CN116354720B - Photopolymerization 3D printing Ce-LuAG ink, application thereof in fluorescent ceramic material and additive manufacturing method thereof - Google Patents
Photopolymerization 3D printing Ce-LuAG ink, application thereof in fluorescent ceramic material and additive manufacturing method thereof Download PDFInfo
- Publication number
- CN116354720B CN116354720B CN202310242643.6A CN202310242643A CN116354720B CN 116354720 B CN116354720 B CN 116354720B CN 202310242643 A CN202310242643 A CN 202310242643A CN 116354720 B CN116354720 B CN 116354720B
- Authority
- CN
- China
- Prior art keywords
- ink
- ceramic
- luag
- fluorescent ceramic
- printing
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 238000010146 3D printing Methods 0.000 title claims abstract description 38
- 238000004519 manufacturing process Methods 0.000 title abstract description 12
- 229910010293 ceramic material Inorganic materials 0.000 title description 9
- 239000000654 additive Substances 0.000 title description 7
- 230000000996 additive effect Effects 0.000 title description 7
- 239000000919 ceramic Substances 0.000 claims abstract description 80
- 238000010438 heat treatment Methods 0.000 claims abstract description 37
- 239000000843 powder Substances 0.000 claims abstract description 30
- 239000012700 ceramic precursor Substances 0.000 claims abstract description 24
- 239000011347 resin Substances 0.000 claims abstract description 8
- 229920005989 resin Polymers 0.000 claims abstract description 8
- 238000005245 sintering Methods 0.000 claims description 35
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 30
- 238000000498 ball milling Methods 0.000 claims description 17
- 238000001513 hot isostatic pressing Methods 0.000 claims description 16
- 238000001816 cooling Methods 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 15
- 238000000137 annealing Methods 0.000 claims description 10
- 239000011259 mixed solution Substances 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 9
- 239000002245 particle Substances 0.000 claims description 8
- 238000007873 sieving Methods 0.000 claims description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- 239000002270 dispersing agent Substances 0.000 claims description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 5
- 229910052593 corundum Inorganic materials 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 229910003443 lutetium oxide Inorganic materials 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 238000002360 preparation method Methods 0.000 claims description 5
- 238000007639 printing Methods 0.000 claims description 5
- 238000004062 sedimentation Methods 0.000 claims description 5
- 230000003068 static effect Effects 0.000 claims description 5
- 239000000725 suspension Substances 0.000 claims description 5
- 238000002834 transmittance Methods 0.000 claims description 5
- 238000005303 weighing Methods 0.000 claims description 5
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- 239000000243 solution Substances 0.000 claims description 4
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 3
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 3
- 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
- 241000252203 Clupea harengus Species 0.000 claims description 2
- 101000720524 Gordonia sp. (strain TY-5) Acetone monooxygenase (methyl acetate-forming) Proteins 0.000 claims description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 2
- 229920002125 Sokalan® Polymers 0.000 claims description 2
- 235000019514 herring Nutrition 0.000 claims description 2
- ZDHCZVWCTKTBRY-UHFFFAOYSA-N omega-Hydroxydodecanoic acid Natural products OCCCCCCCCCCCC(O)=O ZDHCZVWCTKTBRY-UHFFFAOYSA-N 0.000 claims description 2
- 239000004584 polyacrylic acid Substances 0.000 claims description 2
- 239000007790 solid phase Substances 0.000 claims description 2
- GPRLSGONYQIRFK-MNYXATJNSA-N triton Chemical compound [3H+] GPRLSGONYQIRFK-MNYXATJNSA-N 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- 238000013019 agitation Methods 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 26
- 238000000465 moulding Methods 0.000 abstract description 5
- 238000013461 design Methods 0.000 abstract description 2
- 239000000976 ink Substances 0.000 description 47
- 238000012360 testing method Methods 0.000 description 38
- 239000007788 liquid Substances 0.000 description 9
- 238000000016 photochemical curing Methods 0.000 description 9
- 239000006185 dispersion Substances 0.000 description 8
- 230000003287 optical effect Effects 0.000 description 6
- -1 cerium ion Chemical class 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 230000005540 biological transmission Effects 0.000 description 4
- 238000007088 Archimedes method Methods 0.000 description 3
- 229910052684 Cerium Inorganic materials 0.000 description 3
- 244000282866 Euchlaena mexicana Species 0.000 description 3
- 230000001133 acceleration Effects 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 238000000280 densification Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- 239000002223 garnet Substances 0.000 description 3
- 238000005286 illumination Methods 0.000 description 3
- 239000011812 mixed powder Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 238000004626 scanning electron microscopy Methods 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 229920004890 Triton X-100 Polymers 0.000 description 1
- 239000013504 Triton X-100 Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 238000002189 fluorescence spectrum Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/50—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on rare-earth compounds
-
- 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
-
- 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
- C04B35/44—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 aluminates
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3217—Aluminum oxide or oxide forming salts thereof, e.g. bauxite, alpha-alumina
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3224—Rare earth oxide or oxide forming salts thereof, e.g. scandium oxide
- C04B2235/3229—Cerium oxides or oxide-forming salts thereof
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
- C04B2235/656—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes characterised by specific heating conditions during heat treatment
- C04B2235/6562—Heating rate
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
- C04B2235/656—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes characterised by specific heating conditions during heat treatment
- C04B2235/6565—Cooling rate
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
- C04B2235/656—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes characterised by specific heating conditions during heat treatment
- C04B2235/6567—Treatment time
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
- C04B2235/74—Physical characteristics
- C04B2235/77—Density
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
- C04B2235/96—Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance
- C04B2235/9646—Optical properties
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
- C04B2235/96—Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance
- C04B2235/9646—Optical properties
- C04B2235/9653—Translucent or transparent ceramics other than alumina
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Ceramic Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Civil Engineering (AREA)
- Composite Materials (AREA)
Abstract
The invention discloses a photopolymerization 3D printing Ce, which is prepared from LuAG ink, wherein the general formula of the ink is (CexLu 1-x)3Al5O12, wherein x is more than 0 and less than or equal to 0.03. The invention develops a fluorescent ceramic ink suitable for 3D printing, solves the problem of difficult molding of a fluorescent ceramic special-shaped device, has the advantages of no need of a die, simple process, intelligent manufacturing and controllable cost, obtains high-solid-content and low-viscosity ultraviolet light cured ceramic ink by uniformly dispersing fluorescent ceramic precursor powder in photosensitive resin, designs a 3D structure of the device according to actual application scenes, and transmits the cut 3D model to a 3D printer to finally obtain a ceramic blank, and obtains a hyper-hemispherical fluorescent ceramic device after heat treatment.
Description
Technical Field
The invention belongs to the technical field of fluorescent ceramic preparation, and particularly relates to photopolymerized 3D printing Ce-LuAG ink, application of the photopolymerized Ce-LuAG ink in a fluorescent ceramic material and an additive manufacturing method of the photopolymerized Ce-LuAG ink.
Background
The laser illumination technology is an important technical path for realizing white light emission by combining a laser diode with a fluorescent conversion material, and is considered as a powerful competitive technology of next-generation illumination light sources; wherein the fluorescent conversion material has important influence on parameters of the whole light source, such as luminous efficiency, working stability and the like. In recent years, a plurality of green/yellow/red fluorescent materials are adopted in the technical field of laser illumination to expand the spectrum, so that high-quality white light is obtained. The trivalent cerium ion doped lutetium aluminum garnet fluorescent ceramic material is considered as one of fluorescent conversion materials with optimal comprehensive performance, and has high thermal stability and saturation threshold under high-power laser irradiation.
However, the conventional molding process for preparing transparent ceramics has the problems of high cost, complex process and the like, and it is difficult to prepare transparent ceramic devices with complex shapes, so that the application and development of fluorescent ceramics are limited. The method for manufacturing the fluorescent ceramic material by using the additive (3D printing) can freely model and form the fluorescent ceramic material according to the application scene of the fluorescent ceramic material by using computer-aided design software, solves the problems of precision, complex mold process and the like in the traditional preparation process, has short forming period and low process cost, and has great application prospect.
Disclosure of Invention
The invention provides an additive manufacturing mode for forming a free geometric structure of a trivalent cerium ion doped lutetium aluminum garnet ceramic material, in particular to cerium doped lutetium aluminum garnet ceramic ink suitable for an ultraviolet polymerization-based additive manufacturing mode, and a fluorescent ceramic preparation method with a free design structure;
The invention takes intelligent additive manufacturing as a main molding method to realize 3D printing integrated molding of the special-shaped fluorescent ceramic device, and obtains the freely designed fluorescent ceramic material device after heat treatment.
The technical scheme of the invention is realized as follows:
On one hand, the invention provides a photopolymerization 3D printing Ce-LuAG ink, wherein the general formula of the ink is (Ce xLu1-x)3Al5O12, wherein x is more than 0 and less than or equal to 0.03.
In a preferred embodiment, the solid phase content of the photopolymerizable 3D printing Ce/LuAG ink is more than or equal to 50vol%.
In a preferred embodiment, the viscosity of the photopolymerizable 3D printing Ce/LuAG ink is less than or equal to 1000cP@10s -1.
In another aspect, the present invention also provides a method of preparing a photopolymerizable 3D printing ink, comprising the steps of:
(1) According to the mass ratio of 0.1:16.5-49.4:38.4 to 115.5, respectively weighing CeO 2,Al2O3,Lu2O3, mixing, adding an ethanol solution of tetraethoxysilane, ball-milling, drying and sieving to obtain Ce-LuAG ceramic precursor powder;
(2) Adding Ce-LuAG ceramic precursor powder into a dispersion mixed solution of a dispersing agent and a solvent, and continuously stirring to obtain a premix after ultrasonic crushing and dispersion;
(3) Ball milling and stirring the premix and the photosensitive mixed solution, and vacuum defoaming until no bubble is floated out, thereby obtaining the photopolymerization 3D printing Ce: luAG ink.
In a preferred embodiment, the method for preparing a photopolymerizable 3D printing ink according to the invention, wherein the Ce: luAG ceramic precursor powder in step (1) has a particle size of 0.34-0.46 μm.
In a preferred embodiment, the method for preparing the photopolymerization 3D printing ink comprises the steps of (1) enabling the mass ratio of ethanol to ethyl orthosilicate in an ethanol solution of the ethyl orthosilicate to be 0.8-1.2:2, and enabling the ball milling speed to be 256-280r/min; the mesh number of the sieving is 200-250 mesh.
In a preferred embodiment, the suspension static sedimentation rate of the premix in step (2) is 3-6% in the method for preparing a photopolymerizable 3D printing ink according to the invention.
In a preferred embodiment, the method for preparing the photopolymerization 3D printing ink comprises the steps of (2) enabling the mass ratio of the dispersing agent to the solvent to the Ce/LuAG ceramic precursor powder to be 0.1-2:15-30:100, wherein the ultrasonic crushing condition is 80kHz; the continuous stirring is carried out at the temperature of 23-25 ℃ and the humidity of 50-55% under the air pressure of 1.01-1.05X10 -5 Pa.
In a preferred embodiment, the present invention provides a method for preparing a photopolymerizable 3D printing ink, said dispersant being selected from one or more of herring oil, KH560, polyacrylic acid, maleic anhydride, sodium dodecyl sulfate, triton; the solvent is one or more selected from methanol, ethanol, isopropanol, diethyl ether, benzene, toluene, xylene and acetone.
In a preferred embodiment, the method for preparing the photopolymerization 3D printing ink according to the present invention, wherein the photosensitive mixed solution in the step (3) is obtained by dissolving a photoinitiator in a resin.
In a preferred embodiment, the invention provides a method for preparing a photopolymerization 3D printing ink, wherein the mass ratio of the photoinitiator to the resin to the Ce/LuAG ceramic precursor powder is 0.01-0.5:9-12:100; the ball milling and stirring speed is 250r/min; the conditions for vacuum deaeration until no bubbles float are-85 to-80 kPa.
In a preferred embodiment, the present invention is a method of preparing a photopolymerizable 3D printing ink, the photoinitiator is selected from one or more of TPO, TPO-L, bisacylphosphine oxide 819, omnirad184, basf 651; one or more of HDDA, PEGDA, ACMO resins are used.
In yet another aspect, the invention also provides a photopolymerizable 3D printing Ce-LuAG ink prepared by any of the methods described above.
In yet another aspect, the invention also provides a fluorescent ceramic prepared by using the above photopolymerization 3D printing Ce: luAG ink.
In a preferred embodiment, the relative density of the fluorescent ceramic protected by the invention is more than or equal to 99.9%.
In a preferred embodiment, the fluorescent ceramic protected by the invention has a transmittance of not less than 70.95% in the wavelength range of 300-1000 nm.
In yet another aspect, the present invention also provides a method of preparing a fluorescent ceramic, the method comprising the steps of:
(1) Establishing a 3D model, slicing, and printing out a blank;
(2) And (3) pre-sintering the green body, vacuum sintering, hot isostatic pressing sintering and annealing to obtain the fluorescent ceramic.
In a preferred embodiment, the present invention also provides a method for preparing fluorescent ceramics, wherein the opening angle of the 3D model in step (1) is 120-140 °.
In a preferred embodiment, the invention also provides a method for preparing fluorescent ceramics, wherein the presintering in the step (2) is to heat the green body from room temperature to 100-150 ℃ for 6-10h at a heating rate of 1-5 ℃/min; then raising the temperature to 400-500 ℃ at a heating rate of 0.5-1.5 ℃/min, and preserving the temperature for 10-20h; continuously raising the temperature to 1000-1200 ℃ at the speed of 0.1-3 ℃/min, preserving the heat for 10-24h, and then naturally cooling and taking out the pre-sintered body.
In a preferred embodiment, the present invention also provides a method for preparing fluorescent ceramics, wherein in the step (2), the vacuum sintering is performed by raising the temperature of the pre-sintered body from room temperature to 1500-1800 ℃ at a heating rate of 2-10 ℃/min, and preserving the temperature for 1-10 hours; the pressure is 150-300MPa, then naturally cooling, and taking out the vacuum sintered body after naturally cooling and releasing the pressure.
In a preferred embodiment, the invention also provides a method for preparing fluorescent ceramics, wherein in the step (2), the hot isostatic pressing sintering is that the vacuum sintered body is heated from room temperature to 1600-1750 ℃ at a heating rate of 5-6 ℃/min, the pressure is 200MPa, and the temperature is kept for 10 hours, so as to obtain the fluorescent ceramics.
In a preferred embodiment, the invention also provides a method for preparing fluorescent ceramics, wherein in the step (2), the annealing is to heat the fluorescent ceramics from room temperature to 1100-1650 ℃ at 2-10 ℃ per minute under the condition of no pressure in air, and the temperature is kept for 10-30 hours.
The beneficial effects of the invention are as follows: the fluorescent ceramic ink suitable for 3D printing is developed, the problem that a fluorescent ceramic special-shaped device is difficult to mold is solved, and the fluorescent ceramic special-shaped device has the advantages of no need of a mold, simple process, intelligent manufacturing and controllable cost; the fluorescent ceramic precursor powder is uniformly dispersed in the photosensitive resin to obtain ultraviolet-cured ceramic ink with high solid content and low viscosity, a 3D structure of the device is designed according to an actual application scene, and the 3D model is sliced and then transmitted to a 3D printer, so that a ceramic blank is finally obtained; and obtaining the hyper-hemispherical fluorescent ceramic device after heat treatment.
Drawings
FIG. 1A is an X-ray perspective view of a hyper-hemispherical fluorescent ceramic device of example 3;
FIG. 1B is a 3D schematic view of a slice data set of the hyper-hemispherical fluorescence ceramic device of example 3;
FIG. 2 is an ultraviolet polymerization printing hyper-hemispherical ceramic of example 8;
Detailed Description
In order to provide a more concise description, some quantitative representations presented herein are not modified by the term "about". It will be understood that each quantity given herein is intended to refer to an actual given value, whether or not the term "about" is explicitly used, and is also intended to refer to approximations of such given values, including approximations of such given values resulting from experimental and/or measurement conditions, as reasonably deduced by one of ordinary skill in the art.
Establishing a 3D model
The 3D model establishment can be realized by any software capable of realizing 3D model modeling in the prior art.
The invention will be further illustrated by the following examples. It is noted herein that the examples are given solely for the purpose of illustration and are not to be construed as limitations on the scope of the invention, since many insubstantial modifications and variations will become apparent to those skilled in the art in light of the above teachings. The test methods in the following examples, in which specific conditions are not specified, are generally conducted under conventional conditions or under conditions recommended by the manufacturer. All percentages and parts are by weight unless otherwise indicated.
The sources, names and specifications of experimental materials or experimental instruments adopted in the embodiment of the invention are shown in the following table:
the invention is further illustrated below with reference to examples, which should not be taken as limiting the scope of the invention.
Example 1: ce-LuAG ceramic precursor powder
According to the stoichiometric ratio (Ce xLu1-x)3Al5O12, taking x=0.003, respectively accurately weighing CeO 20.1455g,Al2O323.9487g,Lu2O3 55.9125g, mixing to obtain prepared powder, adding 40ml of ethanol and 0.45g of TEOS into the powder, ball milling for 12 hours at a speed of 256r/min, drying the mixed powder, and sieving with a 200-mesh sieve to obtain Ce: luAG ceramic precursor powder for later use.
Test example 1 particle size
Test sample: ce-LuAG ceramic precursor powder prepared in example 1
Test equipment: scanning electron microscopy (Auriga S, zeiss, oberkochen, germany); acceleration voltage: 3kV; magnification factor: 100000 times; wd=6;
Ce-LuAG ceramic precursor powder prepared in example 1 had an average particle size of 0.34. Mu.m.
Example 2: photopolymerization 3D printing Ce-LuAG ink
1G of triton X-100 was dissolved in 100ml of ethanol to obtain a dispersion; 70g of the Ce prepared in the example 1 is weighed and added into the dispersion liquid, and crushed for 15min by using an ultrasonic crusher at 80kHz, and after continuously stirring for 12h under the condition of continuous natural storage in air condition (the temperature is 25 ℃, the humidity is 50 percent and the air pressure is 1.01X10 -5 Pa), the premix liquid is obtained when the static sedimentation rate of the suspension liquid is 5 percent;
Placing the premix into a ball milling tank, and then adding a photosensitive mixed solution obtained by dissolving a photoinitiator 0.1gTPO in 6.1gHDDA and 3.9gPEGDA, and performing ball milling and stirring (250 r/min stirring for 16 h) on a planetary ball mill; and then placing the ink in a vacuum deaerator, deaerating for 10min under the condition of 80kPa until no bubble in the ink floats out, and obtaining the photopolymerization 3D printing Ce: luAG ink for later use.
Test example 2: viscosity test
Test sample: photopolymerizable 3D printing Ce-LuAG ink prepared in example 2
The rheological properties of the ceramic inks were tested using a rotary rheometer (Anton Paar) with a parallel plate diameter of 20 mm. The viscosity was measured at 25℃and the shear rate increased steadily from 0.1 to 1000s -1, using a solvent trap to reduce evaporation.
The viscosity of the photopolymerizable 3D printing Ce, luAG ink prepared in example 2 was 1000cP@10s -1. In photo-curing molding, the viscosity is typically <5000cp@10s -1.
Example 3: blank body
And 3D modeling software is used for establishing a hyper-hemispherical 3D model, the opening angle is 120 degrees, a data set is formed after the 3D model is sliced by a computer, and the data set is transmitted to a Max photo-curing 3D printer produced by Asiga company in Germany. The Ce-LuAG ink prepared in example 2 was placed into the cartridge of a photo-curing 3D printer and the blank was printed out for use.
Example 4: sintering the green body
Sintering the green body comprises four steps, namely presintering, vacuum sintering, hot isostatic pressing sintering and annealing.
Presintering: raising the temperature of the blank prepared in the example 3 from room temperature to 120 ℃ at a heating rate of 2 ℃/min for 6 hours; then the temperature is increased from 30 ℃ to 450 ℃ at the heating rate of 1 ℃/min, and the temperature is kept for 15 hours; continuously heating to 1000 ℃ at the heating rate of 1 ℃/min, preserving heat for 14h, and then naturally cooling to take out the pre-sintered body for later use.
Vacuum sintering: heating the pre-sintered body from room temperature to 1750 ℃ at a heating rate of 5 ℃/min, and preserving heat for 10 hours; and then naturally cooling, and taking out the vacuum sintered body for standby after naturally cooling and releasing pressure.
And (3) hot isostatic pressing sintering: further improving the compactness and optical performance of the ceramic body, heating the vacuum sintered body from room temperature to 1700 ℃ at a heating rate of 5 ℃/min, keeping the pressure of 200MPa, and preserving the temperature for 10 hours to obtain the ceramic sample.
Annealing: and (3) placing the ceramic sample in a muffle furnace, heating the ceramic sample to 1600 ℃ from room temperature at 6 ℃/min under the condition of no pressure in air, and preserving the temperature for 30 hours to eliminate the defects of residual stress and oxygen vacancies, thereby obtaining the fluorescent ceramic for standby.
Test example 3: relative density testing
Test sample: the pre-sintered body prepared in example 4, the vacuum sintered body prepared in example 4, the ceramic sample prepared in example 4
The relative density of the sintered Ce: luAG ceramic structure was determined by archimedes method.
| Sample of | Relative density |
| The pre-sintered body prepared in example 4 | 93％ |
| Vacuum sintered body produced in example 4 | 99％ |
| Example 4 ceramic sample prepared | 99.9％ |
The relative density of the ceramic in the presintering stage must exceed 92%, so that densification can be finally realized through hot isostatic pressing sintering, the relative density of a hot isostatic pressing sintering sample exceeds 99.9%, and the sample has good infrared transmission performance and meets various optical application conditions.
Example 5: ce-LuAG ceramic precursor powder
According to the stoichiometric ratio (Ce xLu1-x)3Al5O12, taking x=0.001, respectively accurately weighing CeO 20.0485g,Al2O323.9428g,Lu2O3 56.0109g, mixing to obtain prepared powder, adding 40ml of ethanol and 0.45g of TEOS into the powder, ball milling for 12 hours at the speed of 280r/min, drying the mixed powder, and sieving with a 250-mesh sieve to obtain Ce/LuAG ceramic precursor powder for later use.
Test example 4 particle size
Test sample: ce-LuAG ceramic precursor powder prepared in example 5
Test equipment: scanning electron microscopy (Auriga S, zeiss, oberkochen, germany); acceleration voltage: 3kV; magnification factor: 100000 times; wd=6;
Ce-LuAG ceramic precursor powder prepared in example 5 had an average particle size of 0.41. Mu.m.
Example 6: photopolymerization 3D printing Ce-LuAG ink
1G of maleic anhydride was dissolved in 100ml of ethanol to obtain a dispersion; 70g of the Ce prepared in the example 5 is weighed and added into the dispersion liquid, and crushed for 15min by using an ultrasonic crusher at 80kHz, and after continuously stirring for 12h under the condition of continuous natural storage in air condition (the temperature is 23 ℃, the humidity is 55 percent and the air pressure is 1.02X10 -5 Pa), the premix liquid is obtained when the static sedimentation rate of the suspension liquid is 3 percent;
Placing the premix into a ball milling tank, and then adding a photosensitive mixed solution obtained by dissolving a photoinitiator 0.1gTPO in 6.1gHDDA and 3.9gACMO, and performing ball milling and stirring (250 r/min stirring for 16 h) on a planetary ball mill; and then placing the ink in a vacuum deaerator, deaerating for 10min under the condition of 80kPa until no bubble in the ink floats out, and obtaining the photopolymerization 3D printing Ce: luAG ink for later use.
Test example 5: viscosity test
Test sample: photopolymerizable 3D printing Ce-LuAG ink prepared in example 6
The rheological properties of the ceramic inks were tested using a rotary rheometer (Anton Paar) with a parallel plate diameter of 20 mm. The viscosity was measured at 25℃and the shear rate increased steadily from 0.1 to 1000s -1, using a solvent trap to reduce evaporation.
The viscosity of the photopolymerizable 3D printing Ce, luAG ink prepared in example 6 was 1051cP@10s -1.
Example 7: blank body
And 3D modeling software is used for establishing a hyper-hemispherical 3D model, the opening angle is 130 degrees, a data set is formed after the 3D model is sliced by a computer, and the data set is transmitted to a Max photo-curing 3D printer produced by Asiga company in Germany. The Ce-LuAG ink prepared in example 6 was placed into the cartridge of a photo-curing 3D printer and the blank was printed out for use.
Example 8: sintering the green body
Sintering the green body comprises four steps, namely presintering, vacuum sintering, hot isostatic pressing sintering and annealing.
Presintering: the green body prepared in example 7 was heat-preserved for 6 hours from room temperature to 150℃at a heating rate of 2℃per minute, and then from 30℃to 500℃at a heating rate of 1℃per minute, and heat-preserved for 15 hours; continuously heating to 1100 ℃ at a heating rate of 1 ℃/min, preserving heat for 14h, and then naturally cooling to take out the pre-sintered body for later use.
Vacuum sintering: heating the pre-sintered body from room temperature to 1740 ℃ at a heating rate of 5 ℃/min, and preserving heat for 10h; and then naturally cooling, and taking out the vacuum sintered body for standby after naturally cooling and releasing pressure.
And (3) hot isostatic pressing sintering: further improving the compactness and optical performance of the ceramic body, heating the vacuum sintered body from room temperature to 1600 ℃ at the heating rate of 6 ℃/min, keeping the pressure of 200MPa, and preserving the temperature for 10 hours to obtain the ceramic sample.
Annealing: and (3) placing the ceramic sample in a muffle furnace, heating the ceramic sample to 1600 ℃ from room temperature at 6 ℃/min under the condition of no pressure in air, and preserving the temperature for 30 hours to eliminate the defects of residual stress and oxygen vacancies, thereby obtaining the fluorescent ceramic for standby.
Test example 6: relative density testing
Test sample: the pre-sintered body prepared in example 8, the vacuum sintered body prepared in example 8, and the ceramic sample prepared in example 8
The relative density of the sintered Ce: luAG ceramic structure was determined by archimedes method.
| Sample of | Relative density |
| Example 8 Pre-sintered body | 94％ |
| Vacuum sintered body produced in example 8 | 99％ |
| Example 8 ceramic sample prepared | 99.91％ |
The relative density of the ceramic in the presintering stage must exceed 92%, so that densification can be finally realized through hot isostatic pressing sintering, the relative density of a hot isostatic pressing sintering sample exceeds 99.9%, and the sample has good infrared transmission performance and meets various optical application conditions.
Example 9: ce-LuAG ceramic precursor powder
According to the stoichiometric ratio (Ce xLu1-x)3Al5O12, taking x=0.002, accurately weighing CeO 20.0970g,Al2O323.9458g,Lu2O3 55.9617g respectively, mixing to obtain prepared powder, adding 40ml of ethanol and 0.45g of TEOS into the powder, ball milling at 267r/min for 12h, drying the mixed powder, and sieving with a 200-mesh sieve to obtain Ce: luAG ceramic precursor powder for later use.
Test example 7 particle size
Test sample: ce-LuAG ceramic precursor powder prepared in example 9
Test equipment: scanning electron microscopy (Auriga S, zeiss, oberkochen, germany); acceleration voltage: 3kV; magnification factor: 100000 times; wd=6;
Ce-LuAG ceramic precursor powder prepared in example 9 had an average particle size of 0.46. Mu.m.
Example 10: photopolymerization 3D printing Ce-LuAG ink
1G of sodium dodecyl sulfate was dissolved in 100ml of ethanol to obtain a dispersion; 70g of the Ce prepared in the example 1 is weighed and added into the dispersion liquid, and crushed for 13min by using an ultrasonic crusher at 80kHz, and under the condition of continuous natural storage in air condition (the temperature is 23 ℃, the humidity is 50 percent, and the air pressure is 1.05X10 -5 Pa), after continuously stirring for 12h, when the static sedimentation rate of the suspension liquid is 6 percent, a premix liquid is obtained;
Placing the premix into a ball milling tank, and then adding a photosensitive mixed solution obtained by dissolving a photoinitiator 0.1gTPO in 6.26gHDDA and 4.12gACMO, and performing ball milling and stirring (250 r/min stirring for 16 h) on a planetary ball mill; and then placing the ink in a vacuum deaerator, deaerating for 9min under the condition of-85 kPa until no bubble in the ink floats out, and obtaining the photopolymerization 3D printing Ce: luAG ink for later use.
Test example 8: viscosity test
Test sample: photopolymerizable 3D printing Ce-LuAG ink prepared in example 10
The rheological properties of the ceramic inks were tested using a rotary rheometer (Viscotester iQ Air, HAAKE) with a parallel plate diameter of 20 mm. The viscosity was measured at 25℃and the shear rate increased steadily from 0.1 to 1000s -1, using a solvent trap to reduce evaporation.
The viscosity of the LuAG ink was 1209cp@10s -1 for photopolymerized 3D printing prepared in example 10.
Example 11: blank body
And 3D modeling software is used for establishing a hyper-hemispherical 3D model, the opening angle is 140 degrees, a data set is formed after the 3D model is sliced by a computer, and the data set is transmitted to a Max photo-curing 3D printer produced by Asiga company in Germany. The Ce-LuAG ink prepared in example 10 was placed into the cartridge of a photo-curing 3D printer and printed out of the blank for use.
Example 12: sintering the green body
Sintering the green body comprises four steps, namely presintering, vacuum sintering, hot isostatic pressing sintering and annealing.
Presintering: raising the temperature of the blank prepared in the example 11 from room temperature to 140 ℃ at a heating rate of 2 ℃/min for 10 hours; then the temperature is increased from 30 ℃ to 480 ℃ at the heating rate of 1 ℃/min, and the temperature is kept for 18 hours; continuously raising the temperature to 1200 ℃ at the speed of 1 ℃/min, preserving the heat for 20 hours, and then naturally cooling and taking out the pre-sintered body.
Vacuum sintering: raising the temperature of the pre-sintered body from room temperature to 1800 ℃ at a heating rate of 5 ℃/min, and preserving the temperature for 10 hours; and then naturally cooling, and taking out the vacuum sintered body after naturally cooling and releasing pressure.
And (3) hot isostatic pressing sintering: further improving the compactness and optical performance of the ceramic body, heating the vacuum sintered body from room temperature to 1750 ℃ at a heating rate of 5 ℃/min, keeping the pressure of 200MPa, and preserving the temperature for 10 hours to obtain the ceramic sample.
Annealing: and (3) placing the ceramic sample in a muffle furnace, heating the ceramic sample to 1650 ℃ from room temperature at 6 ℃/min under the condition of no air pressure, and preserving the temperature for 30 hours to eliminate the defects of residual stress and oxygen vacancy, thus obtaining the fluorescent ceramic for standby.
Test example 9: relative density testing
Test sample: the pre-sintered body prepared in example 12, the vacuum sintered body prepared in example 12, and the ceramic sample prepared in example 12
The relative density of the sintered Ce: luAG ceramic structure was determined by archimedes method.
| Sample of | Relative density |
| EXAMPLE 12 Pre-sintered body prepared | 95％ |
| Vacuum sintered body produced in example 12 | 99％ |
| Ceramic sample prepared in example 12 | 99.96％ |
The relative density of the ceramic in the presintering stage must exceed 92%, so that densification can be finally realized through hot isostatic pressing sintering, the relative density of a hot isostatic pressing sintering sample exceeds 99.9%, and the sample has good infrared transmission performance and meets various optical application conditions.
Test example 10:3D model
And 3D modeling software is used for establishing a hyper-hemispherical 3D model, the opening angle is 120 degrees, a data set is formed after the 3D model is sliced by a computer, and the data set is transmitted to a Max photo-curing 3D printer produced by Asiga company in Germany.
Wherein fig. 1 is a 3D model of a fluorescent ceramic hyper-hemispherical device designed in example 3, with an opening angle of 120 °.
Wherein:
FIG. 1A is an X-ray transmission diagram showing the internal cavity structure of a ceramic body;
Fig. 1B is a 3D diagram of a hypersphere device formed by computer slicing of a 3D model to form a dataset, showing the surface details of the printing entity and simulating the printing process.
Test example 11: transmittance test
Test sample: fluorescent ceramics prepared in example 4
Test equipment: ultraviolet visible light spectrophotometer (UBEST V-560, JASCA, japan)
The testing method comprises the following steps: measuring the transmittance of the sample in the wavelength range of 300-1000 nm;
the fluorescent ceramic prepared in example 4 had a transmittance peak value of 70.95% in the wavelength range of 300-1000 nm.
Test example 12: fluorescence spectrum test
Test sample: fluorescent ceramics prepared in example 8
Test equipment: fluorescence spectrometer (Fluomax-4, jobin Yvon, france);
The testing method comprises the following steps: excitation wavelength 450nm;
Fig. 2 is a diagram showing the fabrication of hyper hemispherical fluorescent ceramic devices of different sizes by photo-curing 3D printing technique in example 8. The sample shown in the figure does not need to be molded by a die, the model size is adjusted by a computer to realize equal scaling of 10:1:1:1:0.8, and the die is not required to be customized again, so that quick manufacturing is realized.
Claims (12)
1. A photopolymerization 3D printing Ce, luAG ink,
The general formula of the ink is (CexLu 1-x) 3Al5O12, wherein x is more than 0 and less than or equal to 0.03,
The solid phase content of the ink is more than or equal to 50vol%,
The preparation method of the ink comprises the following steps:
(1) According to the mass ratio of 0.1:16.5-49.4:38.4 to 115.5, respectively weighing CeO 2,Al2O3,Lu2O3, mixing, adding an ethanol solution of tetraethoxysilane, ball-milling, drying and sieving to obtain Ce-LuAG ceramic precursor powder;
(2) Adding Ce-LuAG ceramic precursor powder into a dispersing mixed solution of a dispersing agent and a solvent, wherein the mass ratio of the dispersing agent to the solvent to the Ce-LuAG ceramic precursor powder is 0.1-2:15-30:100, carrying out ultrasonic crushing and dispersing at 80kHz, and continuously stirring at the temperature of 23-25 ℃ and the humidity of 50-55% under the air pressure of 1.01-1.05X10 -5 Pa to obtain a premix;
(3) Ball milling and stirring the premix and the photosensitive mixed solution, and vacuum defoaming until no bubbles float out to obtain photopolymerization 3D printing Ce: luAG ink;
The photosensitive mixed solution in the step (3) is obtained by dissolving a photoinitiator in resin;
The mass ratio of the photoinitiator to the resin to the Ce/LuAG ceramic precursor powder is 0.01-0.5:9-12:100.
2. The ink of claim 1, wherein the Ce: luAG ceramic precursor powder in step (1) has a particle size of 0.34 to 0.46 μm.
3. The ink according to claim 1, wherein the mass ratio of ethanol to ethyl orthosilicate in the ethanol solution of ethyl orthosilicate in the step (1) is 0.8-1.2:2, and the ball milling speed is 256-280r/min; the mesh number of the sieving is 200-250 mesh.
4. The ink of claim 1 wherein the suspension static sedimentation rate of the premix in step (2) is 3-6%.
5. The ink of claim 1, wherein the dispersant is selected from one or more of herring oil, KH560, polyacrylic acid, maleic anhydride, sodium dodecyl sulfate, triton; the solvent is one or more selected from methanol, ethanol, isopropanol, diethyl ether, benzene, toluene, xylene and acetone.
6. The ink of claim 1, wherein the ball milling agitation is at a rate of 250r/min; the conditions for vacuum deaeration until no bubbles float are-85 to-80 kPa.
7. The ink of claim 6, wherein the photoinitiator is selected from one or more of TPO, TPO L, bisacylphosphine oxides 819, omnirad, 184, basf 651; one or more of HDDA, PEGDA, ACMO resins are used.
8. A fluorescent ceramic prepared by using the ink according to any one of claim 1 to 7,
The relative density of the fluorescent ceramic is more than or equal to 99.9 percent,
The transmittance of the fluorescent ceramic in the wavelength range of 300-1000nm is more than or equal to 70.95 percent,
The preparation method of the fluorescent ceramic comprises the following steps:
(1) Establishing a 3D model with an opening angle of 120-140 degrees, and printing a blank body after slicing;
(2) And (3) pre-sintering the green body, vacuum sintering, hot isostatic pressing sintering and annealing to obtain the fluorescent ceramic.
9. The fluorescent ceramic of claim 8, wherein the pre-sintering in step (2) is to heat the green body from room temperature to 100-150 ℃ for 6-10 hours at a heating rate of 1-5 ℃/min; then raising the temperature to 400-500 ℃ at a heating rate of 0.5-1.5 ℃/min, and preserving the temperature for 10-20h; continuously raising the temperature to 1000-1200 ℃ at the speed of 0.1-3 ℃/min, preserving the heat for 10-24h, and then naturally cooling and taking out the pre-sintered body.
10. The fluorescent ceramic according to claim 8, wherein the vacuum sintering in step (2) is performed by heating the pre-sintered body from room temperature to 1500-1800 ℃ at a heating rate of 2-10 ℃/min, and maintaining the temperature for 1-10 hours; the pressure is 150-300MPa, then naturally cooling, and taking out the vacuum sintered body after naturally cooling and releasing the pressure.
11. The fluorescent ceramic according to claim 8, wherein the hot isostatic pressing sintering in the step (2) is performed by heating the vacuum sintered body from room temperature to 1600-1750 ℃ at a heating rate of 5-6 ℃/min, and maintaining the pressure at 200MPa for 10 hours, thereby obtaining the fluorescent ceramic.
12. The fluorescent ceramic of claim 8, wherein the annealing in step (2) is performed by raising the temperature of the fluorescent ceramic from room temperature to 1100-1650 ℃ at 2-10 ℃/min under air-free conditions, and maintaining the temperature for 10-30 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310242643.6A CN116354720B (en) | 2023-03-14 | 2023-03-14 | Photopolymerization 3D printing Ce-LuAG ink, application thereof in fluorescent ceramic material and additive manufacturing method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310242643.6A CN116354720B (en) | 2023-03-14 | 2023-03-14 | Photopolymerization 3D printing Ce-LuAG ink, application thereof in fluorescent ceramic material and additive manufacturing method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN116354720A CN116354720A (en) | 2023-06-30 |
| CN116354720B true CN116354720B (en) | 2024-07-16 |
Family
ID=86906193
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310242643.6A Active CN116354720B (en) | 2023-03-14 | 2023-03-14 | Photopolymerization 3D printing Ce-LuAG ink, application thereof in fluorescent ceramic material and additive manufacturing method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116354720B (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108218417A (en) * | 2016-12-14 | 2018-06-29 | 中国科学院上海硅酸盐研究所 | A kind of LuAG of lower valency ion doping:Ce, Me scintillating ceramic and preparation method thereof |
| CN110272208A (en) * | 2019-07-18 | 2019-09-24 | 浙江大学 | A kind of green fluorescence glass ceramics and its preparation method and application |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105198449B (en) * | 2015-09-16 | 2018-03-09 | 广东工业大学 | A kind of preparation method of the high ceramic of compact of Stereolithography |
| JP6560835B2 (en) * | 2016-06-02 | 2019-08-14 | シグニファイ ホールディング ビー ヴィ | Filaments for hot melt lamination including electronic components |
| FR3053353B1 (en) * | 2016-06-30 | 2018-07-27 | Aledia | PROCESS FOR PRODUCING PHOTOLUMINESCENT PARTICLES |
| US10961342B2 (en) * | 2016-10-25 | 2021-03-30 | Agency For Science, Technology And Research | Resin formulation and uses thereof |
| CN108456002B (en) * | 2018-02-08 | 2021-03-16 | 广东工业大学 | Method for 3D printing of ceramic component based on photocuring forming and suitable for self-repairing/self-enhancing |
| CN109761608A (en) * | 2019-03-07 | 2019-05-17 | 江苏师范大学 | A method of rodlike composite transparent ceramic is prepared based on direct write molding 3D printing technique |
| CN115259852A (en) * | 2021-04-29 | 2022-11-01 | 江苏师范大学 | High-light-efficiency green light conversion material and preparation method thereof |
| WO2023003511A2 (en) * | 2021-07-19 | 2023-01-26 | Nanyang Technological University | Methods of stereolithography 3d printing of transparent yag ceramics |
| CN115557787B (en) * | 2022-10-14 | 2023-05-12 | 中国科学院上海光学精密机械研究所 | Sesquioxide transparent ceramic and preparation method thereof |
-
2023
- 2023-03-14 CN CN202310242643.6A patent/CN116354720B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108218417A (en) * | 2016-12-14 | 2018-06-29 | 中国科学院上海硅酸盐研究所 | A kind of LuAG of lower valency ion doping:Ce, Me scintillating ceramic and preparation method thereof |
| CN110272208A (en) * | 2019-07-18 | 2019-09-24 | 浙江大学 | A kind of green fluorescence glass ceramics and its preparation method and application |
Non-Patent Citations (1)
| Title |
|---|
| "Three-dimensional printing of transparent ceramics by lithography-based digital projection"，Guangran Zhang，《Additive Manufacturing》，第47卷，第1-9页;Guangran Zhang;《Additive Manufacturing》;第47卷;第1-9页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN116354720A (en) | 2023-06-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106396414B (en) | A kind of low-temperature co-burning ceramic material and preparation method thereof | |
| CN103011614B (en) | A kind of fluorescent glass sheet and preparation method thereof | |
| CN103058633A (en) | Method of YAG composite transparent laser ceramic | |
| CN107285745A (en) | A kind of preparation method and fluorescence associated ceramics of the fluorescence ceramics of alumina host | |
| CN109053182A (en) | A method of YAG base multi-layer compound structure crystalline ceramics is prepared using Isobam gel injection-moulding | |
| US20220064053A1 (en) | Preparation method and use of yellow fluorescent glass ceramic | |
| CN110885244B (en) | Preparation method of yttrium aluminum garnet-based transparent ceramic optical fiber | |
| CN107200588B (en) | Preparation method of aluminum nitride matrix fluorescent ceramic and related fluorescent ceramic | |
| CN108840564A (en) | The phosphate laser neodymium glass of luminescence effect | |
| Li et al. | Preparation and luminescent properties of the coating of phosphor in lead-free glass by multilayer screen-printing | |
| CN108530070A (en) | A kind of fluorescence ceramics and preparation method thereof that the enhancing of surface light trapping structure is luminous | |
| CN116354720B (en) | Photopolymerization 3D printing Ce-LuAG ink, application thereof in fluorescent ceramic material and additive manufacturing method thereof | |
| CN113563059A (en) | Ceramic core slurry for 3D printing and preparation method and application thereof | |
| CN104961471A (en) | Cast film slurry of ultrathin lamination flaky inductor and manufacturing method for cast film of ultrathin lamination flaky inductor | |
| CN104355609B (en) | The mist projection granulating preparation method of YAG base transparent ceramic powder body | |
| CN103319093B (en) | Yb-doped strontium fluorophosphate microcrystal/Yb-doped fluorophosphate glass composite material and preparation method thereof | |
| CN109293358B (en) | Down-conversion luminescent transparent ceramic and preparation method thereof | |
| CN101798181A (en) | Eu-doped high-silica glass and preparation method thereof | |
| CN106698933B (en) | A kind of devitrified glass and its preparation method and application of transparent low melting point | |
| CN107200589B (en) | Preparation method of aluminum nitride matrix fluorescent ceramic and related fluorescent ceramic | |
| CN116396070A (en) | Multi-material laser ceramic and preparation method of integrated 3D printing molding thereof | |
| CN107540367A (en) | A kind of method that non-water-base gel casting prepares garnet-base transparent ceramic | |
| CN104909741A (en) | Preparation method of garnet-type aluminate fluorescence ceramic and prepared fluorescence ceramic | |
| CN109279873B (en) | Ultralow temperature preparation method of indium tin oxide target material | |
| CN112110647B (en) | High-color-rendering-index fluorescent glass applied to laser illumination and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |