CN113754430B - Graded zirconia paste for 3D printing and preparation method and application thereof - Google Patents
Graded zirconia paste for 3D printing and preparation method and application thereof Download PDFInfo
- Publication number
- CN113754430B CN113754430B CN202110894241.5A CN202110894241A CN113754430B CN 113754430 B CN113754430 B CN 113754430B CN 202110894241 A CN202110894241 A CN 202110894241A CN 113754430 B CN113754430 B CN 113754430B
- Authority
- CN
- China
- Prior art keywords
- powder
- zirconia
- graded
- mass
- percent
- 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
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
- C04B35/48—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on zirconium or hafnium oxides, zirconates, zircon or hafnates
-
- 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
- C04B35/622—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
- C04B35/62605—Treating the starting powders individually or as mixtures
- C04B35/6261—Milling
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
- C04B35/62605—Treating the starting powders individually or as mixtures
- C04B35/62625—Wet mixtures
-
- 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
- C04B2235/3225—Yttrium oxide 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
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/50—Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
- C04B2235/54—Particle size related information
- C04B2235/5418—Particle size related information expressed by the size of the particles or aggregates thereof
- C04B2235/5436—Particle size related information expressed by the size of the particles or aggregates thereof micrometer sized, i.e. from 1 to 100 micron
-
- 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
- C04B2235/50—Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
- C04B2235/54—Particle size related information
- C04B2235/5418—Particle size related information expressed by the size of the particles or aggregates thereof
- C04B2235/5445—Particle size related information expressed by the size of the particles or aggregates thereof submicron sized, i.e. from 0,1 to 1 micron
-
- 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
- C04B2235/50—Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
- C04B2235/54—Particle size related information
- C04B2235/5418—Particle size related information expressed by the size of the particles or aggregates thereof
- C04B2235/5454—Particle size related information expressed by the size of the particles or aggregates thereof nanometer sized, i.e. below 100 nm
-
- 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
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Composite Materials (AREA)
- Civil Engineering (AREA)
- Compositions Of Oxide Ceramics (AREA)
Abstract
A graded zirconia paste for 3D printing and a preparation method and application thereof are disclosed, wherein micron zirconia powder and nanometer zirconia powder are uniformly mixed to prepare graded zirconia powder, and the graded zirconia powder, yttrium oxide and aluminum oxide are uniformly mixed; then mixing photosensitive resin and photoinitiator to prepare resin solution; then adding dispersant powder and grinding balls into a ball milling tank, adding the graded zirconia mixed powder, dispersant solid powder and liquid dispersant KOS110 into a resin solution, and carrying out ball milling and defoaming to obtain micron-sized graded zirconia ceramic paste with high solid content; adding the micron-sized graded zirconia ceramic paste with high solid content into a ceramic photocuring printer for printing, taking out after printing is finished, cleaning a sample, putting the sample into a degreasing furnace for degreasing, and putting the sample into a sintering furnace for sintering after degreasing is finished to obtain a final sample; the paste material has high solid content, the shrinkage rate of the structural member prepared by the paste material is small, the defects of crack, warping and the like are not easy to generate, and the thickness of a degreased sample is high.
Description
Technical Field
The invention belongs to the technical field of zirconia ceramic manufacturing, and particularly relates to a graded zirconia paste for 3D printing and a preparation method and application thereof.
Background
The zirconia ceramic is a novel high-technology ceramic, and has the conditions that the precision ceramic has high strength, hardness, high temperature resistance, acid-base corrosion resistance, high chemical stability and the like, and also has higher toughness than common ceramics, so that the zirconia ceramic is also applied to various industries, such as shaft seal bearings, cutting components, dies, automobile parts and the like, and can even be used for human bodies, such as artificial joints.
With the development of industry, the traditional process cannot meet the requirements of high-tech products, the 3D printing rapid prototyping technology is a novel prototyping process which is rapidly developed in recent years, the process can be mainly applied to Fused Deposition Manufacturing (FDM), selective Laser Sintering (SLS) and stereo light Solidification (SLA) technologies in ceramic prototyping at present, the application of the technologies and the subsequent sintering process greatly shorten the prototyping period of ceramic components, and the problem that the design size change or adjustment which cannot be overcome by the traditional process needs to be redesigned and a mold needs to be manufactured is solved.
Although the prior SLA-formed zirconia obtains certain density and bending strength after degreasing and sintering, the solid content of the used printing slurry is low, and the sample shrinks greatly and cracks are easy to generate in the degreasing and sintering process after printing, so that the mechanical property is poor, the degreasing and sintering are easy to deform, the precision control of the sample is not facilitated, and the paste cannot be well applied to the fields with relatively high precision requirements such as electronics, medical treatment and the like, the solid content of the prior zirconia ceramic on the market is 50vol%, the viscosity is more than 500 Pa.S, and if the solid content is increased continuously, the viscosity of the prepared paste is greatly increased, and the paste is not conducive to printing and cleaning. Meanwhile, because the SLA ceramic printing paste has high resin content and is easy to crack and warp during degreasing, the thickness of a prepared sample is generally about 4mm when an SLA printing zirconia sample is printed on the market at present.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide a graded zirconia paste for 3D printing and a preparation method and application thereof.
In order to achieve the purpose, the invention adopts the following technical scheme to realize the purpose:
A3D prints and uses the zirconia cream of gradation, its raw materials include the zirconia powder of gradation, yttria, alumina; photosensitive resin and photoinitiator; a dispersant powder; a liquid dispersant KOS110;
the graded zirconia powder is prepared by uniformly mixing micron zirconia powder and nano zirconia powder according to the mass ratio of (2.5-3.5) to (6.5-7.5);
the mass of the yttrium oxide is 5.2-6.2% of that of the graded zirconia powder;
the mass of the alumina is 0.2 to 0.3 percent of that of the graded zirconia;
the graded zirconia powder, the yttria and the alumina form zirconia mixed powder;
photosensitive resin and photoinitiator form resin solution; the photosensitive resin is a mixture formed by mixing 1, 6-hexanediol diacrylate, trimethylolpropane triacrylate, dipentaerythritol hexaacrylate and epoxy acrylate according to the mass ratio of (3.5-4.5) to (2.8-3.2) to (2.3-2.7) to (0.4-0.6); the addition amount of the photoinitiator is 0.58 to 0.62 percent of the mass of the photosensitive resin;
the zirconium oxide mixed powder accounts for 96.5-98% of the total mass, the dispersant powder accounts for 0.5-1.5% of the total mass, the liquid dispersant KOS110 accounts for 0.5-1.5% of the total mass, and the resin solution accounts for 1.0-1.5% of the total mass.
A preparation method of graded zirconia paste for 3D printing comprises the following steps:
s1, selecting micron zirconia powder and nano zirconia powder, and uniformly mixing the micron zirconia powder and the nano zirconia powder according to the mass ratio of (2.5-3.5) to (6.5-7.5) to prepare graded zirconia powder;
s2, uniformly mixing the graded zirconia powder prepared in the S1 with yttrium oxide and alumina, wherein the mass of the yttrium oxide is 5.2-6.2% of that of the graded zirconia powder, and the mass of the alumina is 0.2-0.3% of that of the graded zirconia powder;
s3, mixing photosensitive resin and a photoinitiator to prepare a resin solution; the photosensitive resin is a mixture formed by mixing 1, 6-hexanediol diacrylate, trimethylolpropane triacrylate, dipentaerythritol hexaacrylate and epoxy acrylate according to the mass ratio of (3.5-4.5) to (2.8-3.2) to (2.3-2.7) to (0.4-0.6); the addition amount of the photoinitiator is 0.58 to 0.62 percent of the mass of the photosensitive resin;
s4, preparing dispersing agent powder by ball milling, adding the dispersing agent powder and grinding balls into a ball milling tank according to the mass ratio of (0.9-1.2) to (1.8-2.2) for ball milling, and then sieving;
and S5, adding the graded zirconia mixed powder prepared in the step S2, the dispersing agent powder prepared in the step S4 and the liquid dispersing agent KOS110 into the resin solution prepared in the step S3 according to a proportion, wherein the zirconia mixed powder accounts for 96.5-98% of the total mass, the dispersing agent powder accounts for 0.5-1.5% of the total mass, the liquid dispersing agent KOS110 accounts for 0.5-1.5% of the total mass, and the resin solution accounts for 1.0-1.5% of the total mass, and performing ball milling and defoaming to prepare the micron-sized graded zirconia ceramic paste with high solid content.
The purity of the zirconia powder is more than 99%.
The yttrium oxide powder in the S2 is used as a stabilizer, and the particle size D50 is 280-330 nm; alumina powder as sintering assistant with grain size D50 of 180-250 nm.
The photoinitiator in S3 is benzoin dimethyl ether or phenyl bis (2, 4, 6-trimethylbenzoyl) phosphine oxide.
The size of the screen mesh in the S4 is 100-120 meshes.
The high solid content micron-grade graded zirconia ceramic paste material in S5 has the solid content of more than or equal to 55 (vol) and the viscosity of less than or equal to 500 Pa.S.
The utility model provides an application of 3D prints with graduation zirconia paste, adds the micron order graduation zirconia ceramic paste of high solid content that makes into ceramic photocuring printer and prints, takes out the sample after accomplishing to print, puts into the degrease stove after rinsing the sample and degreases, after the degrease, puts into the fritting furnace with the sample and sinters and make final sample.
The application comprises the following steps:
and 3, sintering the degreased structural part, wherein the sintering temperature is 1520-1500 ℃, the heat preservation time is 120-150 min, the temperature rising and reducing speed is 1-3 ℃/min, and the final structural part is prepared after sintering.
The thickness of the final structural part can reach 8mm, the density is more than or equal to 95%, and the bending strength is more than or equal to 600MPa.
The ceramic photocuring printer is an SLA ceramic printer, and the wavelength of a light source is 355nm.
Compared with the prior art, the invention has the following beneficial effects:
according to the invention, the solid phase content of the ceramic paste is increased by the mixing proportion of the ceramic powder and the like in the slurry preparation process; the viscosity of the zirconia paste is greatly reduced by introducing the micron zirconia powder through a particle grading method, the solid content of the paste is increased as much as possible while the low viscosity is ensured, and the curing depth is enough and the shrinkage is small when the paste is printed; the photosensitive resin adopts 1, 6-hexanediol diacrylate for dilution, has low shrinkage rate and refractive index, and can reduce the radiation dose; trimethylolpropane triacrylate as a crosslinking modifier; the dipentaerythritol hexaacrylate is a six-functional-group resin, so that the curing efficiency is improved; the epoxy acrylate is a photo-curing prepolymer, and has the characteristics of high hardness and good glossiness after curing. Verification shows that the viscosity of the zirconia ceramic paste with high solid content prepared by adopting the material of the invention and introducing the photosensitive resin with the corresponding mass ratio into the nano powder is moderate, and the solid content is high.
According to the invention, by adjusting the composition and the proportion of the particle size, the viscosity of the ceramic paste is moderate, the solid phase content is high, the solid phase content is more than or equal to 55 (vol)%, the viscosity is less than or equal to 500 Pa.S, and the shrinkage rate is low in the subsequent printing, degreasing and sintering processes through the printed structure of the paste, so that the thickness of the finally prepared sample is more than or equal to 8mm.
According to the invention, through a thinning degreasing process, the degreasing process is divided into five stages, different time is set at different temperature stages, and the lower the temperature rise rate in the degreasing process is, the less the structural member is easy to crack and deform during degreasing, but the too long degreasing time can be caused; the heating rate is high, the degreasing period is short, but deformation and cracking can be caused if the temperature is too high; through the degreasing route, the prepared structural part can be prevented from cracking, the degreasing time can be shortened, and the preparation efficiency is improved.
The final structural member has the advantages of high forming precision, low shrinkage rate, high density, good mechanical property and high bending strength.
Drawings
FIG. 1 is a graph showing degreasing performed in examples 1 to 3 of the present invention.
FIG. 2 is a graph showing sintering curves of examples 1 to 3 of the present invention.
FIG. 3 is a sample prepared in example 1 of the present invention.
FIG. 4 is a sample prepared in example 2 of the present invention.
FIG. 5 is a sample prepared in example 3 of the present invention.
Detailed Description
The invention is described in detail below with reference to the figures and examples.
the graded zirconia powder is prepared by uniformly mixing micron zirconia powder and nano zirconia powder according to the mass ratio of 2.5;
the mass of the yttrium oxide is 5.2 percent of that of the graded zirconia powder;
the mass of the alumina is 0.25 percent of that of the graded zirconia;
the graded zirconia powder, the yttrium oxide and the alumina form zirconia mixed powder;
photosensitive resin and photoinitiator form resin solution; the photosensitive resin is a mixture formed by mixing 1, 6-hexanediol diacrylate, trimethylolpropane triacrylate, dipentaerythritol hexaacrylate and epoxy acrylate according to a mass ratio of 3.5; the addition amount of the photoinitiator is 0.58 percent of the mass of the photosensitive resin;
the zirconium oxide mixed powder accounts for 98% of the total mass, the dispersant powder accounts for 0.5% of the total mass, the liquid dispersant KOS110 accounts for 0.5% of the total mass, and the resin solution accounts for 1.0% of the total mass.
A preparation method of graded zirconia paste for 3D printing comprises the following steps:
s1, in order to improve the uniformity of the material structure, selecting micron zirconia powder and nanometer zirconia powder, and uniformly mixing according to a mass ratio of 2.5;
s2, uniformly mixing the graded zirconia powder prepared in the S1 with yttrium oxide and alumina, wherein the mass of the yttrium oxide is 5.2% of that of the graded zirconia powder, and the mass of the alumina is 0.25% of that of the graded zirconia; yttrium oxide powder is used as a stabilizer, and the particle size D50 is 280nm; alumina powder is used as a sintering aid, and the particle size D50 is 180nm;
s3, mixing photosensitive resin and a photoinitiator to prepare a resin solution; the photosensitive resin is a mixture formed by mixing 1, 6-hexanediol diacrylate, trimethylolpropane triacrylate, dipentaerythritol hexaacrylate and epoxy acrylate according to a mass ratio of 3.5; the addition amount of the photoinitiator is 0.58 percent of the mass of the photosensitive resin;
s4, preparing dispersing agent powder through ball milling, adding the dispersing agent powder and a grinding ball into a ball milling tank according to the mass ratio of 0.9;
s5, adding the graded zirconia mixed powder prepared in the S2, the dispersing agent powder prepared in the S4 and a liquid dispersing agent KOS110 into the resin solution prepared in the S3 in a ratio, wherein the zirconia mixed powder accounts for 98% of the total mass, the dispersing agent powder accounts for 0.5% of the total mass, the KOS110 accounts for 0.5% of the total mass, and the resin solution accounts for 1.0% of the total mass, and performing ball milling and defoaming to prepare a graded zirconia ceramic paste with high solid phase content; the high solid content graded zirconia ceramic paste has the solid content of 57 (vol)%, and the viscosity of 300Pa question mark S.
The purity of the zirconia powder is more than 99%.
The photoinitiator in S3 is benzoin dimethyl ether or phenyl bis (2, 4, 6-trimethylbenzoyl) phosphine oxide.
The utility model provides an application of 3D prints with graduation zirconia paste, adds the micron order graduation zirconia ceramic paste of high solid content that makes into ceramic photocuring printer and prints, takes out the sample after accomplishing to print, puts into the degrease stove after rinsing the sample and degreases, after the degrease, puts into the fritting furnace with the sample and sinters and make final sample.
The application comprises the following steps:
and 3, sintering the degreased structural part, wherein according to the figure 2, the sintering temperature is 1520 ℃, the heat preservation time is 150min, the temperature rise and fall rate is 1 ℃/min, and the final structural part is obtained after sintering.
The ceramic photocuring printer is an SLA ceramic printer, and the wavelength of a light source is 355nm.
The density of the final structural part is 95%, the bending strength is 620MPa, and a sample with the thickness of 9mm after sintering can be prepared, as shown in figure 3.
the graded zirconia powder is prepared by uniformly mixing micro zirconia powder and nano zirconia powder according to the mass ratio of 3;
the mass of the yttrium oxide is 6.2 percent of that of the graded zirconia powder;
the mass of the alumina is 0.3 percent of that of the graded zirconia;
the graded zirconia powder, the yttria and the alumina form zirconia mixed powder;
photosensitive resin and photoinitiator form resin solution; the photosensitive resin is a mixture formed by mixing 1, 6-hexanediol diacrylate, trimethylolpropane triacrylate, dipentaerythritol hexaacrylate and epoxy acrylate according to a mass ratio of 4.5; the addition amount of the photoinitiator is 0.62 percent of the mass of the photosensitive resin;
the zirconia mixed powder accounts for 97.5 percent of the total mass, the dispersant powder accounts for 0.5 percent of the total mass, the liquid dispersant KOS110 accounts for 0.5 percent of the total mass, and the resin solution accounts for 1.5 percent of the total mass.
A preparation method of graded zirconia paste for 3D printing comprises the following steps:
s1, in order to improve the uniformity of material structure, uniformly mixing selected micro zirconia powder and nano zirconia powder according to a mass ratio of 3;
s2, uniformly mixing the graded zirconia powder prepared in the S1 with yttrium oxide and alumina, wherein the mass of the yttrium oxide is 6.2% of that of the graded zirconia powder, and the mass of the alumina is 0.3% of that of the graded zirconia; yttrium oxide powder is used as a stabilizer, and the particle size D50 is 330nm; alumina powder is used as a sintering aid, and the particle size D50 is 250nm;
s3, mixing photosensitive resin and a photoinitiator to prepare a resin solution; the photosensitive resin is a mixture formed by mixing 1, 6-hexanediol diacrylate, trimethylolpropane triacrylate, dipentaerythritol hexaacrylate and epoxy acrylate according to a mass ratio of 4.5; the addition amount of the photoinitiator is 0.62 percent of the mass of the photosensitive resin;
s4, preparing dispersing agent powder by ball milling, adding the dispersing agent powder and the milling balls into a ball milling tank according to the mass ratio of 1.2;
s5, adding the graded zirconia mixed powder prepared in the S2, the dispersing agent powder prepared in the S4 and the liquid dispersing agent KOS110 into the resin solution prepared in the S3 according to a proportion, wherein the zirconia mixed powder accounts for 97.5% of the total mass, the dispersing agent powder accounts for 0.5% of the total mass, the liquid dispersing agent KOS110 accounts for 0.5% of the total mass, and the resin solution accounts for 1.5% of the total mass, performing ball milling and defoaming to prepare micron-grade graded zirconia ceramic paste with high solid content, wherein the solid content is 57 (vol)%, and the viscosity is 410Pa · S;
the purity of the zirconia powder is more than 99 percent;
the photoinitiator in S2 is benzoin dimethyl ether or phenyl bis (2, 4, 6-trimethylbenzoyl) phosphine oxide;
the size of the screen mesh in the S4 is 120 meshes.
The application of the graded zirconia paste for 3D printing is characterized in that the prepared high-solid-content micron-grade graded zirconia ceramic paste is added into a ceramic photocuring printer for printing, a sample is taken out after printing is finished, the sample is placed into a degreasing furnace for degreasing after being cleaned, and the sample is placed into a sintering furnace for sintering after degreasing is finished, so that a final sample is prepared.
The application comprises the following steps:
the ceramic photocuring printer is an SLA ceramic printer, and the wavelength of a light source is 355nm.
The density of the final structural part is 96.4%, the bending strength is 673MPa, and a sample with the thickness of 8mm after sintering can be prepared, as shown in figure 4.
the graded zirconia powder is prepared by uniformly mixing micron zirconia powder and nano zirconia powder according to the mass ratio of 3.5;
the mass of the yttrium oxide is 5.6 percent of that of the graded zirconia powder;
the mass of the alumina is 0.3 percent of that of the graded zirconia;
the graded zirconia powder, the yttrium oxide and the alumina form zirconia mixed powder;
photosensitive resin and photoinitiator form resin solution; the photosensitive resin is a mixture formed by mixing 1, 6-hexanediol diacrylate, trimethylolpropane triacrylate, dipentaerythritol hexaacrylate and epoxy acrylate according to a mass ratio of 4; the addition amount of the photoinitiator is 0.60 percent of the mass of the photosensitive resin;
the zirconia mixed powder accounts for 97.3 percent of the total mass, the dispersant powder accounts for 0.7 percent of the total mass, the liquid dispersant KOS110 accounts for 0.7 percent of the total mass, and the resin solution accounts for 1.3 percent of the total mass.
A preparation method of graded zirconia paste for 3D printing comprises the following steps:
s1, in order to improve the uniformity of the material structure, selecting micro zirconia powder and nano zirconia powder, and uniformly mixing the micro zirconia powder and the nano zirconia powder according to the mass ratio of 3.5;
s2, uniformly mixing the graded zirconia powder prepared in the S1 with yttrium oxide and alumina, wherein the mass of the yttrium oxide is 5.6% of that of the graded zirconia powder, and the mass of the alumina is 0.3% of that of the graded zirconia; yttrium oxide powder is used as a stabilizer, and the particle size D50 is 300nm; alumina powder is used as a sintering aid, and the particle size D50 is 200nm;
s3, mixing photosensitive resin and a photoinitiator to prepare a resin solution; the photosensitive resin is a mixture formed by mixing 1, 6-hexanediol diacrylate, trimethylolpropane triacrylate, dipentaerythritol hexaacrylate and epoxy acrylate according to a mass ratio of 4; the addition amount of the photoinitiator is 0.60 percent of the mass of the photosensitive resin;
s4, preparing dispersing agent powder through ball milling, adding the dispersing agent powder and a grinding ball into a ball milling tank according to the mass ratio of 1.0;
and S5, adding the graded zirconia mixed powder prepared in the S2, the dispersing agent powder prepared in the S4 and the liquid dispersing agent KOS110 into the resin solution prepared in the S3 according to a proportion, wherein the zirconia mixed powder accounts for 97.3% of the total mass, the dispersing agent powder accounts for 0.7% of the total mass, the liquid dispersing agent KOS110 accounts for 0.7% of the total mass, and the resin solution accounts for 1.3% of the total mass, and after ball milling and defoaming, preparing micron-grade graded zirconia ceramic paste with high solid content, the high solid content graded zirconia ceramic paste with 57 (vol) percent of solid content and 480Pa & S of viscosity.
The purity of the zirconia powder is more than 99 percent;
the photoinitiator in S3 is benzoin dimethyl ether or phenyl bis (2, 4, 6-trimethylbenzoyl) phosphine oxide;
the size of the screen mesh in the S4 is 110 meshes.
The utility model provides an application of 3D prints with graduation zirconia paste, adds the micron order graduation zirconia ceramic paste of high solid content that makes into ceramic photocuring printer and prints, takes out the sample after accomplishing to print, puts into the degrease stove after rinsing the sample and degreases, after the degrease, puts into the fritting furnace with the sample and sinters and make final sample.
The application comprises the following steps:
the ceramic photocuring printer is an SLA ceramic printer, and the wavelength of a light source is 355nm.
The density of the final structural part is 97.5%, the bending strength is 730MPa, and a sample with the thickness of 8mm after sintering can be prepared, as shown in figure 5.
Claims (12)
1. The graded zirconia paste for 3D printing is characterized in that raw materials comprise graded zirconia powder, yttrium oxide and aluminum oxide; photosensitive resin and photoinitiator; a dispersant powder; a liquid dispersant KOS110;
the graded zirconia powder is prepared by uniformly mixing micron zirconia powder and nano zirconia powder according to the mass ratio of (2.5-3.5) to (6.5-7.5);
the mass of the yttrium oxide is 5.2-6.2% of that of the graded zirconia powder;
the mass of the alumina is 0.2 to 0.3 percent of that of the graded zirconia;
the graded zirconia powder, the yttria and the alumina form zirconia mixed powder;
photosensitive resin and photoinitiator form resin solution; the photosensitive resin is a mixture formed by mixing 1, 6-hexanediol diacrylate, trimethylolpropane triacrylate, dipentaerythritol hexaacrylate and epoxy acrylate according to the mass ratio of (3.5-4.5) to (2.8-3.2) to (2.3-2.7) to (0.4-0.6); the addition amount of the photoinitiator is 0.58 to 0.62 percent of the mass of the photosensitive resin;
the zirconium oxide mixed powder accounts for 96.5-98% of the total mass, the dispersant powder accounts for 0.5-1.5% of the total mass, the liquid dispersant KOS110 accounts for 0.5-1.5% of the total mass, and the resin solution accounts for 1.0-1.5% of the total mass.
2. A preparation method of graded zirconia paste for 3D printing is characterized by comprising the following steps:
s1, selecting micron zirconia powder and nano zirconia powder, and uniformly mixing the micron zirconia powder and the nano zirconia powder according to the mass ratio of (2.5-3.5) to (6.5-7.5) to prepare graded zirconia powder;
s2, uniformly mixing the graded zirconia powder prepared in the S1 with yttrium oxide and alumina, wherein the mass of the yttrium oxide is 5.2-6.2% of that of the graded zirconia powder, and the mass of the alumina is 0.2-0.3% of that of the graded zirconia powder;
s3, mixing photosensitive resin and a photoinitiator to prepare a resin solution; the photosensitive resin is a mixture formed by mixing 1, 6-hexanediol diacrylate, trimethylolpropane triacrylate, dipentaerythritol hexaacrylate and epoxy acrylate according to the mass ratio of (3.5-4.5) to (2.8-3.2) to (2.3-2.7) to (0.4-0.6); the addition amount of the photoinitiator is 0.58 to 0.62 percent of the mass of the photosensitive resin;
s4, preparing dispersing agent powder by ball milling, adding the dispersing agent powder and grinding balls into a ball milling tank according to the mass ratio of (0.9-1.2) to (1.8-2.2) for ball milling, and then sieving;
s5, adding the graded zirconia mixed powder prepared in the S2, the dispersing agent powder prepared in the S4 and the liquid dispersing agent KOS110 into the resin solution prepared in the S3 according to a proportion, wherein the zirconia mixed powder accounts for 96.5-98% of the total mass, the dispersing agent powder accounts for 0.5-1.5% of the total mass, the liquid dispersing agent KOS110 accounts for 0.5-1.5% of the total mass, and the resin solution accounts for 1.0-1.5% of the total mass, and performing ball milling and defoaming to prepare a micron-grade graded zirconia ceramic paste with high solid phase content;
the yttrium oxide powder in the S2 is used as a stabilizer, and the particle size D50 is 280-330 nm; alumina powder is used as a sintering aid, and the particle size D50 is 180-250 nm;
the photoinitiator in S3 is benzoin dimethyl ether or phenyl bis (2, 4, 6-trimethylbenzoyl) phosphine oxide;
the size of the screen mesh in the S4 is 100-120 meshes;
the solid content of the micron-grade graded zirconia ceramic paste with high solid content in S5 is more than or equal to 55 (vol)%, and the viscosity is less than or equal to 500 Pa.S.
3. Use of a graded zirconia paste for 3D printing according to any one of claims 1 to 2 wherein: adding the prepared micron-sized graded zirconia ceramic paste with high solid content into a ceramic photocuring printer for printing, taking out a sample after printing is finished, cleaning the sample, degreasing the sample in a degreasing furnace, and sintering the sample in a sintering furnace after degreasing is finished to obtain a final sample;
the application comprises the following steps:
step 1, SLA 3D printing is carried out on the micron-sized graded zirconia ceramic paste with high solid content to prepare an initial structural member;
step 2, degreasing the initial structural part to obtain a degreased structural part, wherein the degreasing atmosphere is inert gas; the degreasing process comprises the following steps: the first stage, the temperature is 200-220 ℃, and the time is 120-150 min; the second stage, the temperature is 300-320 ℃, and the time is 120-150 min; the third stage, the temperature is 380-400 ℃, and the time is 120-150 min; the fourth stage, the temperature is 600-620 ℃, and the time is 120-150 min; the fifth stage, the temperature is 1150-1180 ℃, and the time is 120-150 min; the heating rate is 0.1-0.5 ℃/min below 600 ℃ in the degreasing process, and the heating rate is 1-1.5 ℃/min above 600 ℃; the cooling rate is 2-2.5 ℃/min;
step 3, sintering the degreased structural part, wherein the sintering temperature is 1520-1500 ℃, the heat preservation time is 120-150 min, the temperature rise and fall rate is 1-3 ℃/min, and the final structural part is prepared after sintering;
the thickness of the final structural part can reach 8mm, the density is more than or equal to 95%, and the bending strength is more than or equal to 600MPa;
the ceramic photocuring printer is an SLA ceramic printer, and the wavelength of a light source is 355nm.
4. The utility model provides a 3D prints with graduation zirconia paste which characterized in that: the raw materials comprise graded zirconia powder, yttrium oxide and aluminum oxide; photosensitive resin and photoinitiator; a dispersant powder; a liquid dispersant KOS110;
the graded zirconia powder is prepared by uniformly mixing micron zirconia powder and nano zirconia powder according to the mass ratio of 2.5;
the mass of the yttrium oxide is 5.2 percent of that of the graded zirconia powder;
the mass of the alumina is 0.25 percent of that of the graded zirconia;
the graded zirconia powder, the yttrium oxide and the alumina form zirconia mixed powder;
photosensitive resin and photoinitiator form resin solution; the photosensitive resin is a mixture formed by mixing 1, 6-hexanediol diacrylate, trimethylolpropane triacrylate, dipentaerythritol hexaacrylate and epoxy acrylate according to a mass ratio of 3.5; the addition amount of the photoinitiator is 0.58 percent of the mass of the photosensitive resin;
the zirconium oxide mixed powder accounts for 98% of the total mass, the dispersant powder accounts for 0.5% of the total mass, the liquid dispersant KOS110 accounts for 0.5% of the total mass, and the resin solution accounts for 1.0% of the total mass.
5. The preparation method of the graded zirconia paste for 3D printing according to claim 4 is characterized by comprising the following steps:
s1, selecting micron zirconia powder and nano zirconia powder, and uniformly mixing according to a mass ratio of 2.5;
s2, uniformly mixing the graded zirconia powder prepared in the S1 with yttrium oxide and alumina, wherein the mass of the yttrium oxide is 5.2% of that of the graded zirconia powder, and the mass of the alumina is 0.25% of that of the graded zirconia; yttrium oxide powder is used as a stabilizer, and the particle size D50 is 280nm; alumina powder is used as a sintering aid, and the particle size D50 is 180nm;
s3, mixing photosensitive resin and a photoinitiator to prepare a resin solution; the photosensitive resin is a mixture formed by mixing 1, 6-hexanediol diacrylate, trimethylolpropane triacrylate, dipentaerythritol hexaacrylate and epoxy acrylate according to a mass ratio of 3.5; the addition amount of the photoinitiator is 0.58 percent of the mass of the photosensitive resin;
s4, preparing dispersing agent powder through ball milling, adding the dispersing agent powder and a grinding ball into a ball milling tank according to the mass ratio of 0.9;
s5, adding the graded zirconia mixed powder prepared in the S2, the dispersing agent powder prepared in the S4 and a liquid dispersing agent KOS110 into the resin solution prepared in the S3 according to a ratio, wherein the zirconia mixed powder accounts for 98% of the total mass, the dispersing agent powder accounts for 0.5% of the total mass, the KOS110 accounts for 0.5% of the total mass, and the resin solution accounts for 1.0% of the total mass, and performing ball milling and defoaming to prepare a graded zirconia ceramic paste with high solid phase content; the high solid content graded zirconia ceramic paste has the solid content of 57 (vol)%, and the viscosity of 300Pa & S;
the purity of the zirconia powder is more than 99 percent;
the photoinitiator in S3 is benzoin dimethyl ether or phenyl bis (2, 4, 6-trimethylbenzoyl) phosphine oxide.
6. The use of a graded zirconia paste for 3D printing according to claim 4 wherein: adding the prepared micron-sized graded zirconia ceramic paste with high solid content into a ceramic photocuring printer for printing, taking out a sample after printing is finished, cleaning the sample, degreasing the sample in a degreasing furnace, and sintering the sample in a sintering furnace after degreasing is finished to obtain a final sample;
the application comprises the following steps:
step 1, SLA 3D printing is carried out on the micron-sized graded zirconia ceramic paste with high solid content to prepare an initial structural member;
step 2, degreasing the initial structural part to obtain a degreased structural part, wherein the degreasing atmosphere is inert gas; the degreasing process comprises the following steps: the first stage, the temperature is 200 ℃, and the time is 150min; the second stage, the temperature is 300 ℃, and the time is 150min; the third stage, the temperature is 380 ℃, and the time is 150min; the fourth stage, the temperature is 600 ℃, and the time is 150min; the fifth stage, the temperature is 1150 ℃, and the time is 150min; the temperature rise rate of the degreasing process is 0.5 ℃/min below 600 ℃, and the temperature rise rate is 1 ℃/min above 600 ℃; the cooling rate is 2 ℃/min;
step 3, sintering the degreased structural part, wherein the sintering temperature is 1520 ℃, the heat preservation time is 150min, the temperature rising and reducing speed is 1 ℃/min, and the final structural part is prepared after sintering;
the ceramic photocuring printer is an SLA ceramic printer, and the wavelength of a light source is 355nm.
7. The utility model provides a 3D prints with graduation zirconia paste which characterized in that: the raw materials comprise graded zirconia powder, yttrium oxide and aluminum oxide; photosensitive resin and photoinitiator; a dispersant powder; a liquid dispersant KOS110;
the graded zirconia powder is prepared by uniformly mixing micron zirconia powder and nano zirconia powder according to the mass ratio of 3;
the mass of the yttrium oxide is 6.2 percent of that of the graded zirconia powder;
the mass of the alumina is 0.3 percent of that of the graded zirconia;
the graded zirconia powder, the yttrium oxide and the alumina form zirconia mixed powder;
photosensitive resin and photoinitiator form resin solution; the photosensitive resin is a mixture formed by mixing 1, 6-hexanediol diacrylate, trimethylolpropane triacrylate, dipentaerythritol hexaacrylate and epoxy acrylate according to a mass ratio of 4.5; the addition amount of the photoinitiator is 0.62 percent of the mass of the photosensitive resin;
the zirconium oxide mixed powder accounts for 97.5 percent of the total mass, the dispersant powder accounts for 0.5 percent of the total mass, the liquid dispersant KOS110 accounts for 0.5 percent of the total mass, and the resin solution accounts for 1.5 percent of the total mass.
8. The preparation method of the graded zirconia paste for 3D printing according to claim 7, characterized by comprising the following steps:
s1, uniformly mixing the selected micro zirconia powder and nano zirconia powder according to a mass ratio of 3;
s2, uniformly mixing the graded zirconia powder prepared in the S1 with yttrium oxide and alumina, wherein the mass of the yttrium oxide is 6.2% of that of the graded zirconia powder, and the mass of the alumina is 0.3% of that of the graded zirconia; yttrium oxide powder is used as a stabilizer, and the particle size D50 is 330nm; alumina powder is used as a sintering aid, and the particle size D50 is 250nm;
s3, mixing photosensitive resin and a photoinitiator to prepare a resin solution; the photosensitive resin is a mixture formed by mixing 1, 6-hexanediol diacrylate, trimethylolpropane triacrylate, dipentaerythritol hexaacrylate and epoxy acrylate according to a mass ratio of 4.5; the addition amount of the photoinitiator is 0.62 percent of the mass of the photosensitive resin;
s4, preparing dispersing agent powder by ball milling, adding the dispersing agent powder and the milling balls into a ball milling tank according to the mass ratio of 1.2;
s5, adding the graded zirconia mixed powder prepared in the S2, the dispersing agent powder prepared in the S4 and the liquid dispersing agent KOS110 into the resin solution prepared in the S3 according to a proportion, wherein the zirconia mixed powder accounts for 97.5% of the total mass, the dispersing agent powder accounts for 0.5% of the total mass, the liquid dispersing agent KOS110 accounts for 0.5% of the total mass, and the resin solution accounts for 1.5% of the total mass, and after ball milling and defoaming, preparing a high solid content micron-grade graded zirconia ceramic paste, the high solid content micron-grade zirconia ceramic paste with 57 (vol) percent of solid content and 410Pa & S of viscosity;
the purity of the zirconia powder is more than 99 percent;
the photoinitiator in S2 is benzoin dimethyl ether or phenyl bis (2, 4, 6-trimethylbenzoyl) phosphine oxide;
and the size of the screen mesh in the S4 is 120 meshes.
9. The use of a graded zirconia paste for 3D printing according to claim 7 wherein: adding the prepared micron-grade graded zirconia ceramic paste with high solid content into a ceramic photocuring printer for printing, taking out a sample after printing is finished, cleaning the sample, putting the sample into a degreasing furnace for degreasing, and after degreasing is finished, putting the sample into a sintering furnace for sintering to prepare a final sample;
the application comprises the following steps:
step 1, SLA 3D printing is carried out on the micron-sized graded zirconia ceramic paste with high solid content to prepare an initial structural member;
step 2, degreasing the initial structural part to obtain a degreased structural part, wherein the degreasing atmosphere is inert gas; the degreasing process comprises the following steps: the first stage, the temperature is 220 ℃, and the time is 120min; the second stage, the temperature is 320 ℃, and the time is 120min; the third stage, the temperature is 400 ℃, and the time is 120min; the fourth stage, the temperature is 620 ℃, and the time is 120min; the fifth stage, the temperature is 1180 ℃, and the time is 120min; the temperature rise rate below 600 ℃ in the degreasing process is 0.2 ℃/min, and the temperature rise rate above 600 ℃ is 1.5 ℃/min; the cooling rate is 2.5 ℃/min;
step 3, sintering the degreased structural part, wherein the sintering temperature is 1520 ℃, the heat preservation time is 120min, the temperature rise and fall rate is 2 ℃/min, and obtaining the final structural part after sintering;
the ceramic photocuring printer is an SLA ceramic printer, and the wavelength of a light source is 355nm.
10. The utility model provides a 3D prints with graduation zirconia paste which characterized in that: the raw materials comprise graded zirconia powder, yttrium oxide and alumina; photosensitive resin and photoinitiator; a dispersant powder; a liquid dispersant KOS110;
the graded zirconia powder is prepared by uniformly mixing micron zirconia powder and nano zirconia powder according to the mass ratio of 3.5;
the mass of the yttrium oxide is 5.6 percent of that of the graded zirconia powder;
the mass of the alumina is 0.3 percent of that of the graded zirconia;
the graded zirconia powder, the yttria and the alumina form zirconia mixed powder;
photosensitive resin and photoinitiator form resin solution; the photosensitive resin is a mixture formed by mixing 1, 6-hexanediol diacrylate, trimethylolpropane triacrylate, dipentaerythritol hexaacrylate and epoxy acrylate according to a mass ratio of 4; the addition amount of the photoinitiator is 0.60 percent of the mass of the photosensitive resin;
the zirconia mixed powder accounts for 97.3 percent of the total mass, the dispersant powder accounts for 0.7 percent of the total mass, the liquid dispersant KOS110 accounts for 0.7 percent of the total mass, and the resin solution accounts for 1.3 percent of the total mass.
11. The preparation method of the graded zirconia paste for 3D printing according to claim 10 is characterized by comprising the following steps:
s1, selecting micron zirconia powder and nanometer zirconia powder, and uniformly mixing according to a mass ratio of 3.5;
s2, uniformly mixing the graded zirconia powder prepared in the S1 with yttrium oxide and aluminum oxide, wherein the mass of the yttrium oxide is 5.6% of that of the graded zirconia powder, and the mass of the aluminum oxide is 0.3% of that of the graded zirconia powder; yttrium oxide powder is used as a stabilizer, and the particle size D50 is 300nm; alumina powder is used as a sintering aid, and the particle size D50 is 200nm;
s3, mixing photosensitive resin and a photoinitiator to prepare a resin solution; the photosensitive resin is a mixture formed by mixing 1, 6-hexanediol diacrylate, trimethylolpropane triacrylate, dipentaerythritol hexaacrylate and epoxy acrylate according to a mass ratio of 4; the addition amount of the photoinitiator is 0.60 percent of the mass of the photosensitive resin;
s4, preparing dispersing agent powder through ball milling, adding the dispersing agent powder and a grinding ball into a ball milling tank according to the mass ratio of 1.0;
s5, adding the graded zirconia mixed powder prepared in the S2, the dispersing agent powder prepared in the S4 and the liquid dispersing agent KOS110 into the resin solution prepared in the S3 according to a proportion, wherein the zirconia mixed powder accounts for 97.3 percent of the total mass, the dispersing agent powder accounts for 0.7 percent of the total mass, the liquid dispersing agent KOS110 accounts for 0.7 percent of the total mass, and the resin solution accounts for 1.3 percent of the total mass, and after ball milling and defoaming, preparing micron-grade graded zirconia ceramic paste with high solid content, the high solid content graded zirconia ceramic paste with 57 (vol) percent of solid content and 480Pa & S of viscosity;
the purity of the zirconia powder is more than 99 percent;
the photoinitiator in S3 is benzoin dimethyl ether or phenyl bis (2, 4, 6-trimethylbenzoyl) phosphine oxide;
the S4 middle screen mesh the size is 110 meshes.
12. The use of a graded zirconia paste for 3D printing according to claim 10 wherein: adding the prepared micron-sized graded zirconia ceramic paste with high solid content into a ceramic photocuring printer for printing, taking out a sample after printing is finished, cleaning the sample, degreasing the sample in a degreasing furnace, and sintering the sample in a sintering furnace after degreasing is finished to obtain a final sample;
the application comprises the following steps:
step 1, SLA 3D printing is carried out on the micron-sized graded zirconia ceramic paste with high solid content to prepare an initial structural member;
step 2, degreasing the initial structural part to obtain a degreased structural part, wherein the degreasing atmosphere is inert gas; the degreasing process comprises the following steps: the first stage, the temperature is 210 ℃, and the time is 130min; the second stage, the temperature is 310 ℃, and the time is 130min; the third stage, the temperature is 390 ℃, and the time is 130min; the fourth stage, the temperature is 610 ℃, and the time is 130min; the fifth stage, the temperature is 1160 ℃, and the time is 130min; the temperature rise rate below 600 ℃ in the degreasing process is 0.3 ℃/min, and the temperature rise rate above 600 ℃ is 1.2 ℃/min; the cooling rate is 2.2 ℃/min;
step 3, sintering the degreased structural part, wherein the sintering temperature is 1530 ℃, the heat preservation time is 130min, the temperature rise and fall rate is 3 ℃/min, and obtaining the final structural part after sintering;
the ceramic photocuring printer is an SLA ceramic printer, and the wavelength of a light source is 355nm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110894241.5A CN113754430B (en) | 2021-08-05 | 2021-08-05 | Graded zirconia paste for 3D printing and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110894241.5A CN113754430B (en) | 2021-08-05 | 2021-08-05 | Graded zirconia paste for 3D printing and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113754430A CN113754430A (en) | 2021-12-07 |
| CN113754430B true CN113754430B (en) | 2022-10-25 |
Family
ID=78788584
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110894241.5A Active CN113754430B (en) | 2021-08-05 | 2021-08-05 | Graded zirconia paste for 3D printing and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113754430B (en) |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114800767A (en) * | 2022-03-18 | 2022-07-29 | 嘉兴饶稷科技有限公司 | Method for preparing transparent ceramic through one-step forming based on photocuring 3D printing technology |
| CN114921115B (en) * | 2022-03-25 | 2023-05-09 | 深圳职业技术学院 | Yttrium stabilized zirconia ceramic slurry and its preparation method and application |
| CN114505491B (en) * | 2022-04-18 | 2022-06-24 | 天津大学 | Degreasing sintering method for manufacturing formed piece based on nano-particle additive |
| CN117285349B (en) * | 2023-09-05 | 2024-03-08 | 中国地质大学（武汉） | 3D printing color zirconia ceramic slurry and preparation method and application thereof |
| CN118005389B (en) * | 2023-11-30 | 2024-09-13 | 江南大学 | Preparation method of black zirconia manufactured by photocuring additive |
| CN117942267A (en) * | 2024-01-30 | 2024-04-30 | 江南大学 | Method for manufacturing complete denture based on photo-curing additive of Bingham fluid material |
| CN118026655A (en) * | 2024-01-30 | 2024-05-14 | 江南大学 | Method for manufacturing ceramic component by photocuring additive |
| CN117923882B (en) * | 2024-01-31 | 2024-08-16 | 江南大学 | Method for manufacturing transparent alumina bracket based on high-solid high-viscosity ceramic paste |
| CN117944142A (en) * | 2024-01-31 | 2024-04-30 | 江南大学 | Method for manufacturing transparent zirconia ceramic bracket by photocuring additive |
| CN117945754B (en) * | 2024-01-31 | 2024-09-06 | 江南大学 | Method for preparing ceramic false tooth based on photocuring additive manufacturing and microwave sintering technology |
Family Cites Families (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102219534B (en) * | 2011-04-27 | 2013-06-26 | 中国地质大学（武汉） | Method for preparing nano oxide slurry |
| CN105036751B (en) * | 2015-09-06 | 2017-11-03 | 哈尔滨工业大学 | A kind of method that ceramics are prepared using micro-nano size grading |
| CN105967686A (en) * | 2016-05-05 | 2016-09-28 | 青岛大学 | Preparation method of zirconia whole porcelain tooth |
| CN106007709B (en) * | 2016-05-12 | 2019-05-21 | 中南大学 | A kind of method that gel casting forming prepares high-strength ceramic |
| KR101934782B1 (en) * | 2018-01-10 | 2019-01-04 | 에이온 주식회사 | Zirconia dental prosthesis manufacturing system |
| CN109176828B (en) * | 2018-08-16 | 2021-02-05 | 中国船舶重工集团公司第七二五研究所 | Gel injection molding method for large-size planar ceramic blank capable of preventing warping deformation |
| CN109437893B (en) * | 2019-01-09 | 2022-09-02 | 北京理工大学 | High-solid-content/low-viscosity photocuring zirconia 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 |
| CN112500157A (en) * | 2020-12-10 | 2021-03-16 | 湖南人文科技学院 | Method for reducing shrinkage rate of nano zirconia ceramic dry-pressed product |
| CN112679210A (en) * | 2021-01-25 | 2021-04-20 | 佛山市金刚材料科技有限公司 | Electric-melting zirconia ceramic slurry for photocuring 3D printing and preparation method thereof |
-
2021
- 2021-08-05 CN CN202110894241.5A patent/CN113754430B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN113754430A (en) | 2021-12-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN113754430B (en) | Graded zirconia paste for 3D printing and preparation method and application thereof | |
| CN107098714B (en) | Silicon carbide-based ceramic part manufacturing method based on 3DP additive manufacturing technology | |
| CN105198449B (en) | A kind of preparation method of the high ceramic of compact of Stereolithography | |
| CN107353036B (en) | Porous silicon nitride ceramic based on additive manufacturing technology, and preparation method and application thereof | |
| CN113461427B (en) | Photocuring 4D printing ceramic-based precursor slurry, ceramic part and preparation method | |
| CN108083777A (en) | A kind of preparation method of photocuring 3D printing Al-base ceramic slurry and ceramic core | |
| CN108503365B (en) | Silicon carbide ceramic based on photocuring technology and preparation method thereof | |
| CN107721408B (en) | Method for preparing beta-tricalcium phosphate porous bioceramic through 3D printing | |
| CN108947537A (en) | SiC ceramic structural part and preparation method thereof | |
| CN107021771B (en) | Calcium oxide-based ceramic casting mold manufacturing method based on 3D printing technology | |
| CN107377970B (en) | A kind of low cost metal 3D printing method | |
| CN112047727B (en) | Preparation method of 3D printing alumina ceramic material | |
| CN111716488B (en) | Method for manufacturing hollow zirconia false tooth through high-yield 3D printing | |
| CN110803915A (en) | Ceramic photocuring material and preparation method thereof | |
| CA2550481A1 (en) | Method of making ceramic discharge vessels using stereolithography | |
| CN114853450A (en) | Photocuring 3D printing alumina-based ceramic core and preparation method thereof | |
| CN112919887A (en) | Photo-curing alumina ceramic paste and atomization cavity integrated forming method thereof | |
| CN109896862A (en) | A kind of β-SiAlON ceramics of complicated shape and preparation method thereof | |
| CN111777408A (en) | 3D printing high-strength ZTA ceramic substrate material and preparation process | |
| CN113956023A (en) | Method for preparing aluminum oxide ceramic based on sinking type DLP photocuring 3D printing | |
| CN114099769A (en) | Material and method for 3D printing of dental all-ceramic restoration body by using viscoelastic paste | |
| CN114149253A (en) | Photocuring 3D printing low-sintering-shrinkage ceramic core and preparation method thereof | |
| CN114524676A (en) | Photocuring silicon nitride ceramic slurry and preparation method of silicon nitride ceramic | |
| CN112916850B (en) | Metal oxide-doped photocuring 3D printing metal part and preparation method thereof | |
| CN113976917A (en) | Degreasing method for manufacturing precious metal green body through photocuring additive manufacturing |
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 |