CN112500026B - Short-cut quartz fiber reinforced silicon oxide ceramic paste for photocuring and preparation method thereof - Google Patents

Short-cut quartz fiber reinforced silicon oxide ceramic paste for photocuring and preparation method thereof Download PDF

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CN112500026B
CN112500026B CN202011398158.0A CN202011398158A CN112500026B CN 112500026 B CN112500026 B CN 112500026B CN 202011398158 A CN202011398158 A CN 202011398158A CN 112500026 B CN112500026 B CN 112500026B
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CN112500026A (en
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鲍崇高
董文彩
李世佳
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Xian Jiaotong University
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    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B26/00—Compositions of mortars, concrete or artificial stone, containing only organic binders, e.g. polymer or resin concrete
    • C04B26/02—Macromolecular compounds
    • C04B26/04—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C04B26/06—Acrylates
    • 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
    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/00034—Physico-chemical characteristics of the mixtures
    • C04B2111/00181—Mixtures specially adapted for three-dimensional printing (3DP), stereo-lithography or prototyping

Abstract

A light-cured short-cut quartz fiber reinforced silicon oxide ceramic paste and a preparation method thereof are disclosed, wherein bundled short-cut quartz fibers are prepared into single-filament short-cut quartz fibers; then SiO2Mixing the powder with a powder dispersing agent, carrying out ball milling treatment by a ball mill, sieving and drying to obtain a solid mixture; adding a photoinitiator and a silane coupling agent into the resin mixed solution, performing ball milling to obtain a photocuring resin system, adding the photocuring resin system into the solid mixture, simultaneously dripping a light absorbing agent, stirring the mixture into flocculent, then putting the flocculent mixture into a homogenizing mixer for mixing and vacuumizing to obtain a silicon oxide ceramic paste; finally, adding the single-filament chopped quartz fibers into the silicon oxide ceramic paste, and uniformly mixing in a homogenizing mixer to obtain the photocuring chopped quartz fiber reinforced silicon oxide ceramic paste; the obtained paste has the characteristics of high printing precision, high solid content, uniform fiber dispersion and the like.

Description

Short-cut quartz fiber reinforced silicon oxide ceramic paste for photocuring and preparation method thereof
Technical Field
The invention belongs to the technical field of silicon oxide ceramic additive manufacturing, and particularly relates to a short quartz fiber reinforced silicon oxide ceramic paste for photocuring and a preparation method thereof.
Background
The additive manufacturing technology is developed for more than 30 years, the molding technology comprises a fused deposition molding technology, a laser sintering/cladding technology, a three-dimensional light curing molding (SLA) technology and the like, and the additive manufacturing technology has a series of advantages of high molding speed, high precision, capability of quickly finishing manufacturing complex parts and the like. The photocuring forming means that liquid photosensitive resin is used as a raw material, and an ultraviolet light source scans the cured resin layer by layer according to a certain scanning path until printing is finished; the printing precision is high, the technology is mature, and the printing method is an additive manufacturing technology which is better developed and more promising at present. The silicon oxide ceramic has excellent dielectric property, good corrosion resistance and chemical stability, higher high temperature resistance and larger application prospect in the aspects of aerospace, chemical engineering, buildings and the like.
At present, the missile radome material used in China is mainly quartz fiber reinforced silicon oxide ceramic, and is applied in batches in multiple models, and the production mode generally adopts the traditional forming method, such as fiber weaving, dipping, compression molding, hot-pressing injection molding and the like. However, the traditional forming methods have the defects of complex process, long construction period, unstable performance and the like to different degrees, are difficult to realize the design requirements of precise and complex parts, and seriously restrict the further development of the high-performance antenna housing/window. SLA forming realizes the production and manufacture of solid parts by printing layer by layer from bottom to top through a method of gradually accumulating materials without a die, and the produced parts have the characteristics of high precision, simple process, low cost, short period, diversified forming and the like compared with the traditional manufacturing process, thereby being a silicon oxide ceramic forming method with higher forming precision. At present, many colleges and scientific research institutes research the photocuring forming technology of silica ceramic, but there are reports on the research of silica fiber reinforced silica ceramic paste, so how to realize the preparation and SLA forming of silica fiber reinforced silica ceramic paste has important significance for the development of preparing high-performance antenna housing/window.
The configuration of the silica ceramic paste reinforced by quartz fiber for photocuring is one of the key technologies for realizing SLA additive manufacturing and forming of silica ceramic. The sintering performance of the ceramic printing finished product is closely related to the ceramic paste, and the dispersion uniformity of the fibers, the solid content of the paste, the forming precision and the like have direct influence on the final performance of the product.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide the chopped quartz fiber reinforced silicon oxide ceramic paste for photocuring and the preparation method thereof, and the paste has the characteristics of high printing precision, high solid content, uniform fiber dispersion and the like.
In order to achieve the purpose, the invention adopts the technical scheme that:
a light-cured short-cut quartz fiber reinforced silicon oxide ceramic paste comprises spherical SiO2Powder with a density of 2.2 g/ml; the content of SiO25 to 10 weight percent of powder, and the density is 2.2 g/ml; the content of SiO21 to 1.5 weight percent of powder dispersant; with SiO2The volume ratio of the powder to the quartz fiber mixture is (37.0-40.7): (63.0-59.3) the resin mixture solution, the density of which is 1.09 g/ml; a photoinitiator with the content of 1.75wt% of the mass of the resin mixed solution; silane coupling agent with the content of 1-1.5 wt% of the resin mixed solution; the content of the light absorbent is 1-5 per mill of the resin mixed solution;
the SiO2The powder is a mixture of particles with the particle size d 50-1 um and d 50-200 nm mixed according to the mass fraction of 7: 3;
the powder dispersing agent is stearic acid;
the light absorbent is light absorbent N30;
the resin mixed solution is a mixture of monomer hexahydrophthalic acid diglycidyl ether, 1,6 hexanediol diacrylate (HDDA) and dipentaerythritol penta/hexaacrylate (DPHA), and the mass ratio of the monomer hexahydrophthalic acid diglycidyl ether to the monomer 1,6 hexanediol diacrylate (HDDA) to the monomer dipentaerythritol penta/hexaacrylate (DPHA) is 5.5: 3.5: 1.0;
the photoinitiator is diaryl iodonium salt with the content of 1.25wt% of the mass of the monomer hexahydrophthalic acid diglycidyl ether, and benzoin dimethyl ether with the content of 0.5wt% of the mass fraction of the mixture of 1,6 hexanediol diacrylate (HDDA) and dipentaerythritol penta/hexaacrylate (DPHA), wherein the benzoin dimethyl ether can be partially or completely replaced by 2, 4, 6-trimethylbenzoyl diphenyl phosphine oxide, and the diaryl iodonium salt can be partially or completely replaced by diaryl sulfonium salt;
the silane coupling agent is gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane (KH 560).
A preparation method of a chopped quartz fiber reinforced silicon oxide ceramic paste for photocuring comprises the following steps:
step 1: putting the bundle-shaped short-cut quartz fibers into distilled water, boiling at 95 ℃ for 2-5 h, and then drying in an oven at 60 ℃ for 8-12 h; placing the dried bundle-shaped chopped quartz fibers in a degreasing furnace at 400 ℃ for treatment for 4-6 h, and kneading to obtain monofilament chopped quartz fibers;
step 2: respectively weighing SiO with two particle sizes according to the mass ratio2Powder, powder dispersant, light absorbent, resin mixed liquid, photoinitiator and silane coupling agent;
and step 3: mixing SiO2Mixing the powder with a powder dispersant, and performing ball milling treatment by a ball mill
Figure BDA0002816071220000031
5-10 mm, and the addition amount is SiO2The mass of the powder is 1.0-1.5 times, the parameters of the ball mill are set to be 300-350 r/min, and the total time is 12-16 h;
and 4, step 4: sieving the mixture obtained in the step 3 through a 100-mesh sieve, placing the mixture in an oven, and drying at 60 ℃/12 h;
and 5: adding a photoinitiator and a silane coupling agent into the resin mixed solution, placing the resin mixed solution on a ball mill for 250-400 r/min, ball-milling for 3 hours and uniformly mixing to obtain a photocuring resin system, gradually adding the photocuring resin system into the solid mixture obtained in the step 4 according to the mass ratio, simultaneously dropping a light absorbing agent, stirring the mixture to be flocculent, then placing the flocculent mixture into a homogenizing mixer for mixing and vacuumizing, and setting the parameters of the homogenizing mixer to be 1000-1500 r/min-1/20s+2000～2500r﹒min-1/30s+2500～2800r﹒min-1The silicon oxide ceramic paste is obtained after 20 seconds;
step 6: adding the monofilament chopped quartz fibers prepared in the step 1 into the silicon oxide ceramic paste obtained in the step 5, manually stirring, placing in a homogenizing mixer, and setting the parameter to be 2000-2500 r for min-1/20s+2500～2800r﹒min-1And/30 s, mixing twice to obtain the light-curing chopped quartz fiber reinforced silicon oxide ceramic paste.
The invention has the beneficial effects that:
1. the treated monofilament chopped quartz fibers are added into the paste material and uniformly dispersed in the silicon oxide ceramic paste material, so that on one hand, the strength of the material can be improved, and on the other hand, the monofilament chopped quartz fibers can prevent the expansion and extension of cracks and play a role of preventing deformation and cracking in the post-treatment process.
2. The light absorbing agent is added into the paste, so that the light absorption rate of the paste is improved, and the printing precision is improved.
3. The paste materials are mixed in a grading way through the homogenizing mixer, the speed is high, the time is short, and the uniform and stable distribution of the monofilament chopped quartz fibers in the paste materials is facilitated.
Drawings
Fig. 1 shows a product of a light-curing chopped quartz fiber-reinforced silica ceramic paste and the distribution of fibers thereof in example 1 of the present invention, in which the fiber distribution in a single-layer cured sheet is observed with an ultra-deep-field fiberscope, and a) and b) are the light-curing chopped quartz fiber-reinforced silica ceramic paste, and c) is the fiber distribution in the light-curing chopped quartz fiber-reinforced silica ceramic paste (the bars in the frame are monofilament fibers).
Detailed Description
The present invention will be described in detail with reference to examples.
Example 1A chopped Quartz fiber-reinforced silica ceramic paste for photocuring comprising as a component spherical SiO2Powder with a density of 2.2 g/ml; the content of SiO210wt% of powder of a strand-shaped chopped quartz fiber having a density of 2.2 g/ml; the content of SiO21wt% of powder dispersant; with SiO2The volume ratio of the powder to the quartz fiber mixture was 37.0: 63.0 of resin mixed solution, the density is 1.09 g/ml; a photoinitiator with the content of 1.75wt% of the mass of the resin mixed solution; silane coupling agent with the content of 1.5wt percent of the resin mixed solution; the content is 5 per mill of light absorbent of resin mixed solution;
the SiO2The powder is a mixture of particles with the particle size d 50-1 um and d 50-200 nm mixed according to the mass fraction of 7: 3;
the powder dispersing agent is stearic acid;
the light absorbent is light absorbent N30;
the resin mixed solution is a mixture of monomer hexahydrophthalic acid diglycidyl ether, 1,6 hexanediol diacrylate (HDDA) and dipentaerythritol penta/hexaacrylate (DPHA), and the mass ratio of the monomer hexahydrophthalic acid diglycidyl ether to the monomer 1,6 hexanediol diacrylate (HDDA) to the monomer dipentaerythritol penta/hexaacrylate (DPHA) is 5.5: 3.5: 1.0;
the photoinitiator is diaryl iodonium salt with the content of 1.25wt% of the mass of the monomer hexahydrophthalic acid diglycidyl ether, and benzoin dimethyl ether with the content of 0.5wt% of the mass fraction of the mixture of 1,6 hexanediol diacrylate (HDDA) and dipentaerythritol penta/hexaacrylate (DPHA);
the silane coupling agent is gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane (KH 560).
The preparation method of the chopped quartz fiber reinforced silicon oxide ceramic paste for photocuring comprises the following steps:
step 1: weighing bundle-shaped chopped quartz fibers, putting the bundle-shaped chopped quartz fibers into distilled water, boiling the mixture for 2 hours at 95 ℃, and then putting the mixture into an oven to dry the mixture for 8 hours at 60 ℃; placing the dried bundle-shaped chopped quartz fibers in a degreasing furnace at 400 ℃ for treatment for 4 hours, and lightly kneading to obtain monofilament chopped quartz fibers;
step 2: respectively weighing SiO with two particle sizes according to the mass ratio2Powder, powder dispersant, light absorbent, resin mixed liquid, photoinitiator and silane coupling agent;
and step 3: mixing SiO2Mixing the powder with a powder dispersant, and performing ball milling treatment by a ball mill
Figure BDA0002816071220000061
5-10 mm, and the addition amount is SiO2The mass of the powder is 1.5 times, the parameters of the ball mill are set to 350r/min, and the total time is 12 hours;
and 4, step 4: sieving the mixture obtained in the step 3 through a 100-mesh sieve, placing the mixture in an oven, and drying at 60 ℃/12 h;
and 5: adding a photoinitiator and a silane coupling agent into the resin mixed solution, placing the mixture on a ball mill, and carrying out ball milling for 3 hours at a speed of 250r/min to obtain a photocuring resin system; then gradually adding the light-cured resin system into the solid mixture obtained in the step 4, simultaneously dripping the light absorbing agent, stirring the mixture into floccules, and then putting the floccules into a homogenizing mixerLine mix and vacuum, homogenizer Mixer with parameters set to 1500r min-1/20s+2000r﹒min-1/30s+2500r﹒min-1The silicon oxide ceramic paste is obtained after 20 seconds;
step 6: adding the monofilament chopped quartz fibers prepared in the step 1 into the silicon oxide ceramic paste obtained in the step 5, manually stirring, placing in a homogenizing mixer, setting the parameter as 2000r for min-1/20s+2800r﹒min-130s, mixing twice to obtain the photocuring chopped quartz fiber reinforced silica ceramic paste with the volume fraction of 63.0 vol%; as shown in FIG. 1, it can be seen from FIGS. a) and b) that the paste prepared is creamy with moderate viscosity, soft in texture but not easy to flow, and therefore easy to scrape and act as a support during forming; the graph c) is a single-layer solidified sheet of the paste in SLA forming, after being treated for 4 hours at 200 ℃, the fiber distribution of the single-layer solidified sheet is observed by using a super-depth-of-field microscope, and the strip-shaped objects shown in the graph are fibers; as can be seen from fig. c), the fibers are uniformly distributed, and after the doctor blade action, the fibers exhibit a distinct orientation distribution characteristic.
Example 2A chopped Quartz fiber-reinforced silica ceramic paste for photocuring comprising a spherical SiO2Powder with a density of 2.2 g/ml; the content of SiO25wt% of powder of a strand-shaped chopped quartz fiber having a density of 2.2 g/ml; the content of SiO2Powder 1.5wt% of a powder dispersant; with SiO2The volume ratio of the powder to the quartz fiber mixture was 40.7: 59.3, the density is 1.09 g/ml; a photoinitiator with the content of 1.75wt% of the mass of the resin mixed solution; silane coupling agent with the content of 1wt% of the resin mixed liquid; the content is 1 per mill of light absorbent of resin mixed solution;
the SiO2The powder is a mixture of particles with the particle size d 50-1 um and d 50-200 nm mixed according to the mass fraction of 7: 3;
the powder dispersing agent is stearic acid;
the light absorbent is light absorbent N30;
the resin mixed solution is a mixture of monomer hexahydrophthalic acid diglycidyl ether, 1,6 hexanediol diacrylate (HDDA) and dipentaerythritol penta/hexaacrylate (DPHA), and the mass ratio of the monomer hexahydrophthalic acid diglycidyl ether to the monomer 1,6 hexanediol diacrylate (HDDA) to the monomer dipentaerythritol penta/hexaacrylate (DPHA) is 5.5: 3.5: 1.0;
the photoinitiator is diaryl iodonium salt with the content of 1.25wt% of the mass of the monomer hexahydrophthalic acid diglycidyl ether, and 2.4.6-trimethylbenzoyl diphenyl phosphine oxide with the content of 0.5wt% of the mass fraction of the mixture of 1,6 hexanediol diacrylate (HDDA) and dipentaerythritol penta/hexaacrylate (DPHA);
the silane coupling agent is gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane (KH 560).
A preparation method of a chopped quartz fiber reinforced silicon oxide ceramic paste for photocuring comprises the following steps:
step 1: weighing bundle-shaped chopped quartz fibers, putting the bundle-shaped chopped quartz fibers into distilled water, boiling the mixture for 5 hours at 95 ℃, and then putting the mixture into an oven to dry the mixture for 12 hours at 60 ℃; placing the dried bundle-shaped chopped quartz fibers in a degreasing furnace at 400 ℃ for treatment for 6h, and lightly kneading to obtain monofilament chopped quartz fibers;
step 2: respectively weighing SiO with two particle sizes according to the mass ratio2Powder, powder dispersant, light absorbent, resin mixed liquid, photoinitiator and silane coupling agent;
and step 3: mixing SiO2Mixing the powder with a powder dispersant, and performing ball milling treatment by a ball mill
Figure BDA0002816071220000081
5-10 mm, and the addition amount is SiO21.0 time of the powder mass, setting the parameters of the ball mill to be 300r/min, and carrying out ball milling for 16 h;
and 4, step 4: sieving the mixture obtained in the step 3 through a 100-mesh sieve, placing the mixture in an oven, and drying at 60 ℃/12 h;
and 5: adding a photoinitiator and a silane coupling agent into the resin mixed solution, placing the mixture on a ball mill, and carrying out ball milling for 3 hours at the speed of 400r/min to obtain a photocuring resin system; and (3) gradually adding the light-cured resin system into the solid mixture obtained in the step (4), simultaneously dripping the light absorbing agent, stirring the mixture into floccules, then placing the floccules into a homogenizing mixer for mixing, vacuumizing, homogenizing and mixingSetting the Material machine parameter to 1000r min-1/20s+2500r﹒min-1/30s+2800r﹒min-1The silicon oxide ceramic paste is obtained after 20 seconds;
step 6: and (3) adding the monofilament chopped quartz fibers prepared in the step (1) into the silica ceramic paste obtained in the step (5), manually stirring, placing in a homogenizing mixer, setting the parameters to 2500 r-1/20 s +2500 r-1/30 s, and mixing twice to obtain the chopped quartz fiber reinforced silica ceramic paste for photocuring, wherein the volume fraction of the chopped quartz fiber reinforced silica ceramic paste is 59.3 vol%.
Example 3A chopped Quartz fiber-reinforced silica ceramic paste for photocuring comprising as a component spherical SiO2Powder with a density of 2.2 g/ml; the content of SiO2Chopped quartz fiber in the shape of a bundle with 7wt% of powder and the density of 2.2 g/ml; the content of SiO21.2wt% of powder dispersant; with SiO2The volume ratio of the powder to the quartz fiber mixture is 38.1:61.9, and the density is 1.09 g/ml; a photoinitiator with the content of 1.75wt% of the mass of the resin mixed solution; silane coupling agent with the content of 1.3wt percent of the resin mixed solution; the content of the light absorbent is 2.1 per mill of the resin mixed solution;
the SiO2The powder is a mixture of particles with the particle size d 50-1 um and d 50-200 nm mixed according to the mass fraction of 7: 3;
the powder dispersing agent is stearic acid;
the light absorbent is light absorbent N30;
the resin mixed solution is a mixture of monomer hexahydrophthalic acid diglycidyl ether, 1,6 hexanediol diacrylate (HDDA) and dipentaerythritol penta/hexaacrylate (DPHA), and the mass ratio of the monomer hexahydrophthalic acid diglycidyl ether to the monomer 1,6 hexanediol diacrylate (HDDA) to the monomer dipentaerythritol penta/hexaacrylate (DPHA) is 5.5: 3.5: 1.0;
the photoinitiator is diaryl thionine with the content of 1.25wt% of the mass of the monomer hexahydrophthalic acid diglycidyl ether, and benzoin dimethyl ether with the content of 0.5wt% of the mass fraction of the mixture of 1,6 hexanediol diacrylate (HDDA) and dipentaerythritol penta/hexaacrylate (DPHA);
the silane coupling agent is gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane (KH 560).
The preparation method of the chopped quartz fiber reinforced silicon oxide ceramic paste for photocuring comprises the following steps:
step 1: weighing bundle-shaped chopped quartz fibers, putting the bundle-shaped chopped quartz fibers into distilled water, boiling the mixture for 3 hours at 95 ℃, and then putting the mixture into an oven to dry the mixture for 10 hours at 60 ℃; placing the dried bundle-shaped chopped quartz fibers in a degreasing furnace at 400 ℃ for treatment for 5 hours, and lightly kneading to obtain monofilament chopped quartz fibers;
step 2: respectively weighing SiO with two particle sizes according to the mass ratio2Powder, powder dispersant, light absorbent, resin mixed liquid, photoinitiator and silane coupling agent;
and step 3: mixing SiO2Mixing the powder with a powder dispersant, and performing ball milling treatment by a ball mill
Figure BDA0002816071220000091
5-10 mm, and the addition amount is SiO2The weight of the powder is 1.3 times, the parameters of the ball mill are set to 330r/min, and the total time is 14 hours;
and 4, step 4: sieving the mixture obtained in the step 3 through a 100-mesh sieve, placing the mixture in an oven, and drying at 60 ℃/12 h;
and 5: adding a photoinitiator and a silane coupling agent into the resin mixed solution, placing the mixture on a ball mill, and carrying out ball milling for 3 hours at the speed of 350r/min to obtain a photocuring resin system; and then gradually adding the photocuring resin system into the solid mixture obtained in the step 4, simultaneously dripping the light absorbing agent into the mixture, stirring the mixture into floccules, then putting the floccules into a homogenizing mixer for mixing and vacuumizing, and setting the parameter of the homogenizing mixer to 1300r for min-1/20s+2200r﹒min-1/30s+2700r﹒min-1The silicon oxide ceramic paste is obtained after 20 seconds;
step 6: adding the monofilament chopped quartz fibers prepared in the step 1 into the silicon oxide ceramic paste obtained in the step 5, manually stirring, placing in a homogenizing mixer, setting the parameter as 2300r for min-1/20s+2700r﹒min-1And/30 s, mixing twice to obtain the chopped quartz fiber reinforced silica ceramic paste for photocuring, wherein the volume fraction of the paste is 61.9 vol%.

Claims (5)

1. A preparation method of a short-cut quartz fiber reinforced silicon oxide ceramic paste for photocuring is characterized by comprising the following steps: a light-cured short-cut quartz fiber reinforced silicon oxide ceramic paste comprises spherical SiO2Powder with a density of 2.2 g/ml; the content of SiO25-10 wt% of powder, wherein the density of the bundled chopped quartz fiber is 2.2 g/ml; the content of SiO21-1.5 wt% of powder dispersant; with SiO2The volume ratio of the powder to the quartz fiber mixture is (37.0-40.7): (63.0-59.3) the resin mixture solution, the density of which is 1.09 g/ml; a photoinitiator with the content of 1.75wt% of the mass of the resin mixed solution; silane coupling agent with the content of 1-1.5 wt% of resin mixed liquid; the content of the light absorbent is 1-5 per mill of the resin mixed solution;
the SiO2The powder is a mixture with the particle size of d50= 1-2 um and d50=200nm mixed according to the mass fraction of 7: 3;
the powder dispersing agent is stearic acid;
the light absorbent is light absorbent N30;
the resin mixed solution is a mixture of monomer hexahydrophthalic acid diglycidyl ether, 1,6 hexanediol diacrylate (HDDA) and dipentaerythritol penta/hexaacrylate (DPHA), and the mass ratio of the monomer hexahydrophthalic acid diglycidyl ether to the monomer 1,6 hexanediol diacrylate (HDDA) to the monomer dipentaerythritol penta/hexaacrylate (DPHA) is 5.5: 3.5: 1.0;
the photoinitiator is diaryl iodonium salt with the content of 1.25wt% of the mass of the monomer hexahydrophthalic acid diglycidyl ether, and benzoin dimethyl ether with the content of 0.5wt% of the mass fraction of the mixture of 1,6 hexanediol diacrylate (HDDA) and dipentaerythritol penta/hexaacrylate (DPHA);
the silane coupling agent is gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane (KH 560);
the preparation method of the chopped quartz fiber reinforced silicon oxide ceramic paste for photocuring comprises the following steps:
step 1: putting the bundle-shaped chopped quartz fiber into distilled water, boiling for 2h at 95 ℃, and then putting into a drying oven, and drying for 12h at 60 ℃; placing the dried bundle-shaped chopped quartz fibers in a degreasing furnace at 400 ℃ for treatment for 4h, and kneading to obtain monofilament chopped quartz fibers;
step 2: respectively weighing SiO with two particle sizes according to the mass ratio2Powder, powder dispersant, light absorbent, resin mixed liquid, photoinitiator and silane coupling agent;
and step 3: mixing SiO2Mixing the powder and a powder dispersing agent, and carrying out ball milling treatment by a ball mill, wherein the diameter of a milling ball is 5-10 mm, and the addition amount of the milling ball is SiO2The mass of the powder is 1.0-1.5 times, the parameters of the ball mill are set to be 300-350 r/min, and the total time is 12-16 h;
and 4, step 4: sieving the mixture obtained in the step 3 through a 100-mesh sieve, placing the mixture in an oven, and drying at 60 ℃/12 h;
and 5: adding a photoinitiator and a silane coupling agent into the resin mixed solution, placing the mixture on a ball mill for 250r/min, ball-milling for 3h, uniformly mixing to obtain a photocuring resin system, gradually adding the photocuring resin system into the solid mixture obtained in the step 4 according to the mass ratio, simultaneously dripping the light absorbing agent, stirring the mixture to be flocculent, then placing the flocculent mixture into a homogenizing mixer for mixing and vacuumizing, and setting the parameters of the homogenizing mixer to be 1500 r/min-1/20s+2000r﹒min-1 /30s + 2500r﹒min-1The silicon oxide ceramic paste is obtained after 20 seconds;
step 6: adding the monofilament chopped quartz fibers prepared in the step 1 into the silicon oxide ceramic paste obtained in the step 5, manually stirring, placing in a homogenizing mixer, setting the parameter as 2000r for min-1/20s+2800r﹒min-1And/30 s, mixing twice to obtain the light-curing chopped quartz fiber reinforced silicon oxide ceramic paste.
2. The method for preparing a chopped quartz fiber reinforced silica ceramic paste for photocuring as set forth in claim 1, wherein the method comprises the steps of: in the photoinitiator, benzoin bis methyl ether can be partially or completely replaced by 2, 4, 6-trimethylbenzoyl diphenyl phosphine oxide, and diaryl iodonium salt can be partially or completely replaced by diaryl sulfonium salt.
3. A photocuring of claim 1The preparation method of the silica ceramic paste reinforced by the short-cut quartz fiber is characterized by comprising the following steps: a light-cured short-cut quartz fiber reinforced silicon oxide ceramic paste comprises spherical SiO2Powder with a density of 2.2 g/ml; the content of SiO210wt% of powder of a strand-shaped chopped quartz fiber having a density of 2.2 g/ml; the content of SiO21wt% of powder dispersant; with SiO2The volume ratio of the powder to the quartz fiber mixture was 37.0: 63.0 of resin mixed solution, the density is 1.09 g/ml; a photoinitiator with the content of 1.75wt% of the mass of the resin mixed solution; silane coupling agent with the content of 1.5wt percent of the resin mixed solution; the content is 5 per mill of light absorbent of resin mixed solution;
the SiO2The powder is a mixture with the particle size of d50= 1-2 um and d50=200nm mixed according to the mass fraction of 7: 3;
the powder dispersing agent is stearic acid;
the light absorbent is light absorbent N30;
the resin mixed solution is a mixture of monomer hexahydrophthalic acid diglycidyl ether, 1,6 hexanediol diacrylate (HDDA) and dipentaerythritol penta/hexaacrylate (DPHA), and the mass ratio of the monomer hexahydrophthalic acid diglycidyl ether to the monomer 1,6 hexanediol diacrylate (HDDA) to the monomer dipentaerythritol penta/hexaacrylate (DPHA) is 5.5: 3.5: 1.0;
the photoinitiator is diaryl iodonium salt with the content of 1.25wt% of the mass of the monomer hexahydrophthalic acid diglycidyl ether, and benzoin dimethyl ether with the content of 0.5wt% of the mass fraction of the mixture of 1,6 hexanediol diacrylate (HDDA) and dipentaerythritol penta/hexaacrylate (DPHA);
the silane coupling agent is gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane (KH 560);
the preparation method of the chopped quartz fiber reinforced silicon oxide ceramic paste for photocuring comprises the following steps:
step 1: weighing bundle-shaped chopped quartz fibers, putting the bundle-shaped chopped quartz fibers into distilled water, boiling the mixture for 2 hours at 95 ℃, and then putting the mixture into an oven to dry the mixture for 8 hours at 60 ℃; placing the dried bundle-shaped chopped quartz fibers in a degreasing furnace at 400 ℃ for treatment for 4 hours, and lightly kneading to obtain monofilament chopped quartz fibers;
step 2: respectively weighing two kinds of the components according to the mass ratioSiO of particle size2Powder, powder dispersant, light absorbent, resin mixed liquid, photoinitiator and silane coupling agent;
and step 3: mixing SiO2Mixing the powder and a powder dispersing agent, and carrying out ball milling treatment by a ball mill, wherein the diameter of a milling ball is 5-10 mm, and the addition amount of the milling ball is SiO2The mass of the powder is 1.5 times, the parameters of the ball mill are set to 350r/min, and the total time is 12 hours;
and 4, step 4: sieving the mixture obtained in the step 3 through a 100-mesh sieve, placing the mixture in an oven, and drying at 60 ℃/12 h;
and 5: adding a photoinitiator and a silane coupling agent into the resin mixed solution, placing the mixture on a ball mill, and carrying out ball milling for 3 hours at a speed of 250r/min to obtain a photocuring resin system; and then gradually adding the photocuring resin system into the solid mixture obtained in the step 4, simultaneously dripping the light absorbing agent into the mixture, stirring the mixture into floccules, then putting the floccules into a homogenizing mixer for mixing and vacuumizing, wherein the parameter of the homogenizing mixer is set to 1500r for mirror min-1/20s+2000r﹒min-1 /30s + 2500r﹒min-1The silicon oxide ceramic paste is obtained after 20 seconds;
step 6: adding the monofilament chopped quartz fibers prepared in the step 1 into the silicon oxide ceramic paste obtained in the step 5, manually stirring, placing in a homogenizing mixer, setting the parameter as 2000r for min-1/20s+2800r﹒min-1And/30 s, mixing twice to obtain the photocuring chopped quartz fiber reinforced silica ceramic paste with the volume fraction of 63.0 vol%.
4. The method for preparing a chopped quartz fiber reinforced silica ceramic paste for photocuring as set forth in claim 1, wherein the method comprises the steps of: a light-cured short-cut quartz fiber reinforced silicon oxide ceramic paste comprises spherical SiO2Powder with a density of 2.2 g/ml; the content of SiO25wt% of powder of a strand-shaped chopped quartz fiber having a density of 2.2 g/ml; the content of SiO2Powder 1.5wt% of a powder dispersant; with SiO2The volume ratio of the powder to the quartz fiber mixture was 40.7: 59.3, the density is 1.09 g/ml; the content is 1.75wt% of the mass of the resin mixed solutionThe photoinitiator of (1); silane coupling agent with the content of 1wt% of the resin mixed liquid; the content is 1 per mill of light absorbent of resin mixed solution;
the SiO2The powder is a mixture with the particle size of d50= 1-2 um and d50=200nm mixed according to the mass fraction of 7: 3;
the powder dispersing agent is stearic acid;
the light absorbent is light absorbent N30;
the resin mixed solution is a mixture of monomer hexahydrophthalic acid diglycidyl ether, 1,6 hexanediol diacrylate (HDDA) and dipentaerythritol penta/hexaacrylate (DPHA), and the mass ratio of the monomer hexahydrophthalic acid diglycidyl ether to the monomer 1,6 hexanediol diacrylate (HDDA) to the monomer dipentaerythritol penta/hexaacrylate (DPHA) is 5.5: 3.5: 1.0;
the photoinitiator is diaryl iodonium salt with the content of 1.25wt% of the mass of the monomer hexahydrophthalic acid diglycidyl ether, and 2.4.6-trimethylbenzoyl diphenyl phosphine oxide with the content of 0.5wt% of the mass fraction of the mixture of 1,6 hexanediol diacrylate (HDDA) and dipentaerythritol penta/hexaacrylate (DPHA);
the silane coupling agent is gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane (KH 560);
the preparation method of the chopped quartz fiber reinforced silicon oxide ceramic paste for photocuring comprises the following steps:
step 1: weighing bundle-shaped chopped quartz fibers, putting the bundle-shaped chopped quartz fibers into distilled water, boiling the mixture for 5 hours at 95 ℃, and then putting the mixture into an oven to dry the mixture for 12 hours at 60 ℃; placing the dried bundle-shaped chopped quartz fibers in a degreasing furnace at 400 ℃ for treatment for 6h, and lightly kneading to obtain monofilament chopped quartz fibers;
step 2: respectively weighing SiO with two particle sizes according to the mass ratio2Powder, powder dispersant, light absorbent, resin mixed liquid, photoinitiator and silane coupling agent;
and step 3: mixing SiO2Mixing the powder and a powder dispersing agent, and carrying out ball milling treatment by a ball mill, wherein the diameter of a milling ball is 5-10 mm, and the addition amount of the milling ball is SiO21.0 time of the powder mass, setting the parameters of the ball mill to be 300r/min, and carrying out ball milling for 16 h;
and 4, step 4: sieving the mixture obtained in the step 3 through a 100-mesh sieve, placing the mixture in an oven, and drying at 60 ℃/12 h;
and 5: adding a photoinitiator and a silane coupling agent into the resin mixed solution, placing the mixture on a ball mill, and carrying out ball milling for 3 hours at the speed of 400r/min to obtain a photocuring resin system; and then gradually adding the photocuring resin system into the solid mixture obtained in the step 4, simultaneously dripping the light absorbing agent into the mixture, stirring the mixture into floccules, then putting the floccules into a homogenizing mixer for mixing and vacuumizing, wherein the parameter of the homogenizing mixer is set to 1000r for-1/20s+2500r﹒min-1 /30s + 2800r﹒min-1The silicon oxide ceramic paste is obtained after 20 seconds;
step 6: and (3) adding the monofilament chopped quartz fibers prepared in the step (1) into the silica ceramic paste obtained in the step (5), manually stirring, placing in a homogenizing mixer, setting the parameters to 2500 r-1/20 s +2500 r-1/30 s, and mixing twice to obtain the chopped quartz fiber reinforced silica ceramic paste for photocuring, wherein the volume fraction of the chopped quartz fiber reinforced silica ceramic paste is 59.3 vol%.
5. The method for preparing a chopped quartz fiber reinforced silica ceramic paste for photocuring as set forth in claim 1, wherein the method comprises the steps of: a light-cured short-cut quartz fiber reinforced silicon oxide ceramic paste comprises spherical SiO2Powder with a density of 2.2 g/ml; the content of SiO2Chopped quartz fiber in the shape of a bundle with 7wt% of powder and the density of 2.2 g/ml; the content of SiO21.2wt% of powder dispersant; with SiO2The volume ratio of the powder to the quartz fiber mixture is 38.1:61.9, and the density is 1.09 g/ml; a photoinitiator with the content of 1.75wt% of the mass of the resin mixed solution; silane coupling agent with the content of 1.3wt percent of the resin mixed solution; the content of the light absorbent is 2.1 per mill of the resin mixed solution;
the SiO2The powder is a mixture with the particle size of d50= 1-2 um and d50=200nm mixed according to the mass fraction of 7: 3;
the powder dispersing agent is stearic acid;
the light absorbent is light absorbent N30;
the resin mixed solution is a mixture of monomer hexahydrophthalic acid diglycidyl ether, 1,6 hexanediol diacrylate (HDDA) and dipentaerythritol penta/hexaacrylate (DPHA), and the mass ratio of the monomer hexahydrophthalic acid diglycidyl ether to the monomer 1,6 hexanediol diacrylate (HDDA) to the monomer dipentaerythritol penta/hexaacrylate (DPHA) is 5.5: 3.5: 1.0;
the photoinitiator is diaryl thionine with the content of 1.25wt% of the mass of the monomer hexahydrophthalic acid diglycidyl ether, and benzoin dimethyl ether with the content of 0.5wt% of the mass fraction of the mixture of 1,6 hexanediol diacrylate (HDDA) and dipentaerythritol penta/hexaacrylate (DPHA);
the silane coupling agent is gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane (KH 560);
the preparation method of the chopped quartz fiber reinforced silicon oxide ceramic paste for photocuring comprises the following steps:
step 1: weighing bundle-shaped chopped quartz fibers, putting the bundle-shaped chopped quartz fibers into distilled water, boiling the mixture for 3 hours at 95 ℃, and then putting the mixture into an oven to dry the mixture for 10 hours at 60 ℃; placing the dried bundle-shaped chopped quartz fibers in a degreasing furnace at 400 ℃ for treatment for 5 hours, and lightly kneading to obtain monofilament chopped quartz fibers;
step 2: respectively weighing SiO with two particle sizes according to the mass ratio2Powder, powder dispersant, light absorbent, resin mixed liquid, photoinitiator and silane coupling agent;
and step 3: mixing SiO2Mixing the powder and a powder dispersing agent, and carrying out ball milling treatment by a ball mill, wherein the diameter of a milling ball is 5-10 mm, and the addition amount of the milling ball is SiO2The weight of the powder is 1.3 times, the parameters of the ball mill are set to 330r/min, and the total time is 14 hours;
and 4, step 4: sieving the mixture obtained in the step 3 through a 100-mesh sieve, placing the mixture in an oven, and drying at 60 ℃/12 h;
and 5: adding a photoinitiator and a silane coupling agent into the resin mixed solution, placing the mixture on a ball mill, and carrying out ball milling for 3 hours at the speed of 350r/min to obtain a photocuring resin system; and then gradually adding the photocuring resin system into the solid mixture obtained in the step 4, simultaneously dripping the light absorbing agent into the mixture, stirring the mixture into floccules, then putting the floccules into a homogenizing mixer for mixing and vacuumizing, and setting the parameter of the homogenizing mixer to 1300r for min-1/20s+2200r﹒min-1 /30s + 2700r﹒min-1The silicon oxide ceramic paste is obtained after 20 seconds;
step 6: adding the monofilament chopped quartz fibers prepared in the step 1 into the silicon oxide ceramic paste obtained in the step 5, manually stirring, placing in a homogenizing mixer, setting the parameter as 2300r for min-1/20s+2700r﹒min-1And/30 s, mixing twice to obtain the chopped quartz fiber reinforced silica ceramic paste for photocuring, wherein the volume fraction of the paste is 61.9 vol%.
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