CN110803915A - Ceramic photocuring material and preparation method thereof - Google Patents

Ceramic photocuring material and preparation method thereof Download PDF

Info

Publication number
CN110803915A
CN110803915A CN201911249704.1A CN201911249704A CN110803915A CN 110803915 A CN110803915 A CN 110803915A CN 201911249704 A CN201911249704 A CN 201911249704A CN 110803915 A CN110803915 A CN 110803915A
Authority
CN
China
Prior art keywords
ceramic
parts
curing
mixing
photocuring
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN201911249704.1A
Other languages
Chinese (zh)
Inventor
徐坦
刘甫谭
赵方彪
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Ksitri Intelligent Manufacturing Technology Co Ltd
Original Assignee
Ksitri Intelligent Manufacturing Technology Co Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Ksitri Intelligent Manufacturing Technology Co Ltd filed Critical Ksitri Intelligent Manufacturing Technology Co Ltd
Priority to CN201911249704.1A priority Critical patent/CN110803915A/en
Publication of CN110803915A publication Critical patent/CN110803915A/en
Pending legal-status Critical Current

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y10/00—Processes of additive manufacturing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y70/00—Materials specially adapted for additive manufacturing
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—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
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
    • C04B35/63—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B using additives specially adapted for forming the products, e.g.. binder binders
    • C04B35/632—Organic additives
    • 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
    • C04B35/63—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B using additives specially adapted for forming the products, e.g.. binder binders
    • C04B35/632—Organic additives
    • C04B35/634—Polymers
    • C04B35/63404—Polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • 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
    • C04B35/63—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B using additives specially adapted for forming the products, e.g.. binder binders
    • C04B35/638—Removal 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
    • C04B2235/60—Aspects relating to the preparation, properties or mechanical treatment of green bodies or pre-forms
    • C04B2235/602—Making the green bodies or pre-forms by moulding
    • C04B2235/6026—Computer aided shaping, e.g. rapid prototyping
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
    • C04B2235/656—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes characterised by specific heating conditions during heat treatment
    • C04B2235/6562—Heating rate
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
    • C04B2235/656—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes characterised by specific heating conditions during heat treatment
    • C04B2235/6567—Treatment time

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Ceramic Engineering (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Compositions Of Oxide Ceramics (AREA)

Abstract

The invention provides a ceramic photocuring material. The invention avoids the defects generated in the paving process of the ceramic photocuring slurry by adding the rheological additive, improves the paving quality and the layer thickness precision of each layer, and improves the printing and curing quality of each layer. The purpose is to ensure the printing and forming performance of the green body and eliminate the influence of the printing and forming process on the final sintering performance. The invention optimizes the proportion of each component in the premixed liquid and controls the proportion of the curing components, thereby ensuring the strength of the green body, reducing the internal stress generated by curing and avoiding the generation of cracks due to the concentrated release of the internal stress in the degreasing and sintering process. The purpose is to form a reasonable degreasing temperature interval and obtain reliable sintering performance. In addition, the invention does not need to carry out surface modification treatment on the ceramic powder, optimizes the preparation process and is beneficial to industrial production. The aim is to exclude the influence of the slurry properties on the final sintering properties.

Description

Ceramic photocuring material and preparation method thereof
Technical Field
The invention belongs to the technical field of ceramic materials, and particularly relates to a ceramic photocuring material and a preparation method thereof.
Background
The ceramic material has the advantages of high hardness, high strength, wear resistance, high temperature resistance, oxidation resistance, corrosion resistance and the like, and has a wide application range. Ceramic forming technologies such as dry pressing, injection, die casting, gel casting and the like rely on molds and play an important role in the field of standardized production and manufacturing, but due to the characteristics of high ceramic hardness, high brittleness and the like, ceramic parts with high processing and forming precision and complex structures are very difficult to process, and the requirements of personalized ceramic manufacturing are difficult to meet. The additive manufacturing technology manufactures products in a layer-by-layer overlapping mode according to the model data file, so that the limitation of a mold is eliminated, the design is free, the manufacturing is personalized, and the additive manufacturing technology has great potential in the field of high-performance ceramic manufacturing. Among a plurality of ceramic additive manufacturing technologies, the ceramic photocuring forming technology gradually stands out due to high surface precision and the capability of preparing ceramic products with high sintering density and strength.
The ceramic photocuring molding technology is that a ceramic blank is formed by laser curing a photosensitive resin material mixed with ceramic powder, and the ceramic blank is degreased and sintered to obtain a ceramic product with the performance meeting the requirement. The process mainly comprises three links of material preparation, printing and molding and degreasing and sintering. At present, many equipment suppliers can provide materials suitable for printing, and the dispersibility and stability of the materials are basically solved, but most of the materials have poor printing sintering performance, and the fundamental reason is that unreasonable places exist in material resin systems. In the current study, there are mainly two resin systems: solvent-borne resin systems and aqueous resin systems. In the solvent-based resin system, the generated stress is large due to high curing degree, and the sample is easy to crack after degreasing and sintering. In the case of the aqueous resin system, although a slurry having a low viscosity and a high solid content can be prepared, the green curing strength is poor and the deformation is likely to occur. Although the problems of strength, cracks and the like can be improved to a certain extent by adjusting the printing process parameters or the degreasing sintering process, the problems cannot be fundamentally solved.
Patent CN 106673646 a provides a method for preparing zirconia ceramic by 3D printing based on photocuring molding, which is used for solving the technical defects that zirconia ceramic molding has a large dependence on a mold and cannot prepare a complex precise structure.
The patent CN 106810215A prepares ceramic slurry with high solid content and low viscosity, and preliminarily researches the ceramic photocuring forming process.
Patent CN108083817A obtains photocuring 3D printing ceramic slurry with excellent solid content, viscosity and anti-settling property by controlling the proportion of each component with a shovel, thereby avoiding the phenomenon of poor performance caused by settling.
The patent CN109437893A adopts a polymer dispersant to solve the defects of easy delamination, nonuniform dispersion, incapability of long-term storage and the like in slurry products obtained by the traditional ceramic slurry preparation process, and provides a photocuring zirconia ceramic slurry with high solid content and low viscosity and a preparation method thereof.
However, the above-mentioned techniques mainly focus on the solid content, viscosity, dispersion stability, etc. of the slurry, and mainly solve the problem of the compatibility of the ceramic slurry with the ceramic 3D printer. The problem that the ceramic material cannot be molded is solved, and the problems of degreasing and sintering performances such as strength, deformation, cracks and the like after the ceramic 3D printing and molding are not solved from the aspect of material design. In addition, in the prior art, the surface modification treatment is mostly carried out on the ceramic powder before the slurry preparation, so that the preparation process flow is increased, the preparation efficiency of the ceramic slurry is reduced, and the industrial production cannot be realized.
Disclosure of Invention
In view of this, the technical problem to be solved by the present invention is to provide a ceramic photocuring material and a preparation method thereof, and the ceramic photocuring material provided by the present invention does not need to perform surface modification on ceramic powder, so that matching between the material and a 3D printer is ensured, and degreasing and sintering performances of the material after 3D printing and forming are also ensured.
The invention provides a ceramic photocuring material which comprises the following components in percentage by mass (60-90): (10-40) preparing a ceramic powder and a premixed liquid;
the premix comprises the following raw materials in parts by mass:
50-70 parts of photosensitive resin, 0-30 parts of solvent, 1-20 parts of dispersing agent, 0-10 parts of rheological additive, 1-10 parts of defoaming agent, 0.5-3 parts of photoinitiator, 0-10 parts of curing additive and 0-2 parts of curing inhibitor.
Preferably, the ceramic powder is one or more of zirconia, yttria-stabilized zirconia, alumina, zirconia toughened alumina, silica, silicon nitride, silicon carbide, β -calcium phosphate, hydroxyapatite and bioglass, and the particle size of the ceramic powder is D50 and is 0.05-1 μm.
Preferably, the photosensitive resin is one or more of hydroxyethyl methacrylate, 1, 6-hexanediol diacrylate, tripropylene glycol diacrylate, polyethylene glycol diacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol triacrylate, ethoxylated pentaerythritol triacrylate, pentaerythritol tetraacrylate, ethoxylated pentaerythritol tetraacrylate, pentaerythritol tris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptopropionate), acrylamide, and N, N' -methyleneacrylamide.
Preferably, the solvent is selected from one or more of deionized water, ethanol, polyethylene glycol 200, polyethylene glycol 300, polyethylene glycol 400, polyethylene glycol 600 and tetrahydrofuran;
the dispersant is selected from ammonium polyacrylate, polyvinylpyrrolidone, sodium alginate, SOLSPERSE24000, SOLSPERSE3000, MALIALIMTMAKM-0531、MALIALIMTMC-20931、MALIALIMTMSC-1015F、MALIALIMTMOne or more of SC-0708A, BYK-108, BYK-109 and BYK-111;
the rheological additive is selected from ethyl acetoacetate, diethylene glycol diethyl ether, ethylene glycol butyl ester, dibutyl oxalate, dibutyl phthalate, 3-glycidyl ether oxypropyltrimethoxysilane and 3- (methacryloyloxy) propyltrimethoxysilane; one or more of BYK-356 and BYK-361N;
the defoaming agent is selected from one or more of N-octanol, polydimethylsiloxane and Foamex N.
Preferably, the photoinitiator is one or more of PI 2959, PI1173, PI 184, PI 819, PI TPO, benzophenone, benzoin ether compounds and thioxanthone compounds;
the curing auxiliary agent is at least one of Rad2100, Rad2200, Rad2300, Rad2500, Rad2600 and Rad 2700;
the curing inhibitor is one of p-dihydroxybenzene (HQ), hydroxyanisole (MEHQ), 2-tert-butylhydroquinone (MTBHHQ), 2, 5-di-tert-butylhydroquinone (2, 5-DTBHQ) and 2,2,6, 6-tetramethyl-4-hydroxypiperidine nitroxide free radical (polymerization inhibitor-701).
Preferably, the solid content of the ceramic photocuring material is 40-60 vol%, and the viscosity is 1000-5000 cP.
Preferably, the ceramic light-cured material is a slurry or a paste.
The invention also provides a preparation method of the ceramic photocuring material, which comprises the following steps:
A) mixing and stirring photosensitive resin, a solvent, a dispersing agent, a rheological aid, a defoaming agent, a curing aid and a curing inhibitor to obtain a mixture;
B) mixing and stirring ceramic powder and the mixture to obtain a ceramic photocuring material precursor;
C) adding a photoinitiator into the ceramic photocuring material precursor, and mixing and stirring to obtain the ceramic photocuring material precursor.
Preferably, in the step A), the mixing and stirring time is 0.5-2 h;
in the step B), the mixing and stirring time is 8-20 h;
in the step C), the mixing and stirring time is 1-4 h.
Compared with the prior art, the invention provides a ceramic photocuring material which comprises the following components in percentage by mass (60-90): (10-40) preparing a ceramic powder and a premixed liquid; the premix comprises the following raw materials in parts by mass: 50-70 parts of photosensitive resin, 0-30 parts of solvent, 1-20 parts of dispersing agent, 0-10 parts of rheological additive, 1-10 parts of defoaming agent, 0.5-3 parts of photoinitiator, 0-10 parts of curing additive and 0-2 parts of curing inhibitor. The invention optimizes the proportion of each component in the premixed liquid and controls the proportion of the curing components, thereby ensuring the strength of the green body, reducing the internal stress generated by curing and avoiding the generation of cracks due to the concentrated release of the internal stress in the degreasing and sintering process. The purpose is to form a reasonable degreasing temperature interval and obtain reliable sintering performance. In addition, the invention does not need to carry out surface modification treatment on the ceramic powder, optimizes the preparation process and is beneficial to industrial production. The aim is to exclude the influence of the slurry properties on the final sintering properties.
Drawings
FIG. 1 is a scanning electron micrograph of a cross section of a ceramic article prepared in example 3;
FIG. 2 is an optical photograph of the ceramic article obtained in comparative example 2;
FIG. 3 is an optical photograph of the ceramic article obtained in comparative example 2;
FIG. 4 is a scanning electron microscope image of the zirconia photocurable material prepared in comparative example 4 after curing and molding and before sintering.
Detailed Description
The invention provides a ceramic photocuring material which comprises the following components in percentage by mass (60-90): (10-40) preparing a ceramic powder and a premixed liquid;
the premix comprises the following raw materials in parts by mass:
50-70 parts of photosensitive resin, 0-30 parts of solvent, 1-20 parts of dispersing agent, 0-10 parts of rheological additive, 1-10 parts of defoaming agent, 0.5-3 parts of photoinitiator, 0-10 parts of curing additive and 0-2 parts of curing inhibitor.
The preparation raw materials of the ceramic photocuring material provided by the invention comprise the following components in percentage by mass (60-90): (10-40) a ceramic powder and a premix. In some embodiments of the invention, the mass ratio of the ceramic powder to the premixed liquid is (70-80): (20-30).
In the invention, the ceramic powder is one or more of zirconia, yttria-stabilized zirconia, alumina, zirconia-toughened alumina, silica, silicon nitride, silicon carbide, β -calcium phosphate, hydroxyapatite and bioglass, preferably one or more of alumina, zirconia, silicon nitride and silica, the particle size of the ceramic powder is D50, the particle size of the ceramic powder is 0.05-1 μm, preferably 0.1-0.9 μm, and more preferably 0.3-0.7 μm, and the sedimentation rate of ceramic particles is effectively controlled by selecting a proper ceramic particle size, so that the stability of ceramic slurry is improved.
The preparation raw materials of the ceramic light-cured material also comprise a premixed liquid, wherein the premixed liquid comprises the following raw materials in parts by mass:
50-70 parts of photosensitive resin, 0-30 parts of solvent, 1-20 parts of dispersing agent, 0-10 parts of rheological additive, 1-10 parts of defoaming agent, 0.5-3 parts of photoinitiator, 0-10 parts of curing additive and 0-2 parts of curing inhibitor.
Specifically, the premix comprises 50-70 parts of photosensitive resin, preferably 55-65 parts, and more preferably 58-62 parts. The photosensitive resin is selected from hydroxyethyl methacrylate, 1, 6-hexanediol diacrylate, tripropylene glycol diacrylate, polyethylene glycol diacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol triacrylate, ethoxylated pentaerythritol triacrylate, pentaerythritol tetraacrylate, ethoxylated pentaerythritol tetraacrylate, pentaerythritol tris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptopropionate), acrylamide and N, one or more of N' -methylene acrylamide, preferably one or more of trimethylolpropane triacrylate, pentaerythritol tris (3-mercaptopropionate), ethoxylated pentaerythritol tetraacrylate, tripropylene glycol diacrylate, pentaerythritol tetraacrylate and polyethylene glycol diacrylate.
The premix also comprises 0-30 parts of solvent, preferably 5-25 parts, and further preferably 10-20 parts. The solvent is selected from one or more of deionized water, ethanol, polyethylene glycol 200, polyethylene glycol 300, polyethylene glycol 400, polyethylene glycol 600 and tetrahydrofuran, and preferably selected from one or more of polyethylene glycol 200, PEG300, tetrahydrofuran and deionized water.
The premix also comprises 1-20 parts of a dispersant, preferably 5-15 parts, and further preferably 8-12 parts. The dispersant is selected from ammonium polyacrylate, polyvinylpyrrolidone,Sodium alginate, SOLSPERSE24000, SOLSPERSE3000, MALIALIMTMAKM-0531、MALIALIMTMC-20931、MALIALIMTMSC-1015F、MALIALIMTMOne or more of SC-0708A, BYK-108, BYK-109 and BYK-111, preferably MALIALIMTMAKM-0708A、BYK-111、SOLSPERSE24000、MALIALIMTMOne or more of AKM-0531, polyvinylpyrrolidone;
according to the invention, proper dispersing agents are selected for different powder bodies, the photocuring ceramic slurry with high solid content and uniform dispersion is prepared, and meanwhile, the viscosity of the ceramic slurry is ensured to be suitable for a ceramic photocuring printer.
The premix also comprises 0-10 parts of a rheological additive, preferably 1-9 parts, and further preferably 3-7 parts. The rheological additive is selected from ethyl acetoacetate, diethylene glycol diethyl ether, ethylene glycol butyl ester, dibutyl oxalate, dibutyl phthalate, 3-glycidyl ether oxypropyltrimethoxysilane and 3- (methacryloyloxy) propyltrimethoxysilane; BYK-356 and BYK-361N, preferably dibutyl phthalate, ethyl acetoacetate, BYK356 and 3-glycidyloxypropyltrimethoxysilane.
The premix also comprises 1-10 parts of a defoaming agent, preferably 3-8 parts, and further preferably 4-7 parts. The defoaming agent is selected from one or more of N-octanol, polydimethylsiloxane and Foamex N, and is preferably Foamex N, polydimethylsiloxane or N-octanol.
The premix also comprises 0.5-3 parts of a photoinitiator, preferably 1.0-2.5 parts, and further preferably 1.5-2.0 parts. The photoinitiator is one or more of PI 2959, PI1173, PI 184, PI 819, PI TPO, benzophenone, benzoin ether and thioxanthone, preferably one or more of PI 184, PI 819, TPO, benzophenone and PI 2959
The premix also comprises 0-10 parts of a curing assistant, preferably 1-9 parts, and further preferably 3-7 parts. The curing aid is at least one of Rad2100, Rad2200, Rad2300, Rad2500, Rad2600 and Rad2700, preferably Rad2300, Rad2100, Rad2600 and Rad 2500.
The premix also comprises 0-2 parts of a curing inhibitor, preferably 0.5-1.5 parts. The curing inhibitor is one of p-dihydroxybenzene (HQ), hydroxyanisole (MEHQ), 2-tert-butylhydroquinone (MTBHHQ), 2, 5-di-tert-butylhydroquinone (2, 5-DTBHQ) and 2,2,6, 6-tetramethyl-4-hydroxypiperidine nitroxide free radical (polymerization inhibitor-701), and preferably MEHQ and MTBHQ.
The solid content of the ceramic photocuring material is 40-60 vol%, preferably 45-55 vol%, the vol% is volume percentage, and the viscosity is between 1000-5000 cP, preferably 2000-4000 cP, and further preferably 2500-3500 cP.
The ceramic light-cured material is slurry or paste.
The invention also provides a preparation method of the ceramic photocuring material, which comprises the following steps:
A) mixing and stirring photosensitive resin, a solvent, a dispersing agent, a rheological aid, a defoaming agent, a curing aid and a curing inhibitor to obtain a mixture;
in the present invention, the mixing and stirring manner is not particularly limited, and preferably, the mixing and stirring manner is magnetic stirring, ball milling or dynamic mixer mixing and stirring at a certain rotation speed. The mixing and stirring time is 0.5-2 h;
B) mixing and stirring ceramic powder and the mixture to obtain a ceramic photocuring material precursor;
in the present invention, the mixing and stirring method is not particularly limited, and a ball mill or a vacuum dynamic mixer is preferably used for mixing and stirring. The mixing and stirring time is 8-20 h;
C) and adding a photoinitiator into the ceramic photocuring material precursor, and mixing and stirring for 1-4 h.
And after the mixture is mixed, taking out the mixture, bottling and vacuumizing to obtain the ceramic photocuring material.
The ceramic photocuring mainly comprises 3 links: preparing slurry, printing and molding, degreasing and sintering. The invention considers the performance of each flow link from the aspect of the material prepared by the slurry, thereby solving the problems of final sintering strength, cracks and deformation and obtaining reliable sintering performance.
The invention avoids the defects generated in the paving process of the ceramic photocuring slurry by adding the rheological additive, improves the paving quality and the layer thickness precision of each layer, and improves the printing and curing quality of each layer. The purpose is to ensure the printing and forming performance of the green body and eliminate the influence of the printing and forming process on the final sintering performance. The invention optimizes the proportion of each component in the premixed liquid and controls the proportion of the curing components, thereby ensuring the strength of the green body, reducing the internal stress generated by curing and avoiding the generation of cracks due to the concentrated release of the internal stress in the degreasing and sintering process. The purpose is to form a reasonable degreasing temperature interval and obtain reliable sintering performance. In addition, the invention does not need to carry out surface modification treatment on the ceramic powder, optimizes the preparation process and is beneficial to industrial production. The aim is to exclude the influence of the slurry properties on the final sintering properties.
For further understanding of the present invention, the following examples are provided to illustrate the ceramic photocurable material and the preparation method thereof, and the scope of the present invention is not limited by the following examples.
Example 1
(1) Preparing a mixed solution: mixing 45 wt% trimethylolpropane triacrylate, 5 wt% pentaerythritol tris (3-mercaptopropionate), 20 wt% polyethylene glycol 200, and 20 wt% MALIALIIMTMAKM-0708A, 3 wt% of dibutyl phthalate, 3 wt% of Foamex N, 3 wt% of Rad2300 and 0.5 wt% of MEHQ, and mixing by magnetic stirring at 800RPM for 0.5h to obtain a mixed solution.
(2) Mixing the ceramic-mixed liquid: weighing 1000g of mixed liquor prepared in the step (1), pouring the mixed liquor into a material cylinder of a vacuum dispersion stirring mixer, and adding 9000g of particles with the particle size D in portions50After the alumina ceramic powder with the particle size of 0.6 mu m is obtained, the mixture is dispersed and stirred at a high speed for 8 hours to obtain a ceramic-mixed liquid mixture.
(3) Preparing a ceramic photocuring material: and adding 5g of photoinitiator PI 184 into the mixture, stirring at a medium speed for 1h, and vacuumizing to obtain the alumina ceramic photocuring material.
The viscosity of the alumina light-cured material prepared in this example was 2500 cP.
(4) The ceramic product obtained after the slurry is solidified, formed, degreased and sintered has average three-point bending strength of 375MPa and density of 3.85g/cm3. Wherein, the curing and molding equipment: the bolimei ceramic 3D printer CSL 100. Molding parameters are as follows: the thickness of the layer is 0.025mm, the laser power is 0.4W, the scanning speed is 3000mm/s, the scanning interval is 0.025mm, and the scanning times are 1. Degreasing and sintering processes: heating to 400 ℃ at 25 ℃, wherein the heating rate is 0.5 ℃/min; then raising the temperature from 400 ℃ to 550 ℃, wherein the heating rate is 0.1 ℃/min. Then raising the temperature from 550 ℃ to 1650 ℃ at the speed of 5 ℃/min and preserving the temperature for 2 h.
Example 2
(1) Preparing a mixed solution: 70 wt% of 1, 6-hexanediol diacrylate, 10 wt% of BYK111, 10 wt% of ethyl acetoacetate and 7 wt% of polydimethylsiloxane were mixed by a magnetic stirrer at the rotating speed of 800RPM for 0.5h to prepare a mixed solution.
(2) Mixing the ceramic-mixed liquid: weighing 100g of mixed liquor prepared in the step (1), pouring the mixed liquor into a ball mill, and adding 400g of particles with the particle size D in portions50After 1 micron silicon nitride ceramic powder is ground for 20 hours, the ceramic-mixed liquid mixture is prepared.
(3) Preparing a ceramic photocuring material: and adding 1g of photoinitiator PI 184 and 2g of photoinitiator PI 819 into the mixture, ball-milling for 2 hours, taking out, bottling and vacuumizing to obtain the silicon nitride ceramic photocuring material.
The viscosity of the silicon nitride photocuring material prepared in the embodiment is 1300 cP.
(4) The ceramic product obtained after the slurry is solidified, formed, degreased and sintered has the average three-point bending strength of 514MPa and the density of 3.10g/cm3。
Curing and molding equipment: the bolimei ceramic 3D printer CSL 100. Molding parameters are as follows: the thickness of the layer is 0.025mm, the laser power is 0.4W, the scanning speed is 3000mm/s, the scanning interval is 0.025mm, and the scanning times are 1.
Degreasing and sintering processes: heating to 400 ℃ at 25 ℃, wherein the heating rate is 0.5 ℃/min; then raising the temperature from 400 ℃ to 550 ℃, wherein the heating rate is 0.1 ℃/min. Then raising the temperature from 550 ℃ to 1050 ℃ at the speed of 5 ℃/min and preserving the temperature for 1h, then raising the temperature from 550 ℃ to 1450 ℃ at the speed of 5 ℃/min and preserving the temperature for 1h, and then raising the temperature from 1450 ℃ to 1800 ℃ at the speed of 5 ℃/min and preserving the temperature for 2 h.
Example 3
(1) Preparing a mixed solution: 54 wt% of 1, 6-hexanediol diacrylate, 6 wt% of ethoxylated pentaerythritol tetraacrylate, 10 wt% of PEG300, 10 wt% of SOLSPERSE24000, 5 wt% of BYK356, 5% of Foamex N, 4 wt% of Rad2100, 4 wt% of Rad2600, and 1 wt% of MTBHQ were mixed by a magnetic stirrer at 800RPM for 2 hours to prepare a mixed solution.
(2) Mixing the ceramic-mixed liquid: weighing 100g of mixed liquor prepared in the step (1), pouring the mixed liquor into a ball mill, and adding 500g of particles with the particle size D in portions50After the zirconia ceramic powder with the particle size of 0.38 mu m is ground by ball milling for 15h, the ceramic-mixed liquid mixture is prepared.
(3) Preparing a ceramic photocuring material: and adding 1g of TPO into the mixture, ball-milling for 3h, taking out, bottling and vacuumizing to obtain the zirconia ceramic photocuring material.
The viscosity of the zirconia photocurable material prepared in this example was 2000 cP.
(4) The ceramic product obtained after the slurry is solidified, formed, degreased and sintered has average three-point bending strength of 850MPa and density of 5.96g/cm3。
Wherein, the curing and molding equipment: the bolimei ceramic 3D printer CSL 100. Molding parameters are as follows: the thickness of the layer is 0.025mm, the laser power is 0.4W, the scanning speed is 3000mm/s, the scanning interval is 0.025mm, and the scanning times are 1.
Degreasing and sintering processes: heating to 400 ℃ at 25 ℃, wherein the heating rate is 0.5 ℃/min; then raising the temperature from 400 ℃ to 550 ℃, wherein the heating rate is 0.1 ℃/min. Then raising the temperature from 550 ℃ to 1200 ℃ at the speed of 5 ℃/min and preserving the heat for 1h, and then raising the temperature from 1200 ℃ to 1500 ℃ at the speed of 5 ℃/min and preserving the heat for 2h
Example 4
(1) Preparing a mixed solution: 54 wt% of tripropylene glycol diacrylate, 6 wt% of pentaerythritol tetraacrylate, 15 wt% of tetrahydrofuran and 10 wt% of MALIALIIMTMAKM-0531, 5 wt% 3-glycidoxypropyltrimethoxysilane, 5 wt% Foamex N, 2 wt% Rad2300, 2 wt% Rad2500, mixed by magnetic stirrer at 800RPMAnd (5) preparing a mixed solution after 1 hour.
(2) Mixing the ceramic-mixed liquid: weighing 100g of mixed liquor prepared in the step (1), pouring the mixed liquor into a ball mill, and adding 500g of particles with the particle size D500.38 μm zirconium oxide and 300g particle size D50After being made of 0.6 mu m of alumina ceramic powder, the mixture is ball milled for 20 hours to prepare the ceramic-mixed liquid mixture.
(3) Preparing a ceramic photocuring material: and adding 0.5g of photoinitiator PI 184 and 0.5g of benzophenone into the mixture, ball-milling for 4 hours, taking out, bottling and vacuumizing to obtain the zirconia toughened alumina ceramic photocuring material.
The viscosity of the zirconia toughened alumina photocuring material prepared in the embodiment is 2400 cP.
(4) The ceramic product obtained after the slurry is solidified, formed, degreased and sintered has an average three-point bending strength of 453MPa and a density of 4.89g/cm3。
Wherein, the curing and molding equipment: the bolimei ceramic 3D printer CSL 100.
Molding parameters are as follows: the thickness of the layer is 0.025mm, the laser power is 0.4W, the scanning speed is 3000mm/s, the scanning interval is 0.025mm, and the scanning times are 1.
Degreasing and sintering processes: heating to 400 ℃ at 25 ℃, wherein the heating rate is 0.5 ℃/min; then raising the temperature from 400 ℃ to 550 ℃, wherein the heating rate is 0.1 ℃/min. Then raising the temperature from 550 ℃ to 1200 ℃ at the speed of 5 ℃/min and preserving the temperature for 1h, and then raising the temperature from 1200 ℃ to 1600 ℃ at the speed of 5 ℃/min and preserving the temperature for 2 h.
Example 5
(1) Preparing a mixed solution: 62 wt% of polyethylene glycol diacrylate, 30 wt% of deionized water, 2 wt% of polyvinylpyrrolidone and 4% of n-octanol are magnetically stirred and mixed for 1 hour at the rotating speed of 800RPM to prepare a mixed solution.
(2) Mixing the ceramic-mixed liquid: weighing 100g of mixed liquor prepared in the step (1), pouring the mixed liquor into a ball mill, and adding 150g of particles with the particle size D50After 0.05 mu m of silicon oxide ceramic powder is ground for 20 hours, the mixture of ceramic and mixed liquid is prepared.
(3) Preparing a ceramic photocuring material: and adding 2g of PI 2959 into the mixture, ball-milling for 4h, taking out, bottling and vacuumizing to obtain the silicon oxide ceramic photocuring material.
The viscosity of the silicon oxide photocurable material prepared in this example was 2200 cP.
(4) The ceramic product obtained after the slurry is solidified, formed, degreased and sintered has average three-point bending strength of 160MPa and density of 2.11g/cm3.
Wherein, the curing and molding equipment: the bolimei ceramic 3D printer CSL 100.
Molding parameters are as follows: the thickness of the layer is 0.025mm, the laser power is 0.4W, the scanning speed is 3000mm/s, the scanning interval is 0.025mm, and the scanning times are 1.
Degreasing and sintering processes: heating to 400 ℃ at 25 ℃, wherein the heating rate is 0.5 ℃/min; then raising the temperature from 400 ℃ to 550 ℃, wherein the heating rate is 0.1 ℃/min. Then raising the temperature from 550 ℃ to 850 ℃ at the speed of 3 ℃/min and preserving the temperature for 1h, and then raising the temperature from 850 ℃ to 1200 ℃ at the speed of 5 ℃/min and preserving the temperature for 2 h.
Comparative example 1
The particle size D50 for the zirconium oxide used in step (2) of example 3 was 40nm, and the other steps were unchanged. As a result, a slurry cannot be prepared.
Comparative example 2
The ratio of the curing components in the premix in step (1) of example 3 was varied.
Preparing a mixed solution: 72 wt% 1, 6-hexanediol diacrylate and 8 wt% ethoxylated pentaerythritol tetraacrylate, 10 wt% SOLSPERSE24000, 5 wt% BYK356, 4 wt% Foamex N, were mixed by magnetic stirrer at 800RPM for 2h to make a mixed solution. .
The other preparation steps are unchanged.
The viscosity of the zirconia photocurable material prepared in this example was 1800 cP.
The ceramic product obtained after the slurry is solidified, formed, degreased and sintered has a large number of cracks on the surface and a layering phenomenon inside, and the three-point bending strength is measured to be 50 MPa.
Comparative example 3
The rheological aid and the rheology-specific aid in the mixed liquor of example 3 were removed or reduced.
Preparing a mixed solution: 66.6 wt% 1, 6-hexanediol diacrylate, 7.4 wt% ethoxylated pentaerythritol tetraacrylate, 5 wt% PEG300, 10 wt% SOLSPERSE24000, 5 wt% Foamex N, 4 wt% Rad2100, 1 wt% MTBHQ, mixed by a magnetic stirrer at 800RPM for 2h to produce a mixture.
The other preparation steps are unchanged.
The viscosity of the zirconia photocuring material prepared in the example was 1400 cP. The ceramic product obtained after the slurry is solidified, formed, degreased and sintered has the average three-point bending strength of 120MPa and cracks and pores appear inside.
The results of observation of the ceramic products obtained in example 3, comparative example 2 and comparative example 3 by using an optical microscope or an electron microscope are shown in fig. 1-4, fig. 1 is a scanning electron microscope image of the cross section of the ceramic product obtained in example 3, fig. 2 and 3 are optical photographs of the ceramic product obtained in comparative example 2, and fig. 4 is a scanning electron microscope image of the zirconia photocuring material obtained in comparative example 4 after curing and molding and before sintering.
As can be seen from the sintered section in FIG. 1, the zirconia photocuring slurry containing the rheological aid with a proper curing component proportion and a proper content is subjected to curing molding, degreasing and sintering, and the zirconia is sintered compactly without cracks, and finally has high density and high bending strength.
As can be seen from fig. 2 and 3, the excessive content of the curing component in the slurry causes a large amount of internal stress after curing and forming, and the internal stress is intensively released in the degreasing and sintering process to cause cracking on the surface of the sintered body and delamination inside the sintered body, thereby affecting the bending strength.
As can be seen from the electron microscope image of the green body cross section in FIG. 4, if there is no rheological additive in the slurry, the slurry will have uneven spreading or holes during the spreading process, and the curing results in cracks or a large number of holes on the green body cross section. Cracks and holes in the green body remain after degreasing and sintering, resulting in a lower bending strength.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.

Claims (9)

1. The ceramic photocuring material is characterized by comprising the following components in percentage by mass (60-90): (10-40) preparing a ceramic powder and a premixed liquid;
the premix comprises the following raw materials in parts by mass:
50-70 parts of photosensitive resin, 0-30 parts of solvent, 1-20 parts of dispersing agent, 0-10 parts of rheological additive, 1-10 parts of defoaming agent, 0.5-3 parts of photoinitiator, 0-10 parts of curing additive and 0-2 parts of curing inhibitor.
2. The ceramic photocuring material of claim 1, wherein the ceramic powder is one or more of zirconia, yttria-stabilized zirconia, alumina, zirconia toughened alumina, silica, silicon nitride, silicon carbide, β -calcium phosphate, hydroxyapatite and bioglass, and the particle size of the ceramic powder is D50 and is 0.05-1 μm.
3. The ceramic photocurable material according to claim 1, wherein the photosensitive resin is one or more of hydroxyethyl methacrylate, 1, 6-hexanediol diacrylate, tripropylene glycol diacrylate, polyethylene glycol diacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol triacrylate, ethoxylated pentaerythritol triacrylate, pentaerythritol tetraacrylate, ethoxylated pentaerythritol tetraacrylate, pentaerythritol tris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptopropionate), acrylamide and N, N' -methyleneacrylamide.
4. The ceramic photocurable material of claim 1, wherein the solvent is selected from one or more of deionized water, ethanol, polyethylene glycol 200, polyethylene glycol 300, polyethylene glycol 400, polyethylene glycol 600, and tetrahydrofuran;
the dispersant is selected from ammonium polyacrylate, polyvinylpyrrolidone, sodium alginate, SOLSPERSE24000, SOLSPERSE3000, and MALIALIMTMAKM-0531、MALIALIMTMC-20931、MALIALIMTMSC-1015F、MALIALIMTMOne or more of SC-0708A, BYK-108, BYK-109 and BYK-111;
the rheological additive is selected from ethyl acetoacetate, diethylene glycol diethyl ether, ethylene glycol butyl ester, dibutyl oxalate, dibutyl phthalate, 3-glycidyl ether oxypropyltrimethoxysilane and 3- (methacryloyloxy) propyltrimethoxysilane; one or more of BYK-356 and BYK-361N;
the defoaming agent is selected from one or more of N-octanol, polydimethylsiloxane and Foamex N.
5. The ceramic photocurable material according to claim 1, wherein the photoinitiator is one or more of PI 2959, PI1173, PI 184, PI 819, PI TPO, benzophenone, benzoin ethers, thioxanthones;
the curing auxiliary agent is at least one of Rad2100, Rad2200, Rad2300, Rad2500, Rad2600 and Rad 2700;
the curing inhibitor is one of p-dihydroxybenzene (HQ), hydroxyanisole (MEHQ), 2-tert-butylhydroquinone (MTBHHQ), 2, 5-di-tert-butylhydroquinone (2, 5-DTBHQ) and 2,2,6, 6-tetramethyl-4-hydroxypiperidine nitroxide free radical (polymerization inhibitor-701).
6. The ceramic photocurable material of claim 1, wherein the solid content of the ceramic photocurable material is 40-60 vol.% and the viscosity is between 1000-5000 cP.
7. The ceramic photocurable material of claim 1 wherein the ceramic photocurable material is a paste or paste.
8. A method for preparing the ceramic photocuring material as set forth in any one of claims 1 to 7, which comprises the following steps:
A) mixing and stirring photosensitive resin, a solvent, a dispersing agent, a rheological aid, a defoaming agent, a curing aid and a curing inhibitor to obtain a mixture;
B) mixing and stirring ceramic powder and the mixture to obtain a ceramic photocuring material precursor;
C) adding a photoinitiator into the ceramic photocuring material precursor, and mixing and stirring to obtain the ceramic photocuring material precursor.
9. The preparation method according to claim 8, wherein in the step A), the mixing and stirring time is 0.5-2 h;
in the step B), the mixing and stirring time is 8-20 h;
in the step C), the mixing and stirring time is 1-4 h.
CN201911249704.1A 2019-12-09 2019-12-09 Ceramic photocuring material and preparation method thereof Pending CN110803915A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201911249704.1A CN110803915A (en) 2019-12-09 2019-12-09 Ceramic photocuring material and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201911249704.1A CN110803915A (en) 2019-12-09 2019-12-09 Ceramic photocuring material and preparation method thereof

Publications (1)

Publication Number Publication Date
CN110803915A true CN110803915A (en) 2020-02-18

Family

ID=69492768

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201911249704.1A Pending CN110803915A (en) 2019-12-09 2019-12-09 Ceramic photocuring material and preparation method thereof

Country Status (1)

Country Link
CN (1) CN110803915A (en)

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112521162A (en) * 2020-08-13 2021-03-19 江苏薄荷新材料科技有限公司 Preparation process of ceramic slurry for ceramic 3D printing
CN112851339A (en) * 2021-01-29 2021-05-28 华南师范大学 Ceramic slurry for photocuring 3D printing and preparation method of ceramic device thereof
CN113061028A (en) * 2021-05-15 2021-07-02 江苏京科智镕新材料科技有限公司 Preparation method of 3Y-TZP ceramic paste and preparation process of full-mouth planting and fixing prosthesis
CN113208750A (en) * 2021-05-15 2021-08-06 江苏京科智镕新材料科技有限公司 Light-transmission gradual-change dental crown based on stereolithography 3D printing and preparation method
CN113336542A (en) * 2021-05-15 2021-09-03 江苏京科智镕新材料科技有限公司 High-transmittance zirconia ceramic formula, paste preparation method and dental crown preparation method
CN113429210A (en) * 2021-07-16 2021-09-24 嘉兴饶稷科技有限公司 Silicon carbide ceramic slurry with high photosensitive activity and preparation method thereof
CN114455946A (en) * 2022-01-24 2022-05-10 深圳协同创新高科技发展有限公司 Zirconia ceramic powder for photocuring 3D printing and preparation method thereof
CN115703681A (en) * 2021-08-06 2023-02-17 苏州大学 High-yield-stress ceramic stereolithography 3D printing material and preparation method and application thereof
CN116653285A (en) * 2023-07-26 2023-08-29 中南大学 Multi-material additive manufacturing device and method for regulating rheological property of photosensitive slurry
CN116947503A (en) * 2023-07-17 2023-10-27 合润达源(湖北)科技有限公司 Water-based photo-thermal double-effect cured ceramic slurry and preparation method and application thereof

Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106673627A (en) * 2017-01-20 2017-05-17 广东工业大学 Method for preparing toughened aluminum oxide ceramic based on stereo lithography appearance namely 3D printing
CN107540352A (en) * 2017-09-20 2018-01-05 吴江中瑞机电科技有限公司 The preparation and application of 3D printing aluminum oxide toughening ceramic slurry
CN108083777A (en) * 2017-11-10 2018-05-29 山东工业陶瓷研究设计院有限公司 A kind of preparation method of photocuring 3D printing Al-base ceramic slurry and ceramic core
CN108218440A (en) * 2017-12-29 2018-06-29 深圳长朗智能科技有限公司 Light-cured resin based composite ceramic material and ceramic idiosome degreasing method
CN108726997A (en) * 2018-06-07 2018-11-02 山东大学 A kind of aluminium oxide high solid loading light sensitive ceramics 3D printing creme and preparation method thereof
CN109400177A (en) * 2018-10-30 2019-03-01 西安点云生物科技有限公司 For the ceramic material of 3D Stereolithography printing and the preparation method of ceramic objects
CN109437893A (en) * 2019-01-09 2019-03-08 北京理工大学 A kind of high solids content/low viscosity photocuring zirconia ceramics slurry and preparation method thereof
CN109851327A (en) * 2018-12-20 2019-06-07 山东大学 A kind of compound photosensitive creme of silicon carbide/aluminium oxide ceramics and preparation method thereof towards SLA-3D printing
CN110028311A (en) * 2019-04-11 2019-07-19 山东工业陶瓷研究设计院有限公司 A kind of resin combination and ceramic slurry
CN110128116A (en) * 2019-05-30 2019-08-16 西安增材制造国家研究院有限公司 A kind of photocuring ceramic slurry and preparation method thereof
CN110511022A (en) * 2019-09-30 2019-11-29 西安增材制造国家研究院有限公司 A kind of high solid loading zirconia ceramics creme and preparation method, and structural member and preparation method based on it

Patent Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106673627A (en) * 2017-01-20 2017-05-17 广东工业大学 Method for preparing toughened aluminum oxide ceramic based on stereo lithography appearance namely 3D printing
CN107540352A (en) * 2017-09-20 2018-01-05 吴江中瑞机电科技有限公司 The preparation and application of 3D printing aluminum oxide toughening ceramic slurry
CN108083777A (en) * 2017-11-10 2018-05-29 山东工业陶瓷研究设计院有限公司 A kind of preparation method of photocuring 3D printing Al-base ceramic slurry and ceramic core
CN108218440A (en) * 2017-12-29 2018-06-29 深圳长朗智能科技有限公司 Light-cured resin based composite ceramic material and ceramic idiosome degreasing method
CN108726997A (en) * 2018-06-07 2018-11-02 山东大学 A kind of aluminium oxide high solid loading light sensitive ceramics 3D printing creme and preparation method thereof
CN109400177A (en) * 2018-10-30 2019-03-01 西安点云生物科技有限公司 For the ceramic material of 3D Stereolithography printing and the preparation method of ceramic objects
CN109851327A (en) * 2018-12-20 2019-06-07 山东大学 A kind of compound photosensitive creme of silicon carbide/aluminium oxide ceramics and preparation method thereof towards SLA-3D printing
CN109437893A (en) * 2019-01-09 2019-03-08 北京理工大学 A kind of high solids content/low viscosity photocuring zirconia ceramics slurry and preparation method thereof
CN110028311A (en) * 2019-04-11 2019-07-19 山东工业陶瓷研究设计院有限公司 A kind of resin combination and ceramic slurry
CN110128116A (en) * 2019-05-30 2019-08-16 西安增材制造国家研究院有限公司 A kind of photocuring ceramic slurry and preparation method thereof
CN110511022A (en) * 2019-09-30 2019-11-29 西安增材制造国家研究院有限公司 A kind of high solid loading zirconia ceramics creme and preparation method, and structural member and preparation method based on it

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
周张健编著: "《无机非金属材料工艺学》", 31 January 2010, 北京：中国轻工业出版社 *
李涤尘等: "《先进燃气轮机设计制造基础专著系列 高温透平叶片增材制造技术》", 31 October 2016, 西安：西安交通大学出版社 *
盖国胜主编: "《超细粉碎分级技术 理论研究 工艺设计 生产应用》", 31 March 2000, 北京：中国轻工业出版社 *

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112521162A (en) * 2020-08-13 2021-03-19 江苏薄荷新材料科技有限公司 Preparation process of ceramic slurry for ceramic 3D printing
CN112851339A (en) * 2021-01-29 2021-05-28 华南师范大学 Ceramic slurry for photocuring 3D printing and preparation method of ceramic device thereof
CN113061028A (en) * 2021-05-15 2021-07-02 江苏京科智镕新材料科技有限公司 Preparation method of 3Y-TZP ceramic paste and preparation process of full-mouth planting and fixing prosthesis
CN113208750A (en) * 2021-05-15 2021-08-06 江苏京科智镕新材料科技有限公司 Light-transmission gradual-change dental crown based on stereolithography 3D printing and preparation method
CN113336542A (en) * 2021-05-15 2021-09-03 江苏京科智镕新材料科技有限公司 High-transmittance zirconia ceramic formula, paste preparation method and dental crown preparation method
CN113429210A (en) * 2021-07-16 2021-09-24 嘉兴饶稷科技有限公司 Silicon carbide ceramic slurry with high photosensitive activity and preparation method thereof
CN115703681A (en) * 2021-08-06 2023-02-17 苏州大学 High-yield-stress ceramic stereolithography 3D printing material and preparation method and application thereof
CN114455946A (en) * 2022-01-24 2022-05-10 深圳协同创新高科技发展有限公司 Zirconia ceramic powder for photocuring 3D printing and preparation method thereof
CN116947503A (en) * 2023-07-17 2023-10-27 合润达源(湖北)科技有限公司 Water-based photo-thermal double-effect cured ceramic slurry and preparation method and application thereof
CN116653285A (en) * 2023-07-26 2023-08-29 中南大学 Multi-material additive manufacturing device and method for regulating rheological property of photosensitive slurry
CN116653285B (en) * 2023-07-26 2023-11-07 中南大学 Multi-material additive manufacturing device and method for regulating rheological property of photosensitive slurry

Similar Documents

Publication Publication Date Title
CN110803915A (en) Ceramic photocuring material and preparation method thereof
CN108275979B (en) Ceramic material for photocuring 3D printing, ceramic part and preparation method of ceramic part
CN107032797B (en) Ceramic-based interlayer composite material based on photocuring molding and preparation method thereof
CN108218440B (en) Light-cured resin-based ceramic composite material and ceramic blank degreasing method
CN113754430B (en) Graded zirconia paste for 3D printing and preparation method and application thereof
Zou et al. Improving cure performance of Si3N4 suspension with a high refractive index resin for stereolithography-based additive manufacturing
CN108249930B (en) Light-cured resin-based ceramic composite material for providing smooth contour and blank degreasing method
CN102351526B (en) Method for preparing AZO target materials by adopting gel injection molding forming
CN112390626A (en) Preparation of ceramic slurry for 3D printing and 3D printing photocuring forming method thereof
CN105834351B (en) A kind of resistant to elevated temperatures mold material
CN112537948A (en) Photocuring 3D printing manufacturing method of alumina-based ceramic core
CN114853450A (en) Photocuring 3D printing alumina-based ceramic core and preparation method thereof
CN110683842B (en) Biological ceramic slurry for high-performance DLP printing and preparation method thereof
CN118026692B (en) Preparation method and application of silicon carbide ceramic slurry for photo-curing 3D printing
CN114524676B (en) Preparation method of photo-cured silicon nitride ceramic slurry and silicon nitride ceramic
CN114149253A (en) Photocuring 3D printing low-sintering-shrinkage ceramic core and preparation method thereof
CN115872724B (en) Photo-curing 3D printing high-performance eutectic composition ceramic material with complex structure and preparation method thereof
CN101857443B (en) Method for preparing large-sized ceramic grinding balls
WO2021002040A1 (en) Powder for deposition modeling, slurry for deposition modeling, three-dimensional deposition model, sintered body, method for producing slurry for deposition modeling, deposition modeling method and sintering method
CN111302785A (en) High-performance microwave dielectric ceramic and photocuring manufacturing method thereof
CN111014572A (en) White corundum paint for water-based large steel castings and preparation method thereof
CN115180965B (en) Preparation method of polycarbosilane reinforced alumina ceramic slurry and 3D printing photocuring forming process
CN113563055A (en) High-precision ceramic 3D printing paste and preparation method thereof
CN112171848A (en) Photocuring silicon carbide ceramic slurry and preparation method and application thereof
CN116199505B (en) Lamellar interface reinforced photocuring 3D printing ceramic core and preparation method thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination