CN114835511A - Cordierite precursor photocuring paste and preparation method of porous cordierite ceramic with complex structure - Google Patents

Cordierite precursor photocuring paste and preparation method of porous cordierite ceramic with complex structure Download PDF

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CN114835511A
CN114835511A CN202210619570.3A CN202210619570A CN114835511A CN 114835511 A CN114835511 A CN 114835511A CN 202210619570 A CN202210619570 A CN 202210619570A CN 114835511 A CN114835511 A CN 114835511A
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parts
ceramic powder
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composite ceramic
paste
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CN114835511B (en
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鲍崇高
李世佳
董文彩
刘荣臻
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Xian Jiaotong University
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Abstract

A preparation method of cordierite precursor photocuring paste and porous cordierite ceramic with a complex structure comprises the steps of preparing a paste from composite ceramic powder and premixed liquid, wherein the composite ceramic powder is one or two of talc, high-purity alumina powder and high-purity silicon dioxide or diatomite; the premixed liquid is a mixture of composite photosensitive resin, photoinitiator and additive; the preparation of the paste is to mix the composite ceramic powder, then prepare a premixed solution, finally add the composite ceramic powder into the premixed solution one by one, and obtain the cordierite precursor photocuring paste after fully mixing and defoaming by adopting a planetary homogenizer; the preparation of the porous cordierite ceramic with the complex structure comprises the steps of firstly printing a cordierite precursor photocuring paste to obtain a printing sample piece; and then degreasing the printing sample, and finally performing carbon removal and sintering on the degreased printing sample.

Description

Cordierite precursor photocuring paste and preparation method of porous cordierite ceramic with complex structure
Technical Field
The invention relates to the technical field of porous cordierite ceramics, in particular to a cordierite precursor photocuring paste and a preparation method of porous cordierite ceramics with a complex structure.
Background
The porous cordierite ceramic has the performance advantages of low thermal expansion coefficient, good thermal shock resistance, high chemical stability, low dielectric coefficient, good fire resistance and the like, and is widely applied to the fields of electronic packaging, energy regeneration catalysis, refractory materials, high-temperature flue gas filtration and purification, high-pollution wastewater treatment and the like. With the development of modern industry, the demand of various industry fields on cordierite ceramics is expanded from the performance of materials to the structural design, particularly in the fields of energy regeneration catalysis and high-temperature flue gas filtration and purification, and the complicated three-dimensional structural design can provide extremely high macroscopic specific surface area, so that the directional design of different functional demands is realized, and the catalytic efficiency and the purification efficiency are greatly improved. At present, the preparation of structure-function integrated high-performance cordierite porous ceramics by adopting in-situ synthesis (precursor) and a novel forming process is a hot point. However, existing conventional fabrication processes, such as extrusion molding, gel-casting, foaming, sacrificial template molding, etc., do not allow for the design of complex three-dimensional structures because of mold design limitations and the complexity of the fabrication process.
In recent years, the popularization of additive manufacturing technology in the field of ceramic manufacturing provides an effective way for the discovery of the application potential of various ceramics, and the working principle of layer-by-layer material laying and layer-by-layer printing realizes the functional-structure integrated ceramic piece. At present, the processes applied to ceramic additive manufacturing include direct ink printing (DIW), Fused Deposition Modeling (FDM), selective laser sintering/melting (SLS/SLM), stereo light curing engraving molding (SLA), and the like, wherein the SLA technology based on ceramic paste molding has the highest precision and the best surface quality. The key to realize SL A forming is the corresponding ceramic paste, for cordierite ceramics, no cordierite precursor photocureable paste which can be applied to SLA forming exists in the market at present, and the paste prepared by singly using cordierite powder is difficult to realize the regulation and control of the performance of a fired product. And the preparation of the porous cordierite ceramic with the complex structure can be realized only by reasonably applying degreasing and sintering processes.
In summary, the prior art has the following defects: 1. the traditional forming methods such as extrusion forming, foaming forming, gel injection molding and the like can not form porous cordierite ceramics with complex customized structures, so that the use potential of the porous cordierite ceramics in the fields of heat insulation materials, refractory materials, electronic packaging materials and catalyst carriers is greatly limited; the photocuring forming mode can realize the high-efficiency forming of a customized complex structure, but a cordierite precursor photocuring paste which can be used for photocuring forming is lacked at present. 2. At present, most of commonly used precursor powder for preparing cordierite ceramics is high-purity raw material, so that the raw material cost is increased, and the process cost (high firing temperature) is also increased. 3. A complete set of degreasing and sintering processes are needed for a photo-cured formed cordierite precursor body, and no degreasing and sintering process is reported at present.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide a cordierite precursor photocuring paste and a preparation method of porous cordierite ceramic with a complex structure, which can realize photocuring forming of complex parts and in-situ synthesis of cordierite ceramic.
In order to achieve the purpose, the invention adopts the following technical scheme to realize the purpose:
the cordierite precursor photocuring paste comprises composite ceramic powder and premixed liquid, wherein the composite ceramic powder accounts for 30-45 vol% of the paste in parts by volume;
the composite ceramic powder is one of talc, high-purity alumina powder and high-purity silicon dioxide or diatomiteOr both; wherein the particle diameter of the talc is 2.6-45 um, and the content of TiO is 2 、Fe 2 O 3 Less than 3 wt% of total; the grain diameter of the high-purity alumina is 0.3um-5 um; the grain size of the high-purity silicon oxide is between 0.3um and 5 um; the diatomite has a particle size of 1-10um and contains TiO 2 、Fe 2 O 3 Less than 3 wt% of total Na 2 O、K 2 The total content of O is less than 1 percent; the coating comprises, by weight, 40-50 parts of talc, 30-40 parts of high-purity alumina, 0-25 parts of high-purity silicon dioxide and 0-25 parts of diatomite.
The premixed liquid is a mixture of composite photosensitive resin, a photoinitiator and an additive; the composite photosensitive resin is a mixed solution of 1, 6-hexanediol diacrylate, dipentaerythritol hexaacrylate and bisphenol A type epoxy acrylic resin, and the mixed solution is counted by weight parts, 8-10 parts of 1, 6-hexanediol diacrylate, 5-7 parts of dipentaerythritol hexaacrylate and 4-6 parts of bisphenol A type epoxy acrylic resin; the photoinitiator is a free radical photoinitiator, namely benzil dimethyl ether, and the benzil dimethyl ether accounts for 0.5-2% of the total mass of the composite photosensitive resin; the additive comprises a plasticizer and a dispersant, wherein the plasticizer is one or more of polyethylene glycol 200, polyethylene glycol 400 and dibutyl phthalate, the composite photosensitive resin accounts for 64-95 parts by volume, and the dosage of the plasticizer is 5-36 parts; the dispersant is Span80, and the usage amount is 0.5 wt% -5 wt% of the composite ceramic powder.
A preparation method of cordierite precursor photocuring paste comprises the following steps:
1) mixing composite ceramic powder, namely preparing the composite ceramic powder by adopting anhydrous ethanol and agate balls as wet grinding media and using 40-50 parts of talc, 30-40 parts of high-purity alumina, 0-25 parts of high-purity silicon dioxide and 0-25 parts of diatomite according to mass fraction;
the composite ceramic powder comprises the following components in percentage by mass: agate ball: the absolute ethyl alcohol is 1:2:2, the ball milling time is 18-30 hours, and the grain diameter of the composite ceramic powder after ball milling is less than 10 um;
2) according to the mass portion, 8-10 portions of 1, 6-hexanediol diacrylate, 5-7 portions of dipentaerythritol hexaacrylate and 4-6 portions of bisphenol A epoxy acrylic resin are mixed to form composite photosensitive resin; the photoinitiator is a free radical photoinitiator, namely benzil dimethyl ether, and the benzil dimethyl ether accounts for 0.5-2% of the total mass of the composite photosensitive resin; the additive comprises a plasticizer and a dispersant, wherein the plasticizer is one or more of polyethylene glycol 200, polyethylene glycol 400 and dibutyl phthalate, the composite photosensitive resin accounts for 64-95 parts by volume, and the dosage of the plasticizer is 5-36 parts; the dispersant is Span80, and the using amount is 0.5 wt% -5 wt% of the composite ceramic powder; fully mixing the weighed composite photosensitive resin, photoinitiator and additive by adopting a planetary homogenizer to obtain a premixed solution;
3) and (2) gradually adding the composite ceramic powder into the premixed liquid, wherein the premixed liquid accounts for 55-70 parts by volume, and the composite ceramic powder accounts for 30-45 parts by volume, and fully mixing and defoaming by adopting a planetary homogenizer to obtain the cordierite precursor photocuring paste.
The preparation method of the porous cordierite ceramic with the complex structure by utilizing the cordierite precursor photocuring paste comprises the following steps:
1) the printing process comprises the following steps: printing the cordierite precursor photocuring paste to obtain a printing sample piece; laser energy density of 70-567mJ/cm 2 The layering thickness is 25-100 mu m, and the scraper speed is 10-20 mm/s;
2) degreasing process: degreasing the printing sample piece, wherein the degreasing atmosphere is argon, the degreasing process is divided into 6 sections according to a TG curve, and the 6 sections comprise 0-190 ℃, 190-; after degreasing, presintering along with a furnace, raising the temperature to 800 ℃ at the speed of 3 ℃/min, and keeping the temperature for 1 h;
3) the carbon removal-sintering integrated process comprises the following steps: and (2) performing carbon removal-sintering on the degreased printing sample piece, wherein the carbon removal process is divided into 3 stages, namely 0-120 ℃, 120-phase temperature 300 ℃ and 300-phase temperature 500 ℃, wherein the temperature rise rate of the 300-phase temperature 500 ℃ is 1 ℃/min, the heat preservation time of the end point temperature 500 ℃ is 2h, the temperature rise rate of the rest stages is 1 ℃/min-5 ℃/min, the heat preservation time of the end point temperature of each stage is 0.5-2h, then the temperature is raised to the sintering temperature at the rate of 5 ℃/min, the sintering temperature is 1250-phase temperature 1400 ℃, and the heat preservation time is 1-5 h.
Compared with the prior art, the invention has the following beneficial effects:
the invention discloses a cordierite precursor photocuring paste material and a preparation method of porous cordierite ceramic with a complex structure, which solve the problems that a complex ceramic structural member cannot be formed by the traditional process, and cordierite clinker energy consumption is large and sintering member performance is difficult to regulate; the method solves the preparation of porous cordierite ceramic with a customized structure by establishing printing, degreasing and sintering processes matched with cordierite precursor paste, has high forming precision, good surface quality and high forming efficiency, has extremely high structural design flexibility, and provides a new idea for the combination of solid phase synthesis and 3D printing.
Drawings
FIG. 1 is a drawing (a) of a cordierite precursor paste prepared in example 1; panel (b) is a cured sheet prepared using the cordierite precursor paste.
FIG. 2 is a 3D model of example 1; FIG. (b) is a print swatch; FIG. (c) shows a sample degreased; FIG. d shows a sintered sample.
FIG. 3 is an XRD diffraction pattern of the porous cordierite ceramic prepared in example 1.
Detailed Description
The present invention will be further described with reference to the following examples.
Embodiment 1, a cordierite precursor photocuring paste comprises a composite ceramic powder and a premix, wherein the composite ceramic powder accounts for 33 vol% of the paste in terms of volume fraction;
the composite ceramic powderTalc, high purity alumina powder and high purity silica; wherein the particle diameter of the talc is 14.05um, and the content of TiO is 2 、Fe 2 O 3 Less than 3 wt% of total; the grain diameter of the high-purity alumina is 1.61 um; the grain size of the high-purity silicon oxide is 2.15 um; 45 parts of talc, 33 parts of high-purity alumina and 22 parts of high-purity silicon dioxide;
the premixed liquid is a mixture of composite photosensitive resin, a photoinitiator and an additive; the composite photosensitive resin is a mixed solution of 1, 6-hexanediol diacrylate, dipentaerythritol hexaacrylate and bisphenol A type epoxy acrylic resin, and is counted according to parts by weight, 9 parts of 1, 6-hexanediol diacrylate, 6 parts of dipentaerythritol hexaacrylate and 5 parts of bisphenol A type epoxy acrylic resin; the photoinitiator is a free radical photoinitiator, namely benzil dimethyl ether, and the benzil dimethyl ether accounts for 0.5 percent of the total mass of the composite photosensitive resin; the additive comprises a plasticizer and a dispersant, wherein the plasticizer is dibutyl phthalate, and the volume part number of the dibutyl phthalate is 73 parts, and the using amount of the plasticizer is 27 parts; the dispersant is Span80, and the usage amount is 1 wt% of the composite ceramic powder.
A preparation method of cordierite precursor photocuring paste comprises the following steps:
1) mixing the composite ceramic powder, namely preparing the composite ceramic powder by adopting anhydrous ethanol and agate balls as wet grinding media and using 45 parts of talc, 33 parts of high-purity alumina and 22 parts of high-purity silicon dioxide according to mass fraction;
the composite ceramic powder comprises the following components in percentage by mass: agate ball: the absolute ethyl alcohol is 1:2:2, the ball milling time is 24 hours, and the grain diameter of the composite ceramic powder after ball milling is less than 10 um;
2) according to the mass parts, 9 parts of 1, 6-hexanediol diacrylate, 6 parts of dipentaerythritol hexaacrylate and 5 parts of bisphenol A epoxy acrylic resin form composite photosensitive resin; the photoinitiator is a free radical photoinitiator, namely benzil dimethyl ether, and the benzil dimethyl ether accounts for 0.5 percent of the total mass of the composite photosensitive resin; the additive comprises a plasticizer and a dispersant, wherein the plasticizer is dibutyl phthalate, and the plasticizer is 73 parts by volume of the composite photosensitive resin, and the using amount of the dibutyl phthalate is 27 parts by volume; the dispersant is Span80, and the using amount is 1 wt% of the composite ceramic powder; fully mixing the weighed composite photosensitive resin, photoinitiator and additive by adopting a planetary homogenizer to obtain a premixed solution;
3) sequentially adding composite ceramic powder into the premixed liquid, wherein the premixed liquid accounts for 67 parts by volume, the composite ceramic powder accounts for 33 parts by volume, fully mixing and defoaming by adopting a planetary homogenizer to obtain a cordierite precursor photocuring paste, as shown in a diagram (a) in fig. 1, and a diagram (b) is a solidified sheet prepared by adopting the cordierite precursor paste, and as can be seen from the diagram (a) in fig. 1, the cordierite precursor paste prepared by the method disclosed by the invention is smooth in surface, uniform in components, and in an obvious self-supporting paste state, and is free from agglomeration; as can be seen from FIG. 1(b), the printed cured sheet has clear outline and no defects, further illustrating that the ceramic paste prepared by the invention has uniform components and good curing performance.
The preparation method of the porous cordierite ceramic with the complex structure by utilizing the cordierite precursor photocuring paste comprises the following steps:
1) the printing process comprises the following steps: the cordierite precursor photocurable paste was printed according to the model of FIG. 2, Panel (a), with a laser energy density of 191.5mJ/cm 2 The layering thickness is 50 mu m, and the scraper speed is 15 mm/s; as shown in the diagram (b) in FIG. 2, the prepared printing member has complete structure, good surface quality and high dimensional accuracy, which shows that the cordierite precursor paste adopted by the invention has excellent curing performance and rheological property, and the adopted printing process can realize the preparation of a complex customized structure.
2) Degreasing process: degreasing the printing sample piece, wherein the degreasing atmosphere is argon, the degreasing process is divided into 6 sections according to a TG curve, and the 6 sections are respectively 0-190 ℃, 190-; after degreasing, presintering in a furnace, raising the temperature to 800 ℃ at the rate of 3 ℃/min, and keeping the temperature for 1h, as shown in a diagram (c) in FIG. 2, wherein the degreased complex structural part has no defects such as layering and microcracks, which shows that the adopted degreasing process can realize the stable cracking of macromolecules in the printed part and lay a foundation for the sintering of high-efficiency cordierite ceramics in the later period;
3) the carbon removal-sintering integrated process comprises the following steps: and (3) decarbonizing and sintering the degreased printing sample piece, wherein the decarbonizing process is divided into 3 stages, namely 0-120 ℃, 120-phase 300 ℃ and 300-phase 500 ℃, respectively, wherein the temperature rise rate of the 300-phase 500 ℃ is 1 ℃/min, the heat preservation time of the end point temperature of 500 ℃ is 2h, the temperature rise rate of the rest stages is 1 ℃/min, the heat preservation time of the end point temperature of each stage is 0.5h, then the temperature rise rate is 5 ℃/min to the sintering temperature, the sintering temperature is 1400 ℃, the heat preservation time is 1h, and as shown in a graph (d) in fig. 2, the sintered porous cordierite complex piece is not deformed or warped.
The XRD diffraction pattern of the porous cordierite ceramic prepared in this example is shown in FIG. 3, from which it can be seen that a single cordierite phase is obtained from the sintered article after high temperature sintering.
Embodiment 2, a cordierite precursor photocuring paste comprises composite ceramic powder and a premix, wherein the composite ceramic powder accounts for 38 vol% of the paste in terms of volume fraction;
the composite ceramic powder is talc, high-purity alumina powder and diatomite; wherein the particle diameter of the talc is 2.6um, and the content of TiO is 2 、Fe 2 O 3 Less than 3 wt% of total; the grain diameter of the high-purity alumina is 0.3 um; the diatomite has a particle size of 1um and contains TiO 2 、Fe 2 O 3 Less than 3 wt% of total Na 2 O、K 2 The total content of O is less than 1 percent; counting by weight parts, 40 parts of talc, 35 parts of high-purity alumina and 25 parts of diatomite;
the premixed liquid is a mixture of composite photosensitive resin, a photoinitiator and an additive; the composite photosensitive resin is a mixed solution of 1, 6-hexanediol diacrylate, dipentaerythritol hexaacrylate and bisphenol A type epoxy acrylic resin, and is counted according to parts by weight, 8 parts of 1, 6-hexanediol diacrylate, 6 parts of dipentaerythritol hexaacrylate and 6 parts of bisphenol A type epoxy acrylic resin; the photoinitiator is a free radical photoinitiator, namely benzil dimethyl ether, and the benzil dimethyl ether accounts for 1% of the total mass of the composite photosensitive resin; the additive comprises a plasticizer and a dispersant, wherein the plasticizer is polyethylene glycol 400, the volume portion of the polyethylene glycol 400 is counted, the composite photosensitive resin is 90 portions, and the dosage of the plasticizer is 10 portions; the dispersant is Span80, and the usage amount is 5 wt% of the composite ceramic powder.
A preparation method of cordierite precursor photocuring paste comprises the following steps:
1) mixing ceramic composite powder, namely preparing composite ceramic powder by adopting anhydrous ethanol and agate balls as wet grinding media and according to mass fraction, 40 parts of talc, 35 parts of high-purity alumina and 25 parts of diatomite;
the composite ceramic powder comprises the following components in percentage by mass: agate ball: the absolute ethyl alcohol is 1:2:2, the ball milling time is 18 hours, and the grain diameter of the composite ceramic powder after ball milling is less than 10 um;
2) according to the mass parts, a mixed solution of 8 parts of 1, 6-hexanediol diacrylate, 6 parts of dipentaerythritol hexaacrylate and 6 parts of bisphenol A type epoxy acrylic resin forms composite photosensitive resin; the photoinitiator is a free radical photoinitiator, namely benzil dimethyl ether, and the benzil dimethyl ether accounts for 1% of the total mass of the composite photosensitive resin; the additive comprises a plasticizer and a dispersant, wherein the plasticizer is polyethylene glycol 400, the composite photosensitive resin accounts for 90 parts by volume, and the dosage of the polyethylene glycol 400 is 10 parts; the dispersant is Span80, and the using amount is 5 wt% of the mass of the ceramic powder; fully mixing the weighed composite photosensitive resin, photoinitiator and additive by adopting a planetary homogenizer to obtain a premixed solution;
3) and (2) gradually adding the composite ceramic powder into the premixed liquid, wherein the premixed liquid accounts for 62 parts by volume, and the composite ceramic powder accounts for 38 parts by volume, and fully mixing and defoaming by adopting a planetary homogenizer to obtain the cordierite precursor photocuring paste.
The preparation method of the porous cordierite ceramic with the complex structure by utilizing the cordierite precursor photocuring paste comprises the following steps:
1) the printing process comprises the following steps: printing the cordierite precursor photocuring paste to obtain the cordierite precursor photocuring pastePrinting a sample piece; laser energy density 97mJ/cm 2 The layering thickness is 25 mu m, and the scraper speed is 10 mm/s;
2) degreasing process: degreasing the printing sample piece, wherein the degreasing atmosphere is argon, the degreasing process is divided into 6 sections according to a TG curve, and the 6 sections are respectively 0-190 ℃, 190-; after degreasing, presintering along with a furnace, raising the temperature to 800 ℃ at the speed of 3 ℃/min, and keeping the temperature for 1 h;
3) the carbon removal-sintering integrated process comprises the following steps: and (2) performing carbon removal-sintering on the degreased printing sample piece, wherein the carbon removal process is divided into 3 stages, namely 0-120 ℃, 120-300 ℃ and 300-500 ℃, respectively, wherein the temperature rise rate of the 300-500 ℃ is 1 ℃/min, the heat preservation time of the end point temperature of 500 ℃ is 2h, the temperature rise rates of the other stages are 3 ℃/min, the heat preservation time of the end point temperature of each stage is 2h, then the temperature is raised to the sintering temperature at the rate of 5 ℃/min, the sintering temperature is 1350 ℃, and the heat preservation time is 5 h.
Embodiment 3, a cordierite precursor photocuring paste comprises a composite ceramic powder and a premix, wherein the composite ceramic powder accounts for 45 vol% of the paste in terms of volume fraction;
the composite ceramic powder is talc, high-purity alumina powder, high-purity silicon dioxide and diatomite; wherein the particle diameter of the talc is 45um, and the content of TiO 2 、Fe 2 O 3 Less than 3 wt% of total; the grain diameter of the high-purity alumina is 5 um; the grain size of the high-purity silicon oxide is 0.3 um; the diatomite has a particle size of 10um and contains TiO 2 、Fe 2 O 3 Less than 3 wt% of total Na 2 O、K 2 The total content of O is less than 1 percent; counting by weight parts, 40 parts of talc, 35 parts of high-purity alumina, 12.5 parts of high-purity silicon dioxide and 12.5 parts of diatomite;
the premixed liquid is a mixture of composite photosensitive resin, a photoinitiator and an additive; the composite photosensitive resin is a mixed solution of 1, 6-hexanediol diacrylate, dipentaerythritol hexaacrylate and bisphenol A type epoxy acrylic resin, and is counted according to parts by weight, 10 parts of 1, 6-hexanediol diacrylate, 6 parts of dipentaerythritol hexaacrylate and 4 parts of bisphenol A type epoxy acrylic resin; the photoinitiator is a free radical photoinitiator, namely benzil dimethyl ether, and the benzil dimethyl ether accounts for 2% of the total mass of the composite photosensitive resin; the additive comprises a plasticizer and a dispersant, wherein the plasticizer is polyethylene glycol 200, the volume part number is 64 parts, and the using amount of the plasticizer is 36 parts; the dispersant is Span80, and the usage amount is 5 wt% of the composite ceramic powder.
A preparation method of cordierite precursor photocuring paste comprises the following steps:
1) mixing composite ceramic powder, namely preparing the composite ceramic powder by adopting anhydrous ethanol and agate balls as wet grinding media and according to the mass fraction, 40 parts of talc, 35 parts of high-purity alumina, 12.5 parts of high-purity silica and 12.5 parts of diatomite;
the composite ceramic powder comprises the following components in percentage by mass: agate ball: the absolute ethyl alcohol is 1:2:2, the ball milling time is 30 hours, and the grain diameter of the composite ceramic powder after ball milling is less than 10 um;
2) according to the mass parts, 10 parts of 1, 6-hexanediol diacrylate, 6 parts of dipentaerythritol hexaacrylate and 4 parts of bisphenol A epoxy acrylic resin form composite photosensitive resin; the photoinitiator is a free radical photoinitiator, namely benzil dimethyl ether, and the benzil dimethyl ether accounts for 2% of the total mass of the composite photosensitive resin; the additive comprises a plasticizer and a dispersant, wherein the plasticizer is polyethylene glycol 200, the composite photosensitive resin accounts for 64 parts by volume, and the dosage of the polyethylene glycol 200 is 36 parts; the dispersant is Span80, and the using amount is 5 wt% of the mass of the ceramic powder; fully mixing the weighed composite photosensitive resin, photoinitiator and additive by adopting a planetary homogenizer to obtain a premixed solution;
3) and (2) gradually adding the composite ceramic powder into the premixed liquid, wherein the premixed liquid accounts for 55 parts by volume, and the composite ceramic powder accounts for 45 parts by volume, and fully mixing and defoaming by adopting a planetary homogenizer to obtain the cordierite precursor photocuring paste.
The preparation method of the porous cordierite ceramic with the complex structure by utilizing the cordierite precursor photocuring paste comprises the following steps:
1) the printing process comprises the following steps: printing the cordierite precursor photocuring paste to obtain a printing sample piece; laser energy density 300mJ/cm 2 The layering thickness is 50 mu m, and the scraper speed is 10 mm/s;
2) degreasing process: degreasing the printing sample piece, wherein the degreasing atmosphere is argon, the degreasing process is divided into 6 sections according to a TG curve, and the 6 sections are respectively 0-190 ℃, 190-; after degreasing, presintering along with a furnace, raising the temperature to 800 ℃ at the speed of 3 ℃/min, and keeping the temperature for 1 h;
3) the carbon removal-sintering integrated process comprises the following steps: and (2) performing carbon removal-sintering on the degreased printing sample piece, wherein the carbon removal process is divided into 3 stages, namely 0-120 ℃, 120-300 ℃ and 300-500 ℃, respectively, wherein the temperature rise rate of the 300-500 ℃ is 1 ℃/min, the heat preservation time of the end point temperature of 500 ℃ is 2h, the temperature rise rates of the other stages are 3 ℃/min, the heat preservation time of the end point temperature of each stage is 1h, then the temperature is raised to the sintering temperature at the rate of 5 ℃/min, the sintering temperature is 1250 ℃, and the heat preservation time is 5 h.
Embodiment 4, a cordierite precursor photocuring paste comprises a composite ceramic powder and a premix, wherein the composite ceramic powder accounts for 40 vol% of the paste in terms of volume fraction;
the composite ceramic powder is talc, high-purity alumina powder and high-purity silicon dioxide; wherein the particle diameter of the talc is 12um, and the content of TiO 2 、Fe 2 O 3 Less than 3 wt% of total; the grain diameter of the high-purity alumina is 4 um; the grain size of the high-purity silicon oxide is 5 um; counting by weight parts, 50 parts of talc, 40 parts of high-purity alumina and 10 parts of high-purity silicon dioxide;
the premixed liquid is a mixture of composite photosensitive resin, a photoinitiator and an additive; the composite photosensitive resin is a mixed solution of 1, 6-hexanediol diacrylate, dipentaerythritol hexaacrylate and bisphenol A type epoxy acrylic resin, and is counted according to parts by weight, 8 parts of 1, 6-hexanediol diacrylate, 7 parts of dipentaerythritol hexaacrylate and 5 parts of bisphenol A type epoxy acrylic resin; the photoinitiator is a free radical photoinitiator, namely benzil dimethyl ether, and the benzil dimethyl ether accounts for 1% of the total mass of the composite photosensitive resin; the additive comprises a plasticizer and a dispersant, wherein the plasticizer comprises polyethylene glycol 200, polyethylene glycol 400 and dibutyl phthalate, the composite photosensitive resin is 64 parts by volume, the dosage of the plasticizer is 36 parts, and the dosage of each plasticizer is the same, namely 12 parts; the dispersant is Span80, and the usage amount is 0.5 wt% of the composite ceramic powder.
A preparation method of cordierite precursor photocuring paste comprises the following steps:
1) mixing the composite ceramic powder, namely preparing the composite ceramic powder by adopting anhydrous ethanol and agate balls as wet grinding media and according to the mass fraction, 50 parts of talc, 40 parts of high-purity alumina and 10 parts of high-purity silicon dioxide;
the composite ceramic powder comprises the following components in percentage by mass: agate ball: the absolute ethyl alcohol is 1:2:2, the ball milling time is 24 hours, and the grain diameter of the composite ceramic powder after ball milling is less than 10 um;
2) according to the mass parts, a mixed solution of 8 parts of 1, 6-hexanediol diacrylate, 7 parts of dipentaerythritol hexaacrylate and 5 parts of bisphenol A type epoxy acrylic resin forms composite photosensitive resin; the photoinitiator is a free radical photoinitiator, namely benzil dimethyl ether, and the benzil dimethyl ether accounts for 1% of the total mass of the composite photosensitive resin; the additive comprises a plasticizer and a dispersant, wherein the plasticizer comprises polyethylene glycol 200, polyethylene glycol 400 and dibutyl phthalate, the composite photosensitive resin is 64 parts by volume, the dosage of the plasticizer is 36 parts, and the dosage of each plasticizer is the same, namely 12 parts; the dispersant is Span80, and the usage amount is 0.5 wt% of the composite ceramic powder. Fully mixing the weighed composite photosensitive resin, photoinitiator and additive by adopting a planetary homogenizer to obtain a premixed solution;
3) and (2) gradually adding the composite ceramic powder into the premixed liquid, wherein the premixed liquid accounts for 60 parts by volume, and the composite ceramic powder accounts for 40 parts by volume, and fully mixing and defoaming by adopting a planetary homogenizer to obtain the cordierite precursor photocuring paste.
The preparation method of the porous cordierite ceramic with the complex structure by utilizing the cordierite precursor photocuring paste comprises the following steps:
1) the printing process comprises the following steps: printing the cordierite precursor photocuring paste to obtain a printing sample piece; laser energy density 230mJ/cm 2 The layering thickness is 50 mu m, and the scraper speed is 12 mm/s;
2) degreasing process: degreasing the printing sample piece, wherein the degreasing atmosphere is argon, the degreasing process is divided into 6 sections according to a TG curve, and the 6 sections are respectively 0-190 ℃, 190-; after degreasing, presintering along with a furnace, raising the temperature to 800 ℃ at the speed of 3 ℃/min, and keeping the temperature for 1 h;
3) the carbon removal-sintering integrated process comprises the following steps: and (2) performing decarbonization-sintering on the degreased printing sample piece, wherein the decarbonization process is divided into 3 stages, namely 0-120 ℃, 120-phase temperature 300 ℃ and 300-phase temperature 500 ℃, respectively, wherein the temperature rise rate of the 300-phase temperature 500 ℃ is 1 ℃/min, the heat preservation time of the end point temperature 500 ℃ is 2h, the temperature rise rate of the rest stages is 1 ℃/min, the heat preservation time of the end point temperature of each stage is 2h, then the temperature is raised to the sintering temperature at the rate of 5 ℃/min, the sintering temperature is 1350 ℃, and the heat preservation time is 3 h.
Embodiment 5, a cordierite precursor photocuring paste comprises composite ceramic powder and a premix, wherein the composite ceramic powder accounts for 40 vol% of the paste in terms of volume fraction;
the composite ceramic powder is talc, high-purity alumina powder and high-purity silicon dioxide; wherein the particle diameter of the talc is 20um, and the content of TiO 2 、Fe 2 O 3 Less than 3 wt% of total; the grain diameter of the high-purity alumina is 5 um; the grain size of the high-purity silicon oxide is 2 um; 45 parts of talc, 35 parts of high-purity alumina and 20 parts of high-purity silicon dioxide;
the premixed liquid is a mixture of composite photosensitive resin, a photoinitiator and an additive; the composite photosensitive resin is a mixed solution of 1, 6-hexanediol diacrylate, dipentaerythritol hexaacrylate and bisphenol A type epoxy acrylic resin, and is counted according to parts by weight, 9 parts of 1, 6-hexanediol diacrylate, 5 parts of dipentaerythritol hexaacrylate and 6 parts of bisphenol A type epoxy acrylic resin; the photoinitiator is a free radical photoinitiator, namely benzil dimethyl ether, and the benzil dimethyl ether accounts for 1.5 percent of the total mass of the composite photosensitive resin; the additive comprises a plasticizer and a dispersant, wherein the plasticizer comprises polyethylene glycol 400 and dibutyl phthalate, the composite photosensitive resin accounts for 70 parts by volume, the dosage of the plasticizer is 30 parts, and the dosage of each plasticizer is the same, namely 15 parts; the dispersant is Span80, and the usage amount is 2 wt% of the composite ceramic powder.
A preparation method of cordierite precursor photocuring paste comprises the following steps:
1) mixing the composite ceramic powder, namely preparing the composite ceramic powder by adopting anhydrous ethanol and agate balls as wet grinding media and according to mass fraction, 45 parts of talc, 35 parts of high-purity alumina and 20 parts of high-purity silicon dioxide;
the composite ceramic powder comprises the following components in percentage by mass: agate ball: the absolute ethyl alcohol is 1:2:2, the ball milling time is 24 hours, and the grain diameter of the composite ceramic powder after ball milling is less than 10 um;
(2) according to the mass parts, 9 parts of 1, 6-hexanediol diacrylate, 5 parts of dipentaerythritol hexaacrylate and 6 parts of bisphenol A epoxy acrylic resin form composite photosensitive resin; the photoinitiator is a free radical photoinitiator, namely benzil dimethyl ether, and the benzil dimethyl ether accounts for 1.5 percent of the total mass of the composite photosensitive resin; the additive comprises a plasticizer and a dispersant, wherein the plasticizer comprises polyethylene glycol 400 and dibutyl phthalate, the composite photosensitive resin accounts for 70 parts by volume, the dosage of the plasticizer is 30 parts, and the dosage of each plasticizer is the same, namely 15 parts; the dispersant is Span80, and the using amount is 2 wt% of the composite ceramic powder; fully mixing the weighed composite photosensitive resin, photoinitiator and additive by adopting a planetary homogenizer to obtain a premixed solution;
3) and (2) gradually adding the composite ceramic powder into the premixed liquid, wherein the premixed liquid accounts for 60 parts by volume, and the composite ceramic powder accounts for 40 parts by volume, and fully mixing and defoaming by adopting a planetary homogenizer to obtain the cordierite precursor photocuring paste.
The preparation method of the porous cordierite ceramic with the complex structure by utilizing the cordierite precursor photocuring paste comprises the following steps:
1) the printing process comprises the following steps: printing the cordierite precursor photocuring paste to obtain a printing sample piece; laser energy density 230mJ/cm 2 The layering thickness is 50 mu m, and the scraper speed is 12 mm/s;
2) degreasing process: degreasing the printing sample piece, wherein the degreasing atmosphere is argon, the degreasing process is divided into 6 sections according to a TG curve, and the 6 sections are respectively 0-190 ℃, 190-; after degreasing, presintering along with a furnace, raising the temperature to 800 ℃ at the speed of 3 ℃/min, and keeping the temperature for 1 h;
3) the carbon removal-sintering integrated process comprises the following steps: and (2) performing carbon removal-sintering on the degreased printing sample piece, wherein the carbon removal process is divided into 3 stages, namely 0-120 ℃, 120-300 ℃ and 300-500 ℃, respectively, wherein the temperature rise rate of the 300-500 ℃ is 1 ℃/min, the heat preservation time of the end point temperature of 500 ℃ is 2h, the temperature rise rates of the other stages are 1 ℃/min, the heat preservation time of the end point temperature of each stage is 2h, then the temperature is raised to the sintering temperature at the rate of 5 ℃/min, the sintering temperature is 1350 ℃, and the heat preservation time is 3 h.
Embodiment 6, a cordierite precursor photocuring paste comprises a composite ceramic powder and a premix, wherein the composite ceramic powder accounts for 35 vol% of the paste in terms of volume fraction;
the composite ceramic powder is talc, high-purity alumina powder and high-purity silicon dioxide; wherein the particle diameter of the talc is 5um, and the content of TiO 2 、Fe 2 O 3 Less than 3 wt% of total; the grain diameter of the high-purity alumina is 2 um;the grain size of the high-purity silicon oxide is 2 um; 45 parts of talc, 33 parts of high-purity alumina and 22 parts of high-purity silicon dioxide;
the premixed liquid is a mixture of composite photosensitive resin, a photoinitiator and an additive; the composite photosensitive resin is a mixed solution of 1, 6-hexanediol diacrylate, dipentaerythritol hexaacrylate and bisphenol A type epoxy acrylic resin, and is counted according to parts by weight, 9 parts of 1, 6-hexanediol diacrylate, 5 parts of dipentaerythritol hexaacrylate and 6 parts of bisphenol A type epoxy acrylic resin; the photoinitiator is a free radical photoinitiator, namely benzil dimethyl ether, and the benzil dimethyl ether accounts for 1.5 percent of the total mass of the composite photosensitive resin; the additive comprises a plasticizer and a dispersant, wherein the plasticizer comprises polyethylene glycol 200 and dibutyl phthalate, the volume parts of the plasticizer are counted, the composite photosensitive resin is 80 parts, the dosage of the plasticizer is 20 parts, and the dosage of each plasticizer is the same, namely 10 parts; the dispersant was Span80, and the amount used was 4 wt% of the mass of the composite ceramic powder.
A preparation method of cordierite precursor photocuring paste comprises the following steps:
1) mixing the composite ceramic powder, namely preparing the composite ceramic powder by adopting anhydrous ethanol and agate balls as wet grinding media and using 45 parts of talc, 33 parts of high-purity alumina and 22 parts of high-purity silicon dioxide according to mass fraction;
the composite ceramic powder comprises the following components in percentage by mass: agate ball: and (3) absolute ethyl alcohol is 1:2:2, the ball milling time is 24 hours, and the particle size of the composite ceramic powder after ball milling is less than 10 um.
2) According to the mass parts, 9 parts of 1, 6-hexanediol diacrylate, 5 parts of dipentaerythritol hexaacrylate and 6 parts of bisphenol A epoxy acrylic resin form composite photosensitive resin; the photoinitiator is a free radical photoinitiator, namely benzil dimethyl ether, and the benzil dimethyl ether accounts for 1.5 percent of the total mass of the composite photosensitive resin; the additive comprises a plasticizer and a dispersant, wherein the plasticizer comprises polyethylene glycol 200 and dibutyl phthalate, the volume parts of the plasticizer are counted, the composite photosensitive resin is 80 parts, the dosage of the plasticizer is 20 parts, and the dosage of each plasticizer is the same, namely 10 parts; the dispersant is Span80, and the using amount is 4 wt% of the mass of the ceramic powder; fully mixing the weighed composite photosensitive resin, photoinitiator and additive by adopting a planetary homogenizer to obtain a premixed solution;
3) and (2) gradually adding the composite ceramic powder into the premixed liquid, wherein the premixed liquid accounts for 65 parts by volume, the composite ceramic powder accounts for 35 parts by volume, and fully mixing and defoaming by adopting a planetary homogenizer to obtain the cordierite precursor photocuring paste.
The preparation method of the porous cordierite ceramic with the complex structure by utilizing the cordierite precursor photocuring paste comprises the following steps:
1) the printing process comprises the following steps: printing the cordierite precursor photocuring paste to obtain a printing sample piece; laser energy density 567mJ/cm 2 The layering thickness is 100 mu m, and the scraper speed is 20 mm/s;
2) degreasing process: degreasing the printing sample piece, wherein the degreasing atmosphere is argon, the degreasing process is divided into 6 sections according to a TG curve, and the 6 sections are respectively 0-190 ℃, 190-; after degreasing, presintering along with a furnace, raising the temperature to 800 ℃ at the speed of 3 ℃/min, and keeping the temperature for 1 h;
3) the carbon removal-sintering integrated process comprises the following steps: and (2) performing carbon removal-sintering on the degreased printing sample piece, wherein the carbon removal process is divided into 3 stages, namely 0-120 ℃, 120-plus-300 ℃ and 300-plus-500 ℃, respectively, wherein the temperature rise rate of the 300-plus-500 ℃ is 1 ℃/min, the heat preservation time of the end point temperature of 500 ℃ is 2h, the temperature rise rate of the rest stages is 1 ℃/min, the heat preservation time of the end point temperature of each stage is 2h, then the temperature is raised to the sintering temperature at the rate of 5 ℃/min, the sintering temperature is 1400 ℃, and the heat preservation time is 3 h.
Embodiment 7, a cordierite precursor photocuring paste, comprising composite ceramic powder and a premix, wherein the composite ceramic powder is 35 vol% of the paste;
the composite ceramic powder is talc, high-purity alumina powder and high-purity silicon dioxide; wherein the particles of talcHas a diameter of 8um and contains TiO 2 、Fe 2 O 3 Less than 3 wt% of total; the grain diameter of the high-purity alumina is 1 um; the grain diameter of the high-purity silicon oxide is 1 um; 45 parts of talc, 33 parts of high-purity alumina and 22 parts of high-purity silicon dioxide;
the premixed liquid is a mixture of composite photosensitive resin, a photoinitiator and an additive; the composite photosensitive resin is a mixed solution of 1, 6-hexanediol diacrylate, dipentaerythritol hexaacrylate and bisphenol A type epoxy acrylic resin, and is counted according to parts by weight, 9 parts of 1, 6-hexanediol diacrylate, 5 parts of dipentaerythritol hexaacrylate and 6 parts of bisphenol A type epoxy acrylic resin; the photoinitiator is a free radical photoinitiator, namely benzil dimethyl ether, and the benzil dimethyl ether accounts for 1.5 percent of the total mass of the composite photosensitive resin; the additive comprises a plasticizer and a dispersant, wherein the plasticizer comprises polyethylene glycol 200 and polyethylene glycol 400, the composite photosensitive resin accounts for 70 parts by volume, the dosage of the plasticizer is 30 parts, and the dosage of each plasticizer is the same, namely 15 parts; the dispersant is Span80, and the usage amount is 3 wt% of the composite ceramic powder.
A preparation method of cordierite precursor photocuring paste comprises the following steps:
1) mixing the composite ceramic powder, namely preparing the composite ceramic powder by adopting anhydrous ethanol and agate balls as wet grinding media and using 45 parts of talc, 33 parts of high-purity alumina and 22 parts of high-purity silicon dioxide according to mass fraction;
the composite ceramic powder comprises the following components in percentage by mass: agate ball: the absolute ethyl alcohol is 1:2:2, the ball milling time is 24 hours, and the grain diameter of the composite ceramic powder after ball milling is less than 10 um;
2) according to the mass parts, 9 parts of 1, 6-hexanediol diacrylate, 5 parts of dipentaerythritol hexaacrylate and 6 parts of bisphenol A epoxy acrylic resin form composite photosensitive resin; the photoinitiator is a free radical photoinitiator, namely benzil dimethyl ether, and the benzil dimethyl ether accounts for 1.5 percent of the total mass of the composite photosensitive resin; the additive comprises a plasticizer and a dispersant, wherein the plasticizer comprises polyethylene glycol 200 and polyethylene glycol 400, the composite photosensitive resin accounts for 70 parts by volume, the dosage of the plasticizer is 30 parts, and the dosage of each plasticizer is the same, namely 15 parts; the dispersant is Span80, and the using amount is 3 wt% of the mass of the ceramic powder; fully mixing the weighed composite photosensitive resin, photoinitiator and additive by adopting a planetary homogenizer to obtain a premixed solution;
3) and (2) gradually adding the composite ceramic powder into the premixed liquid, wherein the premixed liquid accounts for 65 parts by volume, the composite ceramic powder accounts for 35 parts by volume, and fully mixing and defoaming by adopting a planetary homogenizer to obtain the cordierite precursor photocuring paste.
The preparation method of the porous cordierite ceramic with the complex structure by utilizing the cordierite precursor photocuring paste comprises the following steps:
1) the printing process comprises the following steps: printing the cordierite precursor photocuring paste to obtain a printing sample piece; laser energy density 500mJ/cm 2 The layering thickness is 100 mu m, and the scraper speed is 15 mm/s;
2) degreasing process: degreasing the printing sample piece, wherein the degreasing atmosphere is argon, the degreasing process is divided into 6 sections according to a TG curve, and the 6 sections are respectively 0-190 ℃, 190-; after degreasing, presintering along with a furnace, raising the temperature to 800 ℃ at the speed of 3 ℃/min, and keeping the temperature for 1 h;
3) the carbon removal-sintering integrated process comprises the following steps: and (2) performing carbon removal-sintering on the degreased printing sample piece, wherein the carbon removal process is divided into 3 stages, namely 0-120 ℃, 120-plus-300 ℃ and 300-plus-500 ℃, respectively, wherein the temperature rise rate of the 300-plus-500 ℃ is 1 ℃/min, the heat preservation time of the end point temperature of 500 ℃ is 2h, the temperature rise rate of the rest stages is 1 ℃/min, the heat preservation time of the end point temperature of each stage is 2h, then the temperature is raised to the sintering temperature at the rate of 5 ℃/min, the sintering temperature is 1400 ℃, and the heat preservation time is 2 h.
Embodiment 8, a cordierite precursor photocuring paste, comprising composite ceramic powder and a premix, wherein the composite ceramic powder is 30 vol% of the paste;
the composite ceramic powder is talc, high-purity alumina powder and high-purity silicon dioxide; wherein the particle diameter of the talc is 15um, and the content of TiO 2 、Fe 2 O 3 Less than 3 wt% of total; the grain diameter of the high-purity alumina is 1 um; the particle size of the diatomite is 7 um; counting by weight parts, 45 parts of talc, 30 parts of high-purity alumina and 25 parts of diatomite;
the premixed liquid is a mixture of composite photosensitive resin, a photoinitiator and an additive; the composite photosensitive resin is a mixed solution of 1, 6-hexanediol diacrylate, dipentaerythritol hexaacrylate and bisphenol A type epoxy acrylic resin, and is counted according to parts by weight, 9 parts of 1, 6-hexanediol diacrylate, 5 parts of dipentaerythritol hexaacrylate and 6 parts of bisphenol A type epoxy acrylic resin; the photoinitiator is a free radical photoinitiator, namely benzil dimethyl ether, and the benzil dimethyl ether accounts for 1.5 percent of the total mass of the composite photosensitive resin; the additive comprises a plasticizer and a dispersant, wherein the plasticizer is dibutyl phthalate, the volume parts of the dibutyl phthalate are counted, the composite photosensitive resin is 95 parts, and the dosage of the plasticizer is 5 parts; the dispersant is Span80, and the usage amount is 3 wt% of the composite ceramic powder.
A preparation method of cordierite precursor photocuring paste comprises the following steps:
1) mixing the composite ceramic powder, namely preparing the composite ceramic powder by adopting anhydrous ethanol and agate balls as wet grinding media and using 45 parts of talc, 30 parts of high-purity alumina and 25 parts of diatomite according to mass fraction;
the composite ceramic powder comprises the following components in percentage by mass: agate ball: the absolute ethyl alcohol is 1:2:2, the ball milling time is 24 hours, and the grain diameter of the composite ceramic powder after ball milling is less than 10 um;
2) according to the mass parts, 9 parts of 1, 6-hexanediol diacrylate, 5 parts of dipentaerythritol hexaacrylate and 6 parts of bisphenol A epoxy acrylic resin form composite photosensitive resin; the photoinitiator is a free radical photoinitiator, namely benzil dimethyl ether, and the benzil dimethyl ether accounts for 1.5 percent of the total mass of the composite photosensitive resin; the additive comprises a plasticizer and a dispersant, wherein the plasticizer is dibutyl phthalate, the volume parts of the dibutyl phthalate are counted, the composite photosensitive resin is 95 parts, and the dosage of the plasticizer is 5 parts; the dispersant is Span80, and the using amount is 3 wt% of the mass of the ceramic powder; fully mixing the weighed composite photosensitive resin, photoinitiator and additive by adopting a planetary homogenizer to obtain a premixed solution;
3) and (3) gradually adding the composite ceramic powder into the premixed liquid, wherein the premixed liquid accounts for 70 parts by volume, the composite ceramic powder accounts for 30 parts by volume, and fully mixing and defoaming by adopting a planetary homogenizer to obtain the cordierite precursor photocuring paste.
The preparation method of the porous cordierite ceramic with the complex structure by utilizing the cordierite precursor photocuring paste comprises the following steps:
1) the printing process comprises the following steps: printing the cordierite precursor photocuring paste to obtain a printing sample piece; laser energy density 70mJ/cm 2 The layering thickness is 25 mu m, and the scraper speed is 20 mm/s;
2) degreasing process: degreasing the printing sample piece, wherein the degreasing atmosphere is argon, the degreasing process is divided into 6 sections according to a TG curve, and the 6 sections are respectively 0-190 ℃, 190-; after degreasing, presintering along with a furnace, raising the temperature to 800 ℃ at the speed of 3 ℃/min, and keeping the temperature for 1 h;
3) the carbon removal-sintering integrated process comprises the following steps: and (2) performing carbon removal-sintering on the degreased printing sample piece, wherein the carbon removal process is divided into 3 stages, namely 0-120 ℃, 120-plus-300 ℃ and 300-plus-500 ℃, respectively, wherein the temperature rise rate of the 300-plus-500 ℃ is 1 ℃/min, the heat preservation time of the end point temperature of 500 ℃ is 2h, the temperature rise rate of the rest stages is 1 ℃/min, the heat preservation time of the end point temperature of each stage is 2h, then the temperature is raised to the sintering temperature at the rate of 5 ℃/min, the sintering temperature is 1400 ℃, and the heat preservation time is 3 h.

Claims (7)

1. A cordierite precursor photocuring paste is characterized in that: the paste comprises composite ceramic powder and a premixed liquid, wherein the composite ceramic powder accounts for 30-45 vol% of the paste in parts by volume;
the composite ceramic powder is one or two of talc, high-purity alumina powder and high-purity silicon dioxide or diatomite; counting by weight parts, 40-50 parts of talc, 30-40 parts of high-purity alumina, 0-25 parts of high-purity silicon dioxide and 0-25 parts of diatomite;
the premixed liquid is a mixture of composite photosensitive resin, a photoinitiator and an additive; the composite photosensitive resin is a mixed solution of 1, 6-hexanediol diacrylate, dipentaerythritol hexaacrylate and bisphenol A type epoxy acrylic resin, and the mixed solution is counted by weight parts, 8-10 parts of 1, 6-hexanediol diacrylate, 5-7 parts of dipentaerythritol hexaacrylate and 4-6 parts of bisphenol A type epoxy acrylic resin; the photoinitiator is a free radical photoinitiator, namely benzil dimethyl ether, and the benzil dimethyl ether accounts for 0.5-2% of the total mass of the composite photosensitive resin; the additive comprises a plasticizer and a dispersant, wherein the plasticizer is one or more of polyethylene glycol 200, polyethylene glycol 400 and dibutyl phthalate, the composite photosensitive resin accounts for 64-95 parts by volume, and the dosage of the plasticizer is 5-36 parts; the dispersant is Span80, and the usage amount is 0.5 wt% -5 wt% of the composite ceramic powder.
2. A cordierite precursor photocurable paste according to claim 1 wherein: the particle diameter of the talc is 2.6-45 um, and the content of TiO in the talc 2 、Fe 2 O 3 Less than 3 wt% of total; the grain diameter of the high-purity alumina is 0.3um-5 um; the grain size of the high-purity silicon oxide is between 0.3um and 5 um; the diatomite has a particle size of 1-10 μm and contains TiO 2 、Fe 2 O 3 Less than 3 wt% of total Na 2 O、K 2 The total content of O is less than 1%.
3. The method for preparing a cordierite precursor photocurable paste according to claim 1, comprising the steps of:
1) mixing composite ceramic powder, namely preparing the composite ceramic powder by adopting anhydrous ethanol and agate balls as wet grinding media and using 40-50 parts of talc, 30-40 parts of high-purity alumina, 0-25 parts of high-purity silicon dioxide and 0-25 parts of diatomite according to mass fraction;
the composite ceramic powder comprises the following components in percentage by mass: agate ball: the absolute ethyl alcohol is 1:2:2, the ball milling time is 18-30 hours, and the grain diameter of the composite ceramic powder after ball milling is less than 10 um;
2) according to the mass portion, 8-10 portions of 1, 6-hexanediol diacrylate, 5-7 portions of dipentaerythritol hexaacrylate and 4-6 portions of bisphenol A epoxy acrylic resin are mixed to form composite photosensitive resin; the photoinitiator is a free radical photoinitiator, namely benzil dimethyl ether, and the benzil dimethyl ether accounts for 0.5-2% of the total mass of the composite photosensitive resin; the additive comprises a plasticizer and a dispersant, wherein the plasticizer is one or more of polyethylene glycol 200, polyethylene glycol 400 and dibutyl phthalate, the composite photosensitive resin accounts for 64-95 parts by volume, and the dosage of the plasticizer is 5-36 parts; the dispersant is Span80, and the using amount is 0.5 wt% -5 wt% of the composite ceramic powder; fully mixing the weighed composite photosensitive resin, photoinitiator and additive by adopting a planetary homogenizer to obtain a premixed solution;
3) and (2) gradually adding the composite ceramic powder into the premixed liquid, wherein the premixed liquid accounts for 55-70 parts by volume, the composite ceramic powder accounts for 30-45 parts by volume, and fully mixing and defoaming by adopting a planetary homogenizer to obtain the cordierite precursor photocuring paste.
4. A method for producing a porous cordierite ceramic of a complex structure using the cordierite precursor photocurable paste of claim 1, comprising the steps of:
1) the printing process comprises the following steps: printing the cordierite precursor photocuring paste to obtain a printing sample piece; laser energy density of 70-567mJ/cm 2 The layering thickness is 25-100 mu m, and the scraper speed is 10-20 mm/s;
2) degreasing process: degreasing the printing sample piece, wherein the degreasing atmosphere is argon, the degreasing process is divided into 6 sections according to a TG curve, and the 6 sections are respectively 0-190 ℃, 190-; after degreasing, presintering along with a furnace, raising the temperature to 800 ℃ at the speed of 3 ℃/min, and keeping the temperature for 1 h;
3) the carbon removal-sintering integrated process comprises the following steps: and (2) performing carbon removal-sintering on the degreased printing sample piece, wherein the carbon removal process is divided into 3 stages, namely 0-120 ℃, 120-phase temperature 300 ℃ and 300-phase temperature 500 ℃, wherein the temperature rise rate of the 300-phase temperature 500 ℃ is 1 ℃/min, the heat preservation time of the end point temperature 500 ℃ is 2h, the temperature rise rate of the rest stages is 1 ℃/min-5 ℃/min, the heat preservation time of the end point temperature of each stage is 0.5-2h, then the temperature is raised to the sintering temperature at the rate of 5 ℃/min, the sintering temperature is 1250-phase temperature 1400 ℃, and the heat preservation time is 1-5 h.
5. A cordierite precursor photocuring paste is characterized in that: the paste comprises composite ceramic powder and a premixed liquid, wherein the composite ceramic powder accounts for 33 vol% of the paste in parts by volume;
the composite ceramic powder is talc, high-purity alumina powder and high-purity silicon dioxide; wherein the particle diameter of the talc is 14.05um, and the content of TiO is 2 、Fe 2 O 3 Less than 3 wt% of total; the grain diameter of the high-purity alumina is 1.61 um; the grain size of the high-purity silicon oxide is 2.15 um; 45 parts of talc, 33 parts of high-purity alumina and 22 parts of high-purity silicon dioxide;
the premixed liquid is a mixture of composite photosensitive resin, a photoinitiator and an additive; the composite photosensitive resin is a mixed solution of 1, 6-hexanediol diacrylate, dipentaerythritol hexaacrylate and bisphenol A type epoxy acrylic resin, and is counted according to parts by weight, 9 parts of 1, 6-hexanediol diacrylate, 6 parts of dipentaerythritol hexaacrylate and 5 parts of bisphenol A type epoxy acrylic resin; the photoinitiator is a free radical photoinitiator, namely benzil dimethyl ether, and the benzil dimethyl ether accounts for 0.5 percent of the total mass of the composite photosensitive resin; the additive comprises a plasticizer and a dispersant, wherein the plasticizer is dibutyl phthalate, and the volume part number of the dibutyl phthalate is 73 parts, and the using amount of the plasticizer is 27 parts; the dispersant is Span80, and the usage amount is 1 wt% of the composite ceramic powder.
6. A method of making a cordierite precursor photocurable paste according to claim 5 comprising the steps of:
1) mixing the composite ceramic powder, namely preparing the composite ceramic powder by adopting anhydrous ethanol and agate balls as wet grinding media and using 45 parts of talc, 33 parts of high-purity alumina and 22 parts of high-purity silicon dioxide according to mass fraction;
the composite ceramic powder comprises the following components in percentage by mass: agate ball: the absolute ethyl alcohol is 1:2:2, the ball milling time is 24 hours, and the grain diameter of the composite ceramic powder after ball milling is less than 10 um;
2) according to the mass parts, 9 parts of 1, 6-hexanediol diacrylate, 6 parts of dipentaerythritol hexaacrylate and 5 parts of bisphenol A epoxy acrylic resin form composite photosensitive resin; the photoinitiator is a free radical photoinitiator, namely benzil dimethyl ether, and the benzil dimethyl ether accounts for 0.5 percent of the total mass of the composite photosensitive resin; the additive comprises a plasticizer and a dispersant, wherein the plasticizer is dibutyl phthalate, and the plasticizer is 73 parts by volume of the composite photosensitive resin, and the using amount of the dibutyl phthalate is 27 parts by volume; the dispersant is Span80, and the using amount is 1 wt% of the composite ceramic powder; fully mixing the weighed composite photosensitive resin, photoinitiator and additive by adopting a planetary homogenizer to obtain a premixed solution;
3) and (2) adding the composite ceramic powder into the premixed liquid in a successive manner, wherein the premixed liquid accounts for 67 parts by volume, and the composite ceramic powder accounts for 33 parts by volume, and fully mixing and defoaming by adopting a planetary homogenizer to obtain the cordierite precursor photocuring paste.
7. A method for producing a porous cordierite ceramic of a complex structure using the cordierite precursor photocurable paste according to claim 5, comprising the steps of:
1) the printing process comprises the following steps: printing the cordierite precursor photocuring paste to obtain a printing sample piece; laser energy density of 191.5mJ/cm 2 The layering thickness is 50 mu m, and the scraper speed is 15 mm/s;
2) degreasing process: degreasing the printing sample piece, wherein the degreasing atmosphere is argon, the degreasing process is divided into 6 sections according to a TG curve, and the 6 sections are respectively 0-190 ℃, 190-; after degreasing, presintering along with a furnace, raising the temperature to 800 ℃ at the speed of 3 ℃/min, and keeping the temperature for 1 h;
3) the carbon removal-sintering integrated process comprises the following steps: and (2) performing carbon removal-sintering on the degreased printing sample piece, wherein the carbon removal process is divided into 3 stages, namely 0-120 ℃, 120-phase temperature 300 ℃ and 300-phase temperature 500 ℃, wherein the heating rate of the 300-phase temperature 500 ℃ is 1 ℃/min, the heat preservation time of the end point temperature 500 ℃ is 2h, the heating rate of the rest stages is 1 ℃/min, the heat preservation time of the end point temperature of each stage is 0.5h, then the temperature is raised to the sintering temperature at the rate of 5 ℃/min, the sintering temperature is 1400 ℃, and the heat preservation time is 1 h.
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