CN113370346A - Ceramic preparation method based on photocuring 3D printing ceramic precursor - Google Patents
Ceramic preparation method based on photocuring 3D printing ceramic precursor Download PDFInfo
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- 239000000919 ceramic Substances 0.000 title claims abstract description 136
- 239000012700 ceramic precursor Substances 0.000 title claims abstract description 71
- 238000000016 photochemical curing Methods 0.000 title claims abstract description 64
- 238000010146 3D printing Methods 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 239000000463 material Substances 0.000 claims abstract description 41
- 238000000197 pyrolysis Methods 0.000 claims abstract description 40
- 238000002411 thermogravimetry Methods 0.000 claims abstract description 9
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- 238000000034 method Methods 0.000 claims description 40
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- 239000002243 precursor Substances 0.000 claims description 7
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- B28—WORKING CEMENT, CLAY, OR STONE
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- B28B1/00—Producing shaped prefabricated articles from the material
- B28B1/001—Rapid manufacturing of 3D objects by additive depositing, agglomerating or laminating of material
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y10/00—Processes of additive manufacturing
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- 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
- B33Y40/00—Auxiliary operations or equipment, e.g. for material handling
- B33Y40/20—Post-treatment, e.g. curing, coating or polishing
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- 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
- B33Y50/00—Data acquisition or data processing for additive manufacturing
- B33Y50/02—Data acquisition or data processing for additive manufacturing for controlling or regulating additive manufacturing processes
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Abstract
本发明公开了一种基于光固化3D打印陶瓷前驱体的陶瓷制备方法，包括以下步骤：制备获得光固化陶瓷前驱体材料；进行热重分析，制定热解升温曲线；制备预设尺寸范围的系列尺寸正方体打印件，得到热解后的不同尺寸的正方体陶瓷及热解后线收缩率；获得只概率性产生裂纹的正方体陶瓷的最大尺寸；得到光固化陶瓷前驱体材料不产生确定性裂纹的陶瓷的几何模型最大特征尺寸；获得修改后的待打印几何模型；得到打印件；对打印件，在上述相同条件下进行热解，得到概率性含有裂纹的陶瓷；将含裂纹的陶瓷进行真空下浸渍光固化陶瓷前驱体材料，获得无裂纹的陶瓷。本发明能够解决现有工艺制备陶瓷裂纹多易破碎的技术问题。
The invention discloses a ceramic preparation method based on photo-curing 3D printing ceramic precursor, comprising the following steps: preparing and obtaining a photo-curing ceramic precursor material; conducting thermogravimetric analysis to formulate a pyrolysis heating curve; preparing a series of preset size ranges The size of the cube printed parts is obtained, and the cube ceramics of different sizes after pyrolysis and the linear shrinkage rate after pyrolysis are obtained; the maximum size of the cube ceramics with only probabilistic cracks is obtained; the light-cured ceramic precursor materials are obtained without deterministic cracks. Obtain the modified geometric model to be printed; obtain a printed part; perform pyrolysis on the printed part under the same conditions as above to obtain a ceramic with probabilistic cracks; impregnate the ceramic with cracks under vacuum Light-curing ceramic precursor materials to obtain crack-free ceramics. The invention can solve the technical problem that the ceramic cracks prepared by the existing technology are easily broken.
Description
Technical Field
The invention belongs to the technical field of ceramic preparation, relates to the field of photocuring 3D printing, and particularly relates to a ceramic preparation method based on photocuring 3D printing ceramic precursors.
Background
The non-oxide ceramic has the advantages of high temperature resistance, thermal shock resistance, high strength and the like, so that the non-oxide ceramic is widely applied to high-temperature structural components; however, e.g. SiC, Si3N4And the non-oxide ceramics have high hardness and high brittleness and are difficult to prepare ceramic parts with complex structures. Compared with a 3D printing process of ceramic powder suspension, the process for preparing ceramic by photocuring the 3D printing ceramic precursor effectively solves the problems of difficult forming, difficult sintering of non-oxide ceramic and the like, and fully exerts the forming advantages of the 3D printing technology and the advantages of high density, low preparation temperature, uniform ceramic components and the like of precursor conversion ceramic. Therefore, the process for preparing the ceramic by photocuring the 3D printing ceramic precursor has great popularization value.
Currently, photocuring 3D printing techniques for various ceramic precursors are widely studied. However, due to the pyrolysis shrinkage of the ceramic precursor and the release of the small molecule gas, the ceramic part is very easy to generate surface cracks and even break, and the existing research on the photocuring 3D printing ceramic precursor hardly provides a solution for the cracks generated in the process, so that the ceramic prepared by the process is very easy to break and has no application value.
While there has been a number of studies relating to crack repair, the value of repair has been lost for ceramics where there are a number of cracks, even nearly near fracture. In addition, crack repairing methods such as micro-crack removal and re-filling, dissimilar material filling and bonding, laser repairing and the like cannot remove crack region materials for the inner surface or the special-shaped surface of a complex-shaped structure, and the filled dissimilar materials and the matrix have different material properties such as elastic modulus, thermal expansion coefficient and the like, so that re-cracking after repairing is easily caused when the filled dissimilar materials and the matrix are applied to high-temperature environments such as aerospace, military industry and national defense, and the crack repairing is meaningless.
In conclusion, the problems that ceramic cracks are easy to break and crack repair is not applicable are solved, and the development and popularization of the process for preparing ceramic by photocuring 3D printing ceramic precursors are severely restricted.
Disclosure of Invention
The invention aims to provide a ceramic preparation method based on a photocuring 3D printing ceramic precursor, and aims to solve the technical problem that ceramic cracks are more and easy to break in the existing process.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention discloses a ceramic preparation method based on a photocuring 3D printing ceramic precursor, which comprises the following steps of:
step 1, preparing a photocuring ceramic precursor material;
step 4, obtaining the maximum size of the cubic ceramics only generating cracks probabilistically based on the cubic ceramics with different sizes;
step 5, reversely amplifying the maximum size of the cubic ceramic only generating the probabilistic cracks according to the linear shrinkage rate after pyrolysis to obtain the maximum characteristic size of a geometric model of the ceramic, which is prepared by the photocuring ceramic precursor material and does not generate the deterministic cracks, through a photocuring 3D printing process;
step 6, modifying the region with the characteristic size larger than or equal to the maximum characteristic size of the geometric model in the geometric model to be printed, so that the characteristic size in at least one dimension direction in any region on the geometric model is smaller than the maximum characteristic size of the geometric model, and obtaining the modified geometric model to be printed;
step 7, carrying out photocuring 3D printing forming on the modified geometric model to be printed to obtain a printed piece;
and 9, soaking the ceramic containing the cracks in the obtained probabilistic ceramic containing the cracks in vacuum for a preset time period, and then taking out the ceramic containing the cracks to obtain the crack-free ceramic.
In step 3, the method for preparing a series of cube prints with preset size ranges by using the photo-curing ceramic precursor material specifically comprises the following steps: the photo-curing ceramic precursor material is adopted to prepare a series of cube prints with the side length ranging from 2mm to 10 mm.
The invention has the further improvement that the step 4 specifically comprises the following steps: observing the cubic ceramics with different sizes under a microscope with the same magnification, and recording the maximum crack width and the number of cracks on the surface of the cubic ceramics with different sizes; among them, the cubic ceramics having a maximum crack width of 2 μm or less and a number of cracks of 2 or less are considered to have cracks only probabilistically; the maximum side length of a cubic ceramic having a maximum crack width of 2 μm or less and a number of cracks of 2 or less was set as the maximum size of a cubic ceramic in which cracks were only generated with probability.
The invention is further improved in that the step 6 specifically comprises: and for a geometric model to be printed of the solid part, filling the geometric model with a light unit structure with a wall thickness smaller than the maximum characteristic dimension of the geometric model, so that the characteristic dimension in at least one dimension direction in any area on the geometric model is smaller than the maximum characteristic dimension of the geometric model.
The invention is further improved in that the step 6 specifically comprises: and for the geometric model to be printed of the part with the installation matching surface or the internal surface of the internal structure, reserving the installation matching surface and the internal surface, and filling the residual solid area with a light unit structure, so that the characteristic dimension in at least one dimension direction in any area on the geometric model is smaller than the maximum characteristic dimension of the geometric model.
A further improvement of the invention is that the lightweight cellular structure is one or more of a two-dimensional honeycomb grid, a square grid structure, a three-dimensional lattice, and the like.
The invention has the further improvement that the step 9 specifically comprises the following steps:
(1) soaking the crack-containing ceramic in the obtained probabilistic crack-containing ceramic in vacuum for a preset time period, taking out, and removing the residual photo-cured ceramic precursor material on the surface by using a hot air gun to obtain a ceramic part with the crack containing a precursor;
(2) pyrolyzing the ceramic part containing the precursor in the crack under the same condition in the step 3 to obtain the ceramic part with the crack partially filled;
(3) repeating the step (1) and the step (2) for a plurality of times to obtain the ceramic without cracks.
The invention also provides a ceramic prepared by the preparation method of the ceramic based on the photocuring 3D printing ceramic precursor.
Compared with the prior art, the invention has the following beneficial effects:
the invention discloses a ceramic preparation method based on a photocuring 3D printing ceramic precursor, which is used for controlling crack defects generated by pyrolysis certainty of the photocuring ceramic precursor, determining the size of a sample which only generates cracks probabilistically through a series of (optional, 2-10 mm) cube sample pyrolysis experiments, further determining the maximum characteristic size in a geometric model and modifying the model to obtain the ceramic which only generates crack defects probabilistically. And (3) carrying out crack repairing treatment on the ceramic containing cracks, gradually repairing and filling the cracks through soaking the same ceramic precursor material for several times and carrying out pyrolysis process, and realizing the healing of the cracks. Finally, through the organic combination of the two processes, the crack-free ceramic preparation of the photocuring 3D printing ceramic precursor can be realized. The preparation method provided by the invention creatively solves the problems that ceramic cracks are more and easy to break and crack repair is not suitable for preparing the ceramic precursor for photocuring 3D printing. The method provides a new important step for the existing process of preparing the ceramic by photo-curing the 3D printing ceramic precursor, fully considers the influence of the characteristic size of the geometric model on the cracks, increases the link of further processing the geometric model for controlling the cracks, simultaneously solves the problem that the existing crack repairing technology is not suitable for the ceramic cracks obtained by photo-curing the 3D ceramic precursor, ensures that the crack filling area keeps the same material property as the matrix by dipping the same ceramic precursor and pyrolyzing, and avoids the steps of removing materials in the crack area and the problem that the different materials are easy to cause secondary cracking.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art are briefly introduced below; it is obvious that the drawings in the following description are some embodiments of the invention, and that for a person skilled in the art, other drawings can be derived from them without inventive effort.
FIG. 1 is a schematic flow diagram of a method for preparing a ceramic based on a photocuring 3D printing ceramic precursor according to the present invention;
FIG. 2 is a schematic view of a TD-DSC curve in example 1 of the present invention;
FIG. 3 is a schematic view of a pyrolysis temperature increase curve in example 1 of the present invention;
FIG. 4 is a schematic view of filling a square grid in example 1 of the present invention;
FIG. 5 is an electron microscope photograph of a crack-free square grid ceramic in example 1 of the present invention;
FIG. 6 is an electron microscope image of the crack repairing process in example 1 of the present invention;
fig. 7 is a schematic view of a cell lattice filled in embodiment 2 of the present invention;
FIG. 8 is an electron microscope photograph of a crack-free honeycomb grid ceramic in example 2 of the present invention;
FIG. 9 is a diagram of a rear mirror for crack repair in example 2 of the present invention.
Detailed Description
In order to make the purpose, technical effect and technical solution of the embodiments of the present invention clearer, the following clearly and completely describes the technical solution of the embodiments of the present invention with reference to the drawings in the embodiments of the present invention; it is to be understood that the described embodiments are only some of the embodiments of the present invention. Other embodiments, which can be derived by one of ordinary skill in the art from the disclosed embodiments without inventive faculty, are intended to be within the scope of the invention.
Based on the defects of the prior art, in order to fully exert the advantages of the process for preparing ceramic by photocuring 3D printing ceramic precursors, the problem that ceramic cracks are more and easily broken in the prior art is urgently needed to be solved. In the embodiment of the invention, the adaptability improvement is provided aiming at controlling the crack generation and the crack repair, the number and the size of the cracks can be reduced, the crack repair has certain value, and the two links are organically combined into a new solution idea for preparing the crack-free ceramic.
Referring to fig. 1, a method for preparing a ceramic based on a photocuring 3D printing ceramic precursor according to an embodiment of the present invention includes the following steps:
1) weighing a ceramic precursor, a diluting monomer, a photoinitiator and other additives in a certain mass ratio, ultrasonically vibrating, mixing and defoaming in vacuum to obtain a photocuring ceramic precursor; exemplary, for example, the preparation flow in the chinese invention patent application entitled photocuring 3D printing silicon nitride ceramic precursor, its preparation and forming method, application No. 201910905586.9;
2) carrying out thermogravimetric analysis on the obtained photocuring ceramic precursor, and formulating a pyrolysis temperature rise curve according to the result of the thermogravimetric analysis;
3) preparing a series of cube prints with the side length ranging from 2mm to 10mm, and performing a pyrolysis experiment according to a pyrolysis temperature rise curve to obtain pyrolyzed cube ceramics with different sizes and the linear shrinkage rate after pyrolysis;
4) observing the obtained cubic ceramic samples with different sizes under a microscope with the same magnification, and respectively recording the maximum crack width and the number of cracks on the ceramic surface of the samples with different sizes. Wherein, for the sample with the maximum crack width less than 2 μm and the crack number less than 2, only the probability crack defect is considered to be generated due to the pyrolysis process, and for the sample with the maximum crack width more than 2 μm, the certainty crack is considered to be generated necessarily in the pyrolysis process due to the oversize. Observing the maximum size of the cube samples with the maximum crack width less than 2 μm and the number less than 2 in the record as the maximum size of the cube ceramics which only generates cracks probabilistically;
5) reversely amplifying the maximum size of the sample which is determined in the step 4) and only generates the cracks probabilistically according to the linear shrinkage rate after pyrolysis in the step 2), and obtaining the maximum characteristic size of a geometric model of the ceramic which does not generate the deterministic cracks and is prepared by the photocuring 3D printing process of the photocuring ceramic precursor material corresponding to the step 1);
6) and further modifying the area with the characteristic size larger than the maximum characteristic size in the geometric model to be printed according to the maximum characteristic size of the geometric model, so that the size in one dimension direction in any area on the geometric model is smaller than the maximum characteristic size. For a solid part, other light unit structures such as two-dimensional honeycomb grids, square grids, three-dimensional lattices and the like with the wall thickness smaller than the maximum characteristic dimension can be adopted for filling, so that the dimensions of the modified geometric model in a certain dimension (thickness direction) are smaller than the maximum characteristic dimension. For parts with installation matching surfaces or internal structure internal surfaces, the installation surfaces and the internal surfaces are reserved, and light unit structures are filled in other solid part areas, so that the sizes of the modified geometric models in a certain dimension (thickness direction) are smaller than the maximum characteristic size.
7) Carrying out photocuring 3D printing forming on the obtained modified geometric model to obtain a printed piece;
8) the obtained printed material was pyrolyzed under the same conditions as in step 3) to obtain a ceramic having a probability of cracks. Illustratively, the following: under the same pyrolysis conditions in step 3), although the dimension is controlled to avoid the generation of deterministic cracks, the generation of probabilistic cracks can be caused because the release of gas in the pyrolysis process generates free paths in the ceramic and the shearing deformation caused by the incomplete synchronization of the shrinkage process is uncontrollable, and further the pyrolyzed ceramic contains the probabilistic cracks.
9) Soaking the ceramic containing the cracks in the obtained probabilistic cracked ceramic for 2h in vacuum for the same ceramic precursor material, taking out, removing the residual ceramic precursor on the surface by using a hot air gun at the temperature of 100 ℃, and still retaining the ceramic precursor in the cracks due to the action of surface adsorption force and the like;
10) pyrolyzing the ceramic part containing the precursor in the crack under the same condition in the step 3) again to obtain the ceramic part with the crack partially filled;
11) and (4) repeating the steps 9) to 10) for two to three times, wherein the cracks are almost completely filled, and the crack-free ceramic is obtained.
The ceramic preparation method based on the photocuring 3D printing ceramic precursor disclosed by the embodiment of the invention comprises the steps of firstly, controlling crack defects generated by pyrolysis certainty of the photocuring ceramic precursor, determining the size of a sample which only probabilistically generates cracks through a 2-10 mm series size cube sample pyrolysis experiment, further determining the maximum characteristic size in a geometric model, and modifying the model to obtain the ceramic which only probabilistically generates the crack defects. Secondly, crack repairing treatment is carried out on the ceramic containing cracks, the same ceramic precursor material is soaked for two to three times and the cracks are gradually repaired and filled through a pyrolysis process, and the cracks are healed. Finally, through the organic combination of the two processes, the crack-free ceramic preparation of the photocuring 3D printing ceramic precursor can be realized. The preparation method provided by the invention creatively solves the problems that ceramic cracks are more and easy to break and crack repair is not suitable for preparing the ceramic precursor for photocuring 3D printing. The method provides a new important step for the existing process of preparing the ceramic by photo-curing the 3D printing ceramic precursor, fully considers the influence of the characteristic size of the geometric model on the cracks, increases the link of further processing the geometric model for controlling the cracks, simultaneously solves the problem that the existing crack repairing technology is not suitable for the ceramic cracks obtained by photo-curing the 3D ceramic precursor, ensures that the crack filling area keeps the same material property as the matrix by dipping the same ceramic precursor and pyrolyzing, and avoids the steps of removing materials in the crack area and the problem that the different materials are easy to cause secondary cracking.
Example 1
Referring to fig. 1 to 6, a method for preparing a ceramic based on a photo-curing 3D printing ceramic precursor according to an embodiment of the present invention includes the following steps:
1) weighing the following components in a mass ratio (70-80): (30-20) mixing polyborosilazane and triethylene glycol diacrylate monomers, adding 1.5-2 wt% of photoinitiator and 0.1-1 wt% of hydroquinone, performing ultrasonic oscillation mixing and vacuum defoaming to obtain photocuring polyborosilazane;
2) thermogravimetric analysis is carried out on the obtained photocuring polyborosilazane to obtain a TD-DSC curve shown in figure 2, heat preservation time is set at the temperature point with larger weight loss rate of 170 ℃, 420 ℃ and 960 ℃ of complete ceramic, the temperature is raised at 1 ℃/min, and a pyrolysis temperature rise curve shown in figure 3 is formulated;
3) preparing a series of cube prints with the side length ranging from 3mm to 10mm, and performing a pyrolysis experiment according to a pyrolysis temperature rise curve shown in fig. 3 to obtain 7 groups of pyrolyzed cube ceramics with different sizes, wherein the pyrolyzed cube ceramics uniformly shrink and have the shrinkage rate of 30%;
4) the obtained cubic ceramic samples with different sizes are observed under a microscope with the same magnification, the sizes and the number of cracks on the ceramic surfaces of 7 groups of size samples are respectively recorded as shown in table 1, and the widths of the cracks are gradually reduced along with the reduction of the sizes, and the number of the cracks is generally reduced. Wherein, for the sample size of less than 2 μm in maximum crack width and less than 2 in number of cracks, which is considered to be only a probability crack defect due to the pyrolysis process, the maximum size of the cubic ceramic only generating probability cracks can be determined to be about 3 mm;
5) reversely amplifying the maximum size of the sample which is determined in the step 4) and only generates the deterministic cracks according to the linear shrinkage rate of 30% in the step 3), and obtaining the maximum characteristic size of a geometric model of the ceramic which does not generate the deterministic cracks and is prepared by using the corresponding photocuring ceramic precursor material obtained in the step 1) through a photocuring 3D printing process, wherein the maximum characteristic size is 4.3 mm;
6) as shown in fig. 4, in three-dimensional design software, filling a solid region with a two-dimensional square grid with a wall thickness of 1mm in a 10 × 10mm cube geometric model to be printed to obtain an internal solid hollowed geometric model, wherein the thickness direction of any region of the modified hollowed cube model is 1mm and is smaller than the maximum characteristic dimension by 4.3mm, so that the size requirement of the geometric model which only generates cracks probabilistically is met;
7) carrying out photocuring 3D printing forming on the obtained modified geometric model to obtain a plurality of printed parts;
8) subjecting the plurality of printed materials obtained to pyrolysis simultaneously under the same conditions as in step 3) to obtain a plurality of almost crack-free ceramics and ceramics each containing a probabilistic crack defect as shown in FIG. 5;
9) carrying out vacuum impregnation on the ceramic containing the probabilistic crack defects for 2h, then taking out the ceramic, removing residual polyborosilazane on the surface by using a hot air gun at the temperature of 100 ℃, wherein the polyborosilazane in the cracks is still retained due to the action of surface adsorption force and the like;
10) pyrolyzing the ceramic with the cracks containing polyborosilazane again under the same conditions in the step 3), and observing under an electron microscope to find that the cracks are partially filled and repaired;
11) repeating the steps 9) to 10) twice, and observing under an electron microscope in fig. 6 to find that the original longer cracks are separated into a plurality of extremely short defects by the filling material, so that the ceramic almost without cracks is obtained.
TABLE 1
In embodiment 1 of the present invention, the size of the cube sample is too wide, the maximum characteristic size is not determined accurately enough, and in order to further accurately obtain the maximum characteristic size value, in embodiment 2, the size range of the cube sample is: 2-5 mm and 0.5mm apart. In example 1, the number of crack dipping cracks was two, and the cracks were not completely filled due to the shrinkage of the precursor, and in order to further increase the filling degree of the cracks, in example 2, the number of crack dipping crack repetition times was increased to 3.
Example 2
Referring to fig. 1 and 7 to 9, a method for preparing a ceramic based on a photocuring 3D printing ceramic precursor according to an embodiment of the present invention specifically includes the following steps:
1) weighing the following components in a mass ratio of (80-90): (20-10) mixing polysilazane and triethylene glycol diacrylate monomers, adding 1.5-2 wt% of a photoinitiator, performing ultrasonic oscillation mixing and vacuum defoaming to obtain photocuring polysilazane;
2) performing thermogravimetric analysis on the obtained photocuring polysilazane to obtain a TD-DSC curve, setting heat preservation time at the temperature point with larger weight loss rate of 200 ℃, 450 ℃ and 1050 ℃ of complete ceramic, heating at 1 ℃/min, and formulating a pyrolysis heating curve;
3) preparing a series of cube prints with the side length ranging from 2mm to 5mm, and performing a pyrolysis experiment according to the pyrolysis temperature rise curve in the step 2) to obtain 7 groups of pyrolyzed cube ceramics with different sizes, wherein the pyrolyzed cube ceramics uniformly shrink and have a shrinkage rate of 25%;
4) the obtained cubic ceramic samples with different sizes are observed under a microscope with the same magnification, the sizes and the number of cracks on the ceramic surfaces of 7 groups of size samples are respectively recorded as shown in table 2, and the widths of the cracks are gradually reduced along with the reduction of the sizes, and the number of the cracks is generally reduced. Wherein, for a sample size of 2.5mm in which the maximum crack width is less than 2 μm and the number of cracks is less than 2, it is considered that only probabilistic crack defects are generated due to the pyrolysis process, and it can be determined that the maximum size of the tetragonal ceramic in which only probabilistic cracks are generated is about 2.5 mm;
5) reversely amplifying the maximum size of the sample which is determined in the step 4) and only generates the deterministic cracks according to the linear shrinkage rate of 25% in the step 3), and obtaining the maximum characteristic size of a geometric model of the ceramic which does not generate the deterministic cracks and is prepared by using the corresponding photocuring ceramic precursor material obtained in the step 1) through a photocuring 3D printing process, wherein the maximum characteristic size is 3.3 mm;
6) as shown in fig. 7, in three-dimensional design software, a two-dimensional honeycomb grid with a wall thickness of 1mm is used for filling a solid region of a solid geometric model to be printed to obtain a hollow-out geometric model of an internal solid, and a value that the thickness direction of 1mm is smaller than the maximum characteristic dimension of 3.3mm exists in any region of the modified hollow-out honeycomb model, so that the size requirement of the geometric model which only generates cracks probabilistically is met;
7) carrying out photocuring 3D printing forming on the obtained modified geometric model to obtain a plurality of printed parts;
8) subjecting the plurality of printed materials obtained to pyrolysis simultaneously under the same conditions as in step 3) to obtain a plurality of almost crack-free ceramics and ceramics each containing a probabilistic crack defect as shown in FIG. 8;
9) the method comprises the following steps of (1) carrying out vacuum impregnation on the honeycomb ceramic containing the probabilistic crack defects for 2h, then taking out the honeycomb ceramic, removing residual polysilazane on the surface by using a hot air gun at the temperature of 100 ℃, and still retaining the polysilazane in the cracks due to the action of surface adsorption force and the like;
10) pyrolyzing the honeycomb grid ceramic containing polysilazane in the cracks under the same conditions in the step 3);
11) repeating the steps 9) to 10) for three times, the cracks are almost completely filled, and as is seen in the optical microscope of fig. 9, the original longer cracks are almost filled, and the ceramic with almost no cracks is obtained.
TABLE 2
Although the present invention has been described in detail with reference to the above embodiments, those skilled in the art can make modifications and equivalents to the embodiments of the present invention without departing from the spirit and scope of the present invention, which is set forth in the claims of the present application.
Claims (8)
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