potassium sodium niobate powder;
(2) Uniformly mixing free radical type photosensitive resin, a diluent and a free radical type photoinitiator to obtain a photo-curing resin mixture;
(3) Adding coupling agent modified potassium sodium niobate powder into a photo-curing resin mixture, adding a dispersing agent, an anti-settling agent, a defoaming agent, an adhesion promoter and a toner, ball milling, and vacuum defoaming to obtain the lead-free piezoelectric ceramic slurry for DLP photo-curing 3D printing.
Preferably, the ball milling speed in the step (3) is 4000-5000 r/min, and the ball milling time is 8-10 h.
Therefore, the invention has the following beneficial effects:
(1) According to the invention, the aliphatic polyurethane acrylic ester with specific proportion of di-functional, tri-functional and hexafunctional degrees is selected to be matched with the free radical type photosensitive resin, and the viscosity of the aliphatic polyurethane acrylic ester is adjusted by adopting a low-functional diluent, so that the obtained slurry has high solid volume, low viscosity, good fluidity, high curing reaction speed, high density after sintering, good piezoelectric property and application prospect, and meets the requirement of rapid printing;
(2) According to the invention, the coupling agent is used for carrying out surface modification treatment on the potassium sodium niobate powder, so that the potassium sodium niobate powder has larger steric hindrance, and is matched with a dispersing agent and a certain anti-settling agent for use, so that the settling rate of the powder can be effectively reduced, the settling rate in 30 days is only 5%, and the quality guarantee period of the slurry is greatly prolonged;
(3) According to the invention, the toner is added, the color of the slurry is regulated to be nearly white, so that the light absorption during 3D printing is increased, and the adverse effect of high KNN powder absorbance on the photo-curing of the resin is avoided;
(4) According to the invention, the adhesion promoter is added, so that parts can be better adhered to a forming table of an aluminum alloy material in the printing process, and the success rate of sample printing is increased;
(5) The lead-free potassium sodium niobate-based ceramic slurry for DLP photocuring 3D printing prepared by the invention has high printing precision, can reach 50 mu m, and does not need subsequent processing after degreasing and sintering of a molding structure.
Detailed Description
The invention is further described below in connection with the following detailed description.
In the present invention, all the equipment and raw materials are commercially available or commonly used in the industry, and the methods in the following examples are conventional in the art unless otherwise specified.
General examples
The lead-free piezoelectric ceramic slurry for DLP photocuring 3D printing comprises the following components in parts by weight: 50-75 parts of coupling agent modified potassium sodium niobate powder, 20-36.5 parts of free radical type photosensitive resin, 10-15 parts of diluent, 1-2 parts of free radical type initiator, 1-2 parts of dispersing agent, 0.5-1.5 parts of anti-settling agent, 0.3-1 part of defoamer, 0.1-1 part of adhesion promoter and 0.1-1 part of toner;
the free radical type photosensitive resin comprises difunctional aliphatic polyurethane acrylate, trifunctional aliphatic polyurethane acrylate and hexafunctional aliphatic polyurethane acrylate in a mass ratio of 3-5:1-3:1;
the anti-settling agent is at least one of titanate coupling agent and BYK-410;
the adhesion promoter is at least one of 2-methyl-2-acrylic acid-2-hydroxyethyl phosphate (PM-1), hydroxyethyl methacrylate phosphate (PM-2) and CD 9051;
the toner is liquid nano white UV pigment;
the diluent is at least one selected from hexanediol diacrylate (HDDA), hydroxyethyl acrylate (HEA), isobornyl acrylate (IBOA), tripropylene glycol diacrylate (TPGDA), dipropylene glycol diacrylate (DPGDA), pentaerythritol tetraacrylate (PETEA) and trimethylolpropane triacrylate (TMPTA);
the free radical initiator is at least one selected from 1-hydroxycyclohexyl phenyl ketone (184), phenyl bis (2, 4, 6-trimethylbenzoyl) phosphine oxide (819), 2,4, 6-trimethylbenzoyl-diphenyl phosphine oxide (TPO), ethyl 2,4, 6-trimethylbenzoyl phenyl phosphonate (TPO-L) and 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl ] -1-acetone (659);
the dispersing agent is at least one of BYK-111, BYK-142, triton X-100, PM1590 and triolein;
the defoamer is at least one selected from organic silicon, surfactant and alkane;
the preparation method of the lead-free piezoelectric ceramic slurry for DLP photo-curing 3D printing comprises the following steps:
(1) Preparing coupling agent modified potassium sodium niobate powder: adding sodium potassium niobate powder with the particle size of 400-600 nm into a mixed solution of hydrogen peroxide and absolute ethyl alcohol after sanding, wherein the rotating speed during sanding is 300-500 r/min, the sanding time is 1-2 h, the mass ratio of the sodium potassium niobate powder after sanding to the hydrogen peroxide to the absolute ethyl alcohol is 200-300:30-40:500, the pH value of the system is adjusted to 5.5-6.5, stirring and reacting for 8-10 h, and centrifuging and washing the obtained suspension to obtain the potassium sodium hydroxylate powder; adding a silane coupling agent into the potassium sodium hydroxyl niobate powder, wherein the mass ratio of the potassium sodium hydroxyl niobate powder to the silane coupling agent is 200-300:2, carrying out ultrasonic treatment for 30-40 min, heating to 95-105 ℃ and preserving heat for 1-2 h, centrifuging, washing and drying to obtain the coupling agent modified potassium sodium niobate powder;
(2) Uniformly mixing free radical type photosensitive resin, a diluent and a free radical type photoinitiator to obtain a photo-curing resin mixture;
(3) Adding coupling agent modified potassium sodium niobate powder into a photo-curing resin mixture, adding a dispersing agent, an anti-settling agent, a defoaming agent, an adhesion promoter and a toner, ball milling at a speed of 400-450 r/min for 8-10 h, and then vacuum defoaming to obtain the lead-free piezoelectric ceramic slurry for DLP photo-curing 3D printing.
Example 1:
the lead-free piezoelectric ceramic slurry for DLP photocuring 3D printing comprises the following components in parts by weight: 50 parts of coupling agent modified potassium sodium niobate powder, 35 parts of free radical type photosensitive resin, 10 parts of diluent HDDA (new material for Zhchang), 2 parts of free radical type initiator TPO (new material for Zhchang), 2 parts of dispersant BYK-111 (Pick chemical), 0.5 part of anti-settling agent BYK-410 (Pick chemical), 0.5 part of organosilicon defoamer (dakangnin), 0.1 part of adhesion promoter PM-2 (four-city photoelectric), and 0.1 part of liquid nanometer UV pigment (Shenzhen city Xinjia Yiyi technology, white opacity);
the free radical type photosensitive resin comprises difunctional aliphatic polyurethane acrylate U600 (photo-chemical industry), trifunctional aliphatic polyurethane acrylate YC3165 (Zhchang new material) and hexafunctional aliphatic polyurethane acrylate YC3620 (Zhchang new material) in a mass ratio of 4:2:1;
the preparation method of the lead-free piezoelectric ceramic slurry for DLP photo-curing 3D printing comprises the following steps:
(1) Preparing coupling agent modified potassium sodium niobate powder: adding sodium potassium niobate powder with the average particle size of 500nm into a mixed solution of hydrogen peroxide and absolute ethyl alcohol after sanding, wherein the rotating speed during sanding is 400r/min, the sanding time is 1.5h, the mass ratio of the sodium potassium niobate powder after sanding to the hydrogen peroxide to the absolute ethyl alcohol is 300:30:500, regulating the pH value of the system to 6.0, stirring at the rotating speed of 450r/min for reacting for 8h at room temperature, and centrifuging and washing the obtained suspension to obtain potassium sodium niobate powder; adding a silane coupling agent KH550 into the potassium sodium hydroxyl niobate powder, wherein the mass ratio of the potassium sodium hydroxyl niobate powder to the silane coupling agent KH550 is 300:2, carrying out ultrasonic treatment for 30min, heating to 100 ℃, preserving heat for 1h, centrifuging, washing, drying, and sieving with a 200-mesh sieve to obtain the coupling agent modified potassium sodium niobate powder;
(2) Mixing the free radical type photosensitive resin, the diluent and the free radical type photoinitiator according to a proportion, and stirring for 60min at a rotating speed of 400r/min to obtain a photo-curing resin mixture;
(3) Adding coupling agent modified potassium sodium niobate powder into a photo-curing resin mixture, adding a dispersing agent, an anti-settling agent, a defoaming agent, an adhesion promoter and a toner according to a certain proportion, ball milling at a speed of 4500r/min for 8 hours in a planetary ball mill equipment of B-313, and then performing vacuum defoaming to obtain the lead-free piezoelectric ceramic slurry for DLP photo-curing 3D printing.
Example 2:
the lead-free piezoelectric ceramic slurry for DLP photocuring 3D printing comprises the following components in parts by weight: 75 parts of coupling agent modified potassium sodium niobate powder, 36.5 parts of free radical type photosensitive resin, 15 parts of diluent TPGDA (Zhchang new material), 2 parts of free radical type initiator TPO (Zhchang new material), 2 parts of dispersant BYK-111 (Pick chemical), 1.5 parts of anti-settling agent BYK-410 (Pick chemical), 1 part of organosilicon defoamer (dakangnin), 1 part of adhesion promoter PM-2 (four-city photoelectric), and 1 part of liquid nanometer UV pigment (Shenzhen city Xinjia Yiyi technology, white opacity);
the free radical type photosensitive resin comprises difunctional aliphatic polyurethane acrylate U600 (photo-chemical industry), trifunctional aliphatic polyurethane acrylate YC3165 (Zhchang new material) and hexafunctional aliphatic polyurethane acrylate YC3620 (Zhchang new material) in a mass ratio of 3:3:1;
the preparation method of the lead-free piezoelectric ceramic slurry for DLP photo-curing 3D printing comprises the following steps:
(1) Preparing coupling agent modified potassium sodium niobate powder: adding sodium potassium niobate powder with the average particle size of 500nm into a mixed solution of hydrogen peroxide and absolute ethyl alcohol after sanding, wherein the rotating speed during sanding is 400r/min, the sanding time is 2h, the mass ratio of the sodium potassium niobate powder after sanding to the hydrogen peroxide to the absolute ethyl alcohol is 200:30:500, regulating the pH value of the system to 6.0, stirring at the rotating speed of 450r/min for reacting for 8h at room temperature, and centrifuging and washing the obtained suspension to obtain potassium sodium hydroxylate powder; adding a silane coupling agent KH550 into the potassium sodium hydroxyl niobate powder, wherein the mass ratio of the potassium sodium hydroxyl niobate powder to the silane coupling agent KH550 is 200:2, carrying out ultrasonic treatment for 30min, heating to 100 ℃, preserving heat for 1h, centrifuging, washing, drying, and sieving with a 200-mesh sieve to obtain the coupling agent modified potassium sodium niobate powder;
(2) Mixing the free radical type photosensitive resin, the diluent and the free radical type photoinitiator according to a proportion, and stirring for 60min at a rotating speed of 400r/min to obtain a photo-curing resin mixture;
(3) Adding coupling agent modified potassium sodium niobate powder into a photo-curing resin mixture, adding a dispersing agent, an anti-settling agent, a defoaming agent, an adhesion promoter and a toner according to a certain proportion, ball milling at a speed of 4500r/min for 8 hours in a planetary ball mill equipment of B-313, and then performing vacuum defoaming to obtain the lead-free piezoelectric ceramic slurry for DLP photo-curing 3D printing.
Example 3:
the lead-free piezoelectric ceramic slurry for DLP photocuring 3D printing comprises the following components in parts by weight: 60 parts of coupling agent modified potassium sodium niobate powder, 30 parts of free radical type photosensitive resin, 15 parts of diluent IBOA (new material for Zhchang), 1 part of free radical type initiator TPO (new material for Zhchang), 1 part of dispersant BYK-111 (Pick chemical), 1.5 parts of anti-settling agent BYK-410 (Pick chemical), 0.5 part of organosilicon defoamer (dakangnin), 0.5 part of adhesion promoter PM-2 (four-city photoelectric), and 0.5 part of liquid nanometer UV pigment (Shenzhen city Xinjia Yiyi technology, white opacity);
the free radical type photosensitive resin comprises difunctional aliphatic polyurethane acrylate U600 (photo-chemical industry), trifunctional aliphatic polyurethane acrylate YC3165 (Zhchang new material) and hexafunctional aliphatic polyurethane acrylate YC3620 (Zhchang new material) in a mass ratio of 5:1:1;
the preparation method of the lead-free piezoelectric ceramic slurry for DLP photo-curing 3D printing comprises the following steps:
(1) Preparing coupling agent modified potassium sodium niobate powder: adding sodium potassium niobate powder with the average particle size of 500nm into a mixed solution of hydrogen peroxide and absolute ethyl alcohol after sanding, wherein the rotating speed during sanding is 400r/min, the sanding time is 2h, the mass ratio of the sodium potassium niobate powder after sanding to the hydrogen peroxide to the absolute ethyl alcohol is 250:30:500, regulating the pH value of the system to 6.0, stirring at the rotating speed of 450r/min for reacting for 8h at room temperature, and centrifuging and washing the obtained suspension to obtain potassium sodium hydroxylate powder; adding a silane coupling agent KH550 into the potassium sodium hydroxyl niobate powder, wherein the mass ratio of the potassium sodium hydroxyl niobate powder to the silane coupling agent KH550 is 250:2, carrying out ultrasonic treatment for 30min, heating to 100 ℃, preserving heat for 1h, centrifuging, washing, drying, and sieving with a 200-mesh sieve to obtain the coupling agent modified potassium sodium niobate powder;
(2) Mixing the free radical type photosensitive resin, the diluent and the free radical type photoinitiator according to a proportion, and stirring for 60min at a rotating speed of 400r/min to obtain a photo-curing resin mixture;
(3) Adding coupling agent modified potassium sodium niobate powder into a photo-curing resin mixture, adding a dispersing agent, an anti-settling agent, a defoaming agent, an adhesion promoter and a toner according to a certain proportion, ball milling at a speed of 4500r/min for 8 hours in a planetary ball mill equipment of B-313, and then performing vacuum defoaming to obtain the lead-free piezoelectric ceramic slurry for DLP photo-curing 3D printing.
Comparative example 1:
comparative example 1 is different from example 1 in that the radical type photosensitive resin was entirely the difunctional aliphatic urethane acrylate U600, and the rest was the same as in example 1.
Comparative example 2:
comparative example 2 is different from example 1 in that the radical type photosensitive resin was entirely trifunctional aliphatic urethane acrylate YC3165, and the rest was the same as in example 1.
Comparative example 3:
comparative example 3 is different from example 1 in that the radical type photosensitive resin was entirely hexafunctional aliphatic urethane acrylate YC3620, and the rest was the same as in example 1.
Comparative example 4:
comparative example 4 differs from example 1 in that no toner was added to the slurry, and the remainder was the same as in example 1.
Comparative example 5:
comparative example 5 is different from example 1 in that A-171 (novel sandisk material) was used as the adhesion promoter, and the rest was the same as in example 1.
Comparative example 6:
comparative example 6 differs from example 1 in that no anti-settling agent was added to the slurry, and the remainder was the same as in example 1.
Comparative example 7:
comparative example 7 differs from example 1 in that fumed silica was used as an anti-settling agent, and the remainder was the same as in example 1.
Comparative example 8:
comparative example 8 differs from example 1 in that hydroxyethyl methacrylate (HEMA) was used as a diluent, and the rest was the same as in example 1.
The properties of the slurries prepared in the above examples and comparative examples and the properties of the 3D printed ceramic materials thereof were tested, and the results are shown in tables 1 and 2;
wherein, the viscosity of the slurry is measured by an NDJ-8S viscometer;
the sedimentation rate test method comprises the following steps: taking 50g of slurry, sealing and preserving, pouring the slurry into a new beaker every 120 hours, and measuring the quality of ceramic particles and slurry deposited at the bottom of the original beaker so as to obtain a sedimentation rate;
the method for testing the slice thickness and the piezoelectric performance of the ceramic material comprises the following steps: performing 3D printing forming on the slurry by using DLP equipment based on a light curing principle, firstly measuring the maximum exposure thickness (slice thickness) of each layer, printing to obtain a final sample, placing the sample into a box-type furnace for glue discharging, sequentially heating to 200 ℃ at 0.15 ℃/min, respectively preserving heat for 3 hours at 400 ℃, sequentially heating to 550 ℃ at 600 ℃ at 0.25 ℃/min, respectively preserving heat for 2.5 hours, and naturally cooling; then heating to 1050 ℃ at 5 ℃/min in air atmosphere, preserving heat for 4 hours, and naturally cooling to obtain a sintered KNN ceramic sample; coating silver paste on the front and back sides of the sintered KNN ceramic sample, drying in the air, and calcining at 600 ℃ for 30min; the silicone oil is heated to 120 ℃ and polarized for 20min by using 3kV/mm direct current; testing the piezoelectric properties d thereof by measuring a quasi-static analyzer 33 。
Table 1: slurry and 3D printed ceramic material performance test results
Table 2: sedimentation rate test results
As can be seen from tables 1 and 2, the slurries prepared by the formulations and methods of examples 1-3 have lower viscosity, larger slice thickness and strong photocuring ability; and the ceramic material printed by 3D printing has good piezoelectric property (D 33 ）。
In contrast, the slurry of the comparative example 1 only adopts the difunctional aliphatic polyurethane acrylate as the free radical photosensitive resin, the slurry has higher viscosity, slow curing speed and low forming strength, and the piezoelectric performance of the printed ceramic material is obviously reduced compared with that of the example 1; in comparative example 2, only trifunctional aliphatic urethane acrylate was used as the radical type photosensitive resin, and the slice thickness and final printing performance of the paste were also reduced as compared with example 1; in comparative example 3, only hexafunctional aliphatic urethane acrylate was used as the radical type photosensitive resin, the viscosity of the paste was too low, the shrinkage after curing was high, and the printing accuracy was lowered, and the piezoelectric properties of the ceramic material after printing were remarkably lowered as compared with example 1.
Since the slurry of comparative example 4 was free of toner and the KNN powder had a large absorbance and adversely affected the photo-curing of the resin, the slice thickness and the piezoelectric properties of the sample were significantly reduced as compared with those of example 1.
The adhesion promoter a-171 was used in the paste of comparative example 5 instead of the adhesion promoter in the present invention, and since the silane coupling agent a-171 was lower in year and had a large negative influence on curing, the cut thickness of the paste (curing effect was lowered) and the piezoelectric properties of the final print were significantly lowered as compared with those in example 1.
The slurry of the comparative example 6 is not added with an anti-settling agent, the settling rate of the powder is obviously improved compared with that of the slurry of the example 1, the settling rate of 30d exceeds 5%, and the quality guarantee period of the slurry is shortened; in comparative example 7, fumed silica was used as an anti-settling agent, and although the settling rate of the powder could be controlled to a low level, the viscosity of the slurry increased significantly, affecting the photocuring performance thereof, and the piezoelectric performance of the finally produced sample was significantly reduced.
The type of diluent was changed in comparative example 8, and HEMA was used as the diluent, and the viscosity was low, the flexibility was good, and the curing effect was poor because of mono-functionality alone, resulting in a significant decrease in the photo-curing property of the slurry and the piezoelectric property of the sample as compared with example 1.
Claims (10)
1. The lead-free piezoelectric ceramic slurry for DLP photocuring 3D printing is characterized by comprising the following components in parts by weight: 50-75 parts of coupling agent modified potassium sodium niobate powder, 20-36.5 parts of free radical type photosensitive resin, 10-15 parts of diluent, 1-2 parts of free radical type initiator, 1-2 parts of dispersing agent, 0.5-1.5 parts of anti-settling agent, 0.3-1 part of defoamer, 0.1-1 part of adhesion promoter and 0.1-1 part of toner;
the free radical type photosensitive resin comprises difunctional aliphatic polyurethane acrylate, trifunctional aliphatic polyurethane acrylate and hexafunctional aliphatic polyurethane acrylate in a mass ratio of 3-5:1-3:1;
the diluent is at least one selected from hexanediol diacrylate, hydroxyethyl acrylate, isobornyl acrylate, tripropylene glycol diacrylate, dipropylene glycol diacrylate, pentaerythritol tetraacrylate and trimethylolpropane triacrylate;
the anti-settling agent is at least one of titanate coupling agent and BYK-410;
the adhesion promoter is at least one of 2-methyl-2-acrylic acid-2-hydroxyethyl phosphate, hydroxyethyl methacrylate phosphate and CD 9051;
the toner is liquid nano white UV pigment.
2. The lead-free piezoelectric ceramic paste for DLP photo-curing 3D printing according to claim 1, wherein the radical initiator is at least one selected from the group consisting of 1-hydroxycyclohexyl phenyl ketone, phenyl bis (2, 4, 6-trimethylbenzoyl) phosphine oxide, 2,4, 6-trimethylbenzoyl-diphenyl phosphine oxide, ethyl 2,4, 6-trimethylbenzoyl phenyl phosphonate, and 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl ] -1-propanone.
3. The lead-free piezoelectric ceramic paste for DLP photo-curing 3D printing according to claim 1, wherein the dispersant is at least one selected from BYK-111, BYK-142, triton X-100, PM1590 and triolein.
4. The lead-free piezoelectric ceramic paste for DLP photo-curing 3D printing according to claim 1, wherein said antifoaming agent is at least one selected from the group consisting of silicones, surfactants and alkanes.
5. The lead-free piezoelectric ceramic slurry for DLP photocuring 3D printing according to claim 1, wherein the preparation method of the coupling agent modified potassium sodium niobate powder is as follows: a) Adding sanded potassium sodium niobate powder into a mixed solution of hydrogen peroxide and absolute ethyl alcohol, and reacting to obtain hydroxylated potassium sodium niobate powder; b) And (3) reacting the potassium sodium hydroxyl niobate powder with a silane coupling agent to obtain the coupling agent modified potassium sodium niobate powder.
6. The lead-free piezoelectric ceramic slurry for DLP photocuring 3D printing according to claim 5, wherein in the step A), potassium sodium niobate powder is sanded, added into a mixed solution of hydrogen peroxide and absolute ethyl alcohol, the pH of a system is adjusted to 5.5-6.5, and after stirring reaction for 8-10 hours, the obtained suspension is centrifuged and washed to obtain potassium sodium niobate hydroxide powder; the mass ratio of the potassium sodium niobate powder after sanding to the hydrogen peroxide and the absolute ethyl alcohol is 200-300:30-40:500.
7. The lead-free piezoelectric ceramic slurry for DLP photo-curing 3D printing according to claim 5 or 6, wherein the particle size of the potassium sodium niobate powder in the step a) is 400 to 600nm; the rotating speed during sanding is 300-500 r/min, and the sanding time is 1-2 h.
8. The lead-free piezoelectric ceramic slurry for DLP photocuring 3D printing according to claim 5 or 6, wherein in the step B), a silane coupling agent is added into potassium sodium hydroxyl niobate powder, the ultrasonic treatment is carried out for 30-40 min, the mixture is heated to 95-105 ℃ and kept for 1-2 h, and the potassium sodium hydroxyl niobate powder modified by the coupling agent is obtained after centrifugation, washing and drying; the mass ratio of the potassium sodium hydroxyl niobate powder to the silane coupling agent is 200-300:2.
9. A method for preparing the lead-free piezoelectric ceramic slurry for DLP photocuring 3D printing according to any one of claims 1 to 8, comprising the steps of:
(1) Preparing coupling agent modified potassium sodium niobate powder;
(2) Uniformly mixing free radical type photosensitive resin, a diluent and a free radical type photoinitiator to obtain a photo-curing resin mixture;
(3) Adding coupling agent modified potassium sodium niobate powder into a photo-curing resin mixture, adding a dispersing agent, an anti-settling agent, a defoaming agent, an adhesion promoter and a toner, ball milling, and vacuum defoaming to obtain the lead-free piezoelectric ceramic slurry for DLP photo-curing 3D printing.
10. The preparation method according to claim 9, wherein the ball milling speed in the step (3) is 4000-5000 r/min and the ball milling time is 8-10 h.
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