CN114075069A - Alumina ceramic slurry for photocuring 3D printing, preparation method and alumina ceramic - Google Patents
Alumina ceramic slurry for photocuring 3D printing, preparation method and alumina ceramic Download PDFInfo
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- CN114075069A CN114075069A CN202010810938.5A CN202010810938A CN114075069A CN 114075069 A CN114075069 A CN 114075069A CN 202010810938 A CN202010810938 A CN 202010810938A CN 114075069 A CN114075069 A CN 114075069A
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 title claims abstract description 122
- 239000002002 slurry Substances 0.000 title claims abstract description 51
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 238000000016 photochemical curing Methods 0.000 title claims abstract description 22
- 238000010146 3D printing Methods 0.000 title claims abstract description 20
- 239000000178 monomer Substances 0.000 claims abstract description 63
- 239000011347 resin Substances 0.000 claims abstract description 63
- 229920005989 resin Polymers 0.000 claims abstract description 63
- 239000000843 powder Substances 0.000 claims abstract description 59
- 239000002270 dispersing agent Substances 0.000 claims abstract description 21
- 238000002156 mixing Methods 0.000 claims abstract description 18
- 239000003085 diluting agent Substances 0.000 claims abstract description 17
- 239000000203 mixture Substances 0.000 claims abstract description 16
- 230000002378 acidificating effect Effects 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 12
- 230000001588 bifunctional effect Effects 0.000 claims abstract description 10
- 125000000524 functional group Chemical group 0.000 claims abstract description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 33
- 238000000498 ball milling Methods 0.000 claims description 28
- 238000005516 engineering process Methods 0.000 claims description 13
- 238000000465 moulding Methods 0.000 claims description 13
- IAXXETNIOYFMLW-COPLHBTASA-N [(1s,3s,4s)-4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl] 2-methylprop-2-enoate Chemical compound C1C[C@]2(C)[C@@H](OC(=O)C(=C)C)C[C@H]1C2(C)C IAXXETNIOYFMLW-COPLHBTASA-N 0.000 claims description 9
- 239000003999 initiator Substances 0.000 claims description 9
- 229940119545 isobornyl methacrylate Drugs 0.000 claims description 9
- YDKNBNOOCSNPNS-UHFFFAOYSA-N methyl 1,3-benzoxazole-2-carboxylate Chemical compound C1=CC=C2OC(C(=O)OC)=NC2=C1 YDKNBNOOCSNPNS-UHFFFAOYSA-N 0.000 claims description 9
- 239000002245 particle Substances 0.000 claims description 9
- -1 tri (propoxy) triacrylate Chemical compound 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 8
- 238000012986 modification Methods 0.000 claims description 7
- 230000004048 modification Effects 0.000 claims description 7
- 239000002202 Polyethylene glycol Substances 0.000 claims description 4
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- 229920001223 polyethylene glycol Polymers 0.000 claims description 4
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-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
- 238000012545 processing Methods 0.000 claims description 3
- 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 2
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 claims description 2
- 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 2
- YIKSHDNOAYSSPX-UHFFFAOYSA-N 1-propan-2-ylthioxanthen-9-one Chemical compound S1C2=CC=CC=C2C(=O)C2=C1C=CC=C2C(C)C YIKSHDNOAYSSPX-UHFFFAOYSA-N 0.000 claims description 2
- FTALTLPZDVFJSS-UHFFFAOYSA-N 2-(2-ethoxyethoxy)ethyl prop-2-enoate Chemical compound CCOCCOCCOC(=O)C=C FTALTLPZDVFJSS-UHFFFAOYSA-N 0.000 claims 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 claims description 2
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims description 2
- 244000028419 Styrax benzoin Species 0.000 claims description 2
- 235000000126 Styrax benzoin Nutrition 0.000 claims description 2
- 235000008411 Sumatra benzointree Nutrition 0.000 claims description 2
- 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 2
- 229960002130 benzoin Drugs 0.000 claims description 2
- 125000004386 diacrylate group Chemical group 0.000 claims description 2
- 235000019382 gum benzoic Nutrition 0.000 claims description 2
- OTRIMLCPYJAPPD-UHFFFAOYSA-N methanol prop-2-enoic acid Chemical compound OC.OC.OC(=O)C=C.OC(=O)C=C OTRIMLCPYJAPPD-UHFFFAOYSA-N 0.000 claims description 2
- RZFODFPMOHAYIR-UHFFFAOYSA-N oxepan-2-one;prop-2-enoic acid Chemical compound OC(=O)C=C.O=C1CCCCCO1 RZFODFPMOHAYIR-UHFFFAOYSA-N 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- 238000001723 curing Methods 0.000 abstract description 5
- 230000007547 defect Effects 0.000 abstract description 4
- 239000007790 solid phase Substances 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 14
- 239000007787 solid Substances 0.000 description 8
- 239000000919 ceramic Substances 0.000 description 7
- 235000019441 ethanol Nutrition 0.000 description 7
- 238000005086 pumping Methods 0.000 description 6
- 238000007873 sieving Methods 0.000 description 6
- 229940113115 polyethylene glycol 200 Drugs 0.000 description 5
- 239000000047 product Substances 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005452 bending Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- XVZXOLOFWKSDSR-UHFFFAOYSA-N Cc1cc(C)c([C]=O)c(C)c1 Chemical group Cc1cc(C)c([C]=O)c(C)c1 XVZXOLOFWKSDSR-UHFFFAOYSA-N 0.000 description 1
- YFPJFKYCVYXDJK-UHFFFAOYSA-N Diphenylphosphine oxide Chemical compound C=1C=CC=CC=1[P+](=O)C1=CC=CC=C1 YFPJFKYCVYXDJK-UHFFFAOYSA-N 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 238000007641 inkjet printing Methods 0.000 description 1
- 238000000462 isostatic pressing Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000000110 selective laser sintering Methods 0.000 description 1
- 238000007569 slipcasting Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000010345 tape casting Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
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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
- C04B35/10—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 aluminium oxide
- C04B35/111—Fine ceramics
- C04B35/1115—Minute sintered entities, e.g. sintered abrasive grains or shaped particles such as platelets
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y10/00—Processes of additive manufacturing
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y70/00—Materials specially adapted for additive manufacturing
- B33Y70/10—Composites of different types of material, e.g. mixtures of ceramics and polymers or mixtures of metals and biomaterials
-
- 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
- B33Y80/00—Products made by additive manufacturing
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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
- C04B35/622—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
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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
- C04B35/622—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
- C04B35/62605—Treating the starting powders individually or as mixtures
- C04B35/6261—Milling
- C04B35/62615—High energy or reactive ball milling
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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
- C04B35/622—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
- C04B35/62605—Treating the starting powders individually or as mixtures
- C04B35/62625—Wet mixtures
- C04B35/6264—Mixing media, e.g. organic solvents
Abstract
The invention provides alumina ceramic slurry for photocuring 3D printing, a preparation method and alumina ceramic, which can effectively overcome the technical defects of low solid phase content, poor curing and forming precision, low mechanical property of products and the like in the traditional alumina ceramic slurry preparation process. The method comprises the following steps: step 1, modifying alumina powder by using a macromolecular dispersant containing acidic groups; and 2, mixing the modified alumina powder obtained in the step 1, a resin monomer composition, a photoinitiator and a diluent to obtain alumina ceramic slurry, wherein the resin monomer composition is composed of a monofunctional group resin monomer, a bifunctional group resin monomer and a resin monomer with more than three functional groups, and the mass ratio of the monofunctional group resin monomer to the bifunctional group resin monomer is 1.8-3: 4-7: 0.5-3.2.
Description
Technical Field
The invention belongs to the technical field of functional ceramic preparation, relates to alumina ceramic slurry for photocuring 3D printing, a preparation method and alumina ceramic, and particularly relates to alumina ceramic slurry for photocuring 3D printing (DLP technology), a preparation method and alumina ceramic
Background
The alumina ceramic has the advantages of high mechanical strength, high resistivity, good electrical insulation, high melting point, good corrosion resistance, excellent chemical stability and the like, and is widely applied to the fields of machinery, electronic and electric power, chemical industry, medicine, building and other high-tech fields. The preparation method comprises the following steps: isostatic pressing, dry pressing, extrusion molding, tape casting, slip casting, gel casting, freeze molding, cryo-gelation molding, and the like. When the components are prepared by the processes, molds with corresponding shapes need to be prepared according to the shapes of the components, if the structures of the components are slightly changed, the molds need to be prepared again or samples need to be machined, and therefore, the preparation cost is increased.
With the development of industry, these conventional molding processes have not been able to meet the requirements of some special fields. Different from the traditional material reduction manufacturing technology, the 3D printing ceramic has the advantages of short manufacturing period, low cost, convenient processing, strong operability and the like, and the existing 3D printing preparation method of the alumina ceramic mainly comprises a fused deposition molding technology, a selective laser sintering technology, a layered entity molding technology, an ink-jet printing molding technology, a three-dimensional printing molding technology and a photocuring molding technology. Compared with other forming technologies, photocuring (DLP) technology is easier to prepare high-strength and high-density alumina ceramic, has the advantages of high precision, printable complex structure and the like, and is the most ideal printing technology for preparing alumina ceramic.
Currently, when light-cured molding is used to prepare alumina ceramics, the following problems exist (CN201710051789.7, CN201710035499.3, CN201711047163.5, cuulan, university of guangdong industry, master paper, 2019): (1) the affinity between the alumina powder and the resin is poor, so that the solid content of the ceramic slurry prepared from the unmodified powder is low, and even if the powder is modified by a dispersant, the solid content is still lower than 55 vol%; (2) the variety of the resin monomers used by the alumina powder slurry is less or the proportion of each component is not given, and the shape precision is influenced when a slightly large-size complex structural member is prepared or a formed bent sample strip is cured and shrunk greatly, so that the mechanical property of a final product cannot be evaluated, even if the mechanical property is evaluated to be lower than 400 Mpa; (3) part of the slurry adopts oligomer to regulate and control the shape precision, but the solid content of the slurry is relatively low due to the large viscosity of the oligomer. These three major problems have limited the development of stereolithography and alumina ceramic applications. Although scholars (Chartier, Journal of Materials Science,37:2002, Abouliatim, Journal of the European Ceramic Society,29:2009, li khau, tsunshi university master's paper, 2016) have attempted to solve the above problems by modifying the alumina powder, compounding the particle size, or adjusting the resin ratio, none of the effects are obvious.
Disclosure of Invention
The invention aims to overcome the defects in the prior art, provides alumina ceramic slurry for photocuring 3D printing, a preparation method and alumina ceramic, and can effectively overcome the technical defects of low solid content, poor curing and forming precision, low mechanical property of products and the like in the traditional alumina ceramic slurry preparation process.
The technical solution of the invention is as follows:
according to a first aspect, there is provided a method of preparing a photocurable alumina ceramic paste for 3D printing, the method comprising the steps of:
step 1, modifying alumina powder by using a macromolecular dispersant containing acidic groups;
and 2, mixing the modified alumina powder obtained in the step 1, a resin monomer composition, a photoinitiator and a diluent to obtain the alumina ceramic slurry, wherein the resin monomer composition is composed of a monofunctional resin monomer, a bifunctional resin monomer and a resin monomer with more than three functional groups, and the mass ratio of the monofunctional resin monomer to the bifunctional resin monomer is 1.8-3: 4-7: 0.5-3.2.
Further, the acidic group-containing polymeric dispersant is at least one selected from BYK111, BYK180, KMT029A and KMT 3023.
Further, the modification of the alumina powder by using the polymeric dispersant containing the acidic group specifically comprises: the preparation method comprises the steps of dissolving the macromolecular dispersing agent containing the acidic group in an organic solvent, mixing with alumina powder, carrying out ball milling, drying and plugging.
Preferably, in the step 1, mixing and ball milling are carried out for 3-6 h, and then drying is carried out at 40-60 ℃ and 60-mesh sieving is carried out.
Further, the organic solvent is ethanol, and the mass ratio of the alumina powder to the ethanol is 1: 2-3.
Further, the high molecular type dispersing agent containing acidic groups accounts for 1-3 wt% of the mass of the alumina.
Further, the alumina powder body comprises nano-scale alumina ceramic powder particles and micron-scale flaky alumina ceramic powder particles, and the average particle sizes of the alumina powder body and the micron-scale flaky alumina ceramic powder particles are respectively 20-50 nm and 1-2 mu m; the mass ratio is 20-30 wt% and 70-80 wt% respectively.
In the resin monomer composition, the monofunctional group resin monomer is one or more of isobornyl methacrylate, isobornyl acrylate, hydroxyethyl methacrylate, ethoxyethoxyethyl acrylate and caprolactone acrylate; the bifunctional resin monomer is one or more of 1, 6-hexanediol diacrylate, propoxylated neopentyl glycol diacrylate, polyethylene glycol diacrylate and tricyclodecyl dimethanol diacrylate; the resin monomer with more than three functional groups is one or more of trimethylolpropane triacrylate, tri (propoxy) triacrylate and pentaerythritol tetraacrylate.
Further, in the step 2, the volume ratio of the modified alumina powder to the resin monomer composition to the diluent is 55-65: 30-35: 5-10; the initiator accounts for 1.25 to 2.5 percent of the mass of the resin monomer composition;
further, the initiator comprises one or more of (2, 4, 6-trimethylbenzoyl) diphenylphosphine oxide, benzoin bis-methyl ether, isopropyl thioxanthone; the diluent is one or more of polyethylene glycol or derivatives thereof.
Preferably, in the step 2, the mixing process is: mixing and ball-milling for a certain time, and then vacuum pumping for 0.5-1 h.
Preferably, in the step 2, the ball milling medium is alumina, the diameter of the ball milling medium is 1-3 mm, the ball milling medium is spherical, the material-ball ratio is 1: 2-3, the rotation speed of the ball mill is 280 r/min-340 r/min, and the ball milling time is 2-4 h.
According to a second aspect, an alumina ceramic slurry for photocuring 3D printing is provided, and the ceramic slurry is prepared by the preparation method.
According to a third aspect, an alumina ceramic is provided, which is prepared by using the alumina ceramic slurry or the alumina prepared by the method as a raw material and adopting a DLP photocuring molding technology.
Compared with the prior art, the invention has the beneficial effects that:
firstly, carrying out surface modification pretreatment on alumina powder by adopting a polymeric dispersant containing acidic groups, so that the affinity with resin is enhanced, and the stability and solid content of slurry are improved; on the basis, when the modified aluminum oxide powder slurry is compounded, a monofunctional group resin monomer, a bifunctional group resin monomer and a resin monomer with more than three functional groups are selected according to a specific proportion, and different types of resin monomers with specific proportions have synergistic effect with the modified aluminum oxide powder, so that the affinity with a substrate, the strength of a blank body and the shrinkage rate of the resin can be improved, the curing shrinkage of a complex structural member and a bending strip in the preparation process can be reduced, and the shape precision is improved; the invention further optimizes the ceramic performance through the gradation of the flaky alumina and the nano-particles, the flaky alumina not only can weaken the scattering of light and improve the dimensional precision, but also can be beneficial to slurry leveling under the condition of high solid content to facilitate the molding of a green body, and the nano-particles have larger surface area and are beneficial to sintering and improving the density. The synergistic effect of the three components can prepare alumina ceramic with the solid content of 55-65 vol% and the bending strength of not less than 400Mpa, and the defects of the existing alumina ceramic prepared by photocuring and forming are overcome.
Drawings
Fig. 1 shows a 1600 ℃ sintered structure provided in example 1.
Detailed Description
The following provides a detailed description of specific embodiments of the present invention. In the following description, for purposes of explanation and not limitation, specific details are set forth in order to provide a thorough understanding of the present invention. However, it will be apparent to one skilled in the art that the present invention may be practiced in other embodiments that depart from these specific details.
It should be noted that, in order to avoid obscuring the present invention by unnecessary details, only the device structure and/or the processing steps closely related to the scheme according to the present invention are shown, and other details not closely related to the present invention are omitted.
Example 1
Step 1: pretreating alumina powder, namely firstly dissolving a dispersant BYK111 (2.5 wt% of the mass of alumina) in absolute ethyl alcohol, then mixing the absolute ethyl alcohol with alumina powder (40 nm of 20 wt% and 2 mu m of 80 wt%), carrying out ball milling for 5 hours, and then drying the slurry at 50 ℃ and sieving the dried slurry with a 60-mesh sieve, wherein the mass ratio of the alumina powder to the ethanol is 1: 2.5;
step 2: preparing slurry, namely mixing and ball-milling the alumina powder pretreated in the step 1, resin monomers (isobornyl methacrylate, propoxylated neopentyl glycol diacrylate and tri (propoxy) triacrylate) and a diluent polyethylene glycol 200 in a mass ratio of 2.5:5:1.5), and performing vacuum pumping for 0.5h to obtain alumina ceramic slurry; wherein, the alumina powder: resin monomer: the volume ratio of the diluent is 58:32: 10; the initiator accounts for 1.5 percent of the mass of the monomer, the ball milling medium is spherical alumina with the diameter of 2mm, the material-ball ratio is 1:2, the rotating speed of the ball mill is 300r/min, and the ball milling time is 2 hours.
An alumina ceramic member was prepared based on the slurry of this example using DLP photocuring molding technique, as shown in fig. 1, fig. 1 shows a structure after sintering at 1600 ℃, with dimensions of 40 × 40 × 80 mm. Therefore, the resin shrinkage rate can be adjusted by different types of resin monomers with specific proportions, the curing shrinkage in the preparation process of a complex structural member can be reduced, the shape precision is improved, a large-size sample piece is printed, and the sample piece is easy to warp if the sample piece is not compounded and printed.
Example 2
Step 1: pretreating alumina powder, namely firstly dissolving a dispersant BYK111 (1 wt% of the mass of alumina) in absolute ethyl alcohol, then mixing and ball-milling the mixture with alumina powder (20 wt% of 40nm and 80 wt% of 2 mu m) for 5 hours, and then drying the slurry at 50 ℃ and sieving the dried slurry with a 60-mesh sieve, wherein the mass ratio of the alumina powder to the ethanol is 1: 2.5;
step 2: preparing slurry, namely mixing and ball-milling the alumina powder pretreated in the step 1, resin monomers (isobornyl methacrylate, propoxylated neopentyl glycol diacrylate and tri (propoxy) triacrylate) and a diluent polyethylene glycol 200 in a mass ratio of 2.5:5:1.5), and performing vacuum pumping for 0.5h to obtain alumina ceramic slurry; wherein, the alumina powder: resin monomer: the volume ratio of the diluent is 58:32: 10; the initiator accounts for 1.5 percent of the mass of the monomer, the ball milling medium is spherical alumina with the diameter of 2mm, the material-ball ratio is 1:2, the rotating speed of the ball mill is 300r/min, and the ball milling time is 2 hours.
Example 3
Step 1: pretreating alumina powder, namely firstly dissolving a dispersant BYK180 (3 wt% of the mass of alumina) in absolute ethyl alcohol, then mixing and ball-milling the mixture with alumina powder (20 wt% of 40nm and 80 wt% of 2 mu m) for 5 hours, and then drying the slurry at 50 ℃ and sieving the dried slurry with a 60-mesh sieve, wherein the mass ratio of the alumina powder to the ethanol is 1: 2.5;
step 2: preparing slurry, namely mixing and ball-milling the alumina powder pretreated in the step 1, resin monomers (isobornyl methacrylate, propoxylated neopentyl glycol diacrylate and tri (propoxy) triacrylate) and a diluent polyethylene glycol 200 in a mass ratio of 2.5:5:1.5), and performing vacuum pumping for 0.5h to obtain alumina ceramic slurry; wherein, the alumina powder: resin monomer: the volume ratio of the diluent is 58:32: 10; the initiator accounts for 1.5 percent of the mass of the monomer, the ball milling medium is spherical alumina with the diameter of 2mm, the material-ball ratio is 1:2, the rotating speed of the ball mill is 300r/min, and the ball milling time is 2 hours.
Example 4
Step 1: pretreating alumina powder, namely firstly dissolving a dispersant BYK111 (2.5 wt% of the mass of alumina) in absolute ethyl alcohol, then mixing the absolute ethyl alcohol with alumina powder (40 nm of 20 wt% and 2 mu m of 80 wt%), carrying out ball milling for 5 hours, and then drying the slurry at 50 ℃ and sieving the dried slurry with a 60-mesh sieve, wherein the mass ratio of the alumina powder to the ethanol is 1: 2.5;
step 2: preparing slurry, namely mixing and ball-milling the mixture of the alumina powder pretreated in the step 1, resin monomers (isobornyl methacrylate, propoxylated neopentyl glycol diacrylate and tri (propoxy) triacrylate in a mass ratio of 1.8:4:0.5), 2, 4, 6-trimethylbenzoyl) diphenyl phosphine oxide and a diluent polyethylene glycol 200, and performing vacuum pumping for 0.5h to obtain alumina ceramic slurry; wherein, the alumina powder: resin monomer: the volume ratio of the diluent is 58:32: 10; the initiator accounts for 1.5 percent of the mass of the monomer, the ball milling medium is spherical alumina with the diameter of 2mm, the material-ball ratio is 1:2, the rotating speed of the ball mill is 300r/min, and the ball milling time is 2 hours.
Example 5
Step 1: pretreating alumina powder, namely firstly dissolving a dispersant BYK111 (2.5 wt% of the mass of alumina) in absolute ethyl alcohol, then mixing the absolute ethyl alcohol with alumina powder (40 nm of 20 wt% and 2 mu m of 80 wt%), carrying out ball milling for 5 hours, and then drying the slurry at 50 ℃ and sieving the dried slurry with a 60-mesh sieve, wherein the mass ratio of the alumina powder to the ethanol is 1: 2.5;
step 2: preparing slurry, namely mixing and ball-milling the alumina powder pretreated in the step 1, resin monomers (isobornyl methacrylate, propoxylated neopentyl glycol diacrylate and tri (propoxy) triacrylate) and a diluent polyethylene glycol 200 in a mass ratio of 3:7:3.2), (2, 4, 6-trimethylbenzoyl) diphenyl phosphine oxide and vacuum pumping for 0.5h to obtain alumina ceramic slurry; wherein, the alumina powder: resin monomer: the volume ratio of the diluent is 58:32: 10; the initiator accounts for 1.5 percent of the mass of the monomer, the ball milling medium is spherical alumina with the diameter of 2mm, the material-ball ratio is 1:2, the rotating speed of the ball mill is 300r/min, and the ball milling time is 2 hours.
Comparative example 1
The only difference from example 1 is that the alumina powder was not pretreated with the acidic group-containing polymeric dispersant.
Comparative example 2
The only difference from example 1 is that the acidic group-containing polymeric dispersant was added directly in step 2 without prior pretreatment of the alumina powder for modification.
Comparative example 3
The only difference from example 1 is that the resin monomer species is only isobornyl methacrylate.
Comparative example 4
The only difference from example 1 is that the resin monomer species is only propoxylated neopentyl glycol diacrylate.
Comparative example 5
The only difference from example 1 is that the resin monomer species is only tris (propoxy) triacrylate.
Comparative example 6
The only difference from example 1 is: the mass ratio of the resin monomer (mixture of isobornyl methacrylate, propoxylated neopentyl glycol diacrylate, tris (propoxy) triacrylate) was 2.5:5: 5).
Comparative example 7
The only difference from example 1 is that only 40nm alumina powder was used.
The properties of the products obtained by the above examples and comparative examples using the same test standard are shown in table 1.
TABLE 1 results of performance test of products obtained in examples and comparative examples
As can be seen from Table 1, in examples 1 to 5 and comparative examples 1 to 7, the alumina is modified by using the high-parting dispersant containing acidic groups (comparative examples 1 to 2, no modification exists, and the addition sequence does not achieve the effect of the examples), and is coordinated with the monofunctional resin monomer, the bifunctional resin monomer and the resin monomer with more than three functional groups in a specific ratio (comparative examples 3 to 5, a single resin monomer, comparative examples 6 to 7, the content of the resin monomer does not achieve the effect of the examples within the range limited by the invention), and the alumina of different types is compounded (comparative example 8), so that the curing thickness, the solid content and the mechanical property of the product are greatly improved.
Features that are described and/or illustrated above with respect to one embodiment may be used in the same way or in a similar way in one or more other embodiments and/or in combination with or instead of the features of the other embodiments.
It should be emphasized that the term "comprises/comprising" when used herein, is taken to specify the presence of stated features, integers, steps or components but does not preclude the presence or addition of one or more other features, integers, steps, components or groups thereof.
The many features and advantages of these embodiments are apparent from the detailed specification, and thus, it is intended by the appended claims to cover all such features and advantages of these embodiments which fall within the true spirit and scope thereof. Further, since numerous modifications and changes will readily occur to those skilled in the art, it is not desired to limit the embodiments of the invention to the exact construction and operation illustrated and described, and accordingly, all suitable modifications and equivalents may be resorted to, falling within the scope thereof.
The invention has not been described in detail and is in part known to those of skill in the art.
Claims (10)
1. A preparation method of alumina ceramic slurry for photocuring 3D printing is characterized by comprising the following steps:
step 1, modifying alumina powder by using a macromolecular dispersant containing acidic groups;
and 2, mixing the modified alumina powder obtained in the step 1, a resin monomer composition, a photoinitiator and a diluent to obtain alumina ceramic slurry, wherein the resin monomer composition is composed of a monofunctional group resin monomer, a bifunctional group resin monomer and a resin monomer with more than three functional groups, and the mass ratio of the monofunctional group resin monomer to the bifunctional group resin monomer is 1.8-3: 4-7: 0.5-3.2.
2. The method of preparing the alumina ceramic paste for photo-curing 3D printing according to claim 1, wherein the polymeric dispersant containing acidic groups is at least one selected from BYK111, BYK180, KMT029A, KMT 3023.
3. The preparation method of the alumina ceramic slurry for photocuring 3D printing according to claim 1, wherein the modification of the alumina powder by using the acidic group-containing polymeric dispersant specifically comprises: the preparation method comprises the steps of dissolving the macromolecular dispersing agent containing the acidic group in an organic solvent, mixing with alumina powder, carrying out ball milling, drying and plugging.
4. The preparation method of the alumina ceramic slurry for photocuring 3D printing according to claim 3, wherein the organic solvent is ethanol, and the mass ratio of the alumina powder to the ethanol is 1: 2-3.
5. The method for preparing the alumina ceramic slurry for photocuring 3D printing according to claim 1 or 2, wherein the polymeric dispersant containing an acidic group accounts for 1 to 3 wt% of the mass of alumina.
6. The preparation method of the alumina ceramic slurry for photocuring 3D printing according to any one of claims 1 to 5, wherein the alumina powder comprises nano-scale alumina ceramic powder particles and micron-scale flaky alumina ceramic powder particles, and the average particle diameters of the alumina ceramic powder particles are respectively 20-50 nm and 1-2 μm; the mass ratio is 20-30 wt% and 70-80 wt% respectively.
7. The method for preparing the alumina ceramic paste for photocuring 3D printing according to claim 1, wherein the monofunctional resin monomer in the resin monomer composition is one or more of isobornyl methacrylate, isobornyl acrylate, hydroxyethyl methacrylate, ethoxyethoxyethyl acrylate and caprolactone acrylate; the bifunctional resin monomer is one or more of 1, 6-hexanediol diacrylate, propoxylated neopentyl glycol diacrylate, polyethylene glycol diacrylate and tricyclodecyl dimethanol diacrylate; the resin monomer with more than three functional groups is one or more of trimethylolpropane triacrylate, tri (propoxy) triacrylate and pentaerythritol tetraacrylate; the initiator comprises one or more of (2, 4, 6-trimethylbenzoyl) diphenylphosphine oxide, benzoin dimethyl ether and isopropyl thioxanthone; the diluent is one or more of polyethylene glycol or derivatives thereof.
8. The preparation method of the alumina ceramic slurry for photocuring 3D printing according to claims 1-6, wherein in the step 2, the volume ratio of the modified alumina powder to the resin monomer composition to the diluent is 55-65: 30-35: 5-10; the initiator accounts for 1.25 to 2.5 percent of the mass of the resin monomer composition.
9. An alumina ceramic slurry for photocuring 3D printing, which is characterized by being prepared by the preparation method of claims 1-8.
10. The alumina ceramic is characterized by being prepared by taking the alumina ceramic slurry of claim 9 or the alumina ceramic slurry prepared by the method of claims 1 to 8 as a raw material and adopting a DLP (digital light processing) photocuring molding technology.
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