阅读说明：本技术 一种3d打印复杂结构陶瓷制件及其制备方法与应用 (3D printing ceramic part with complex structure and preparation method and application thereof ) 是由 朱光达 侯仪 赵宁 徐坚 崔可建 于 2020-05-26 设计创作，主要内容包括：本发明公开一种3D打印复杂结构陶瓷制件及其制备方法与应用。制备方法包括如下步骤：(1)对柔性聚合物基陶瓷前驱体制件进行变形操作,并固定其变形后的形状；制备所述柔性聚合物基陶瓷前驱体的组合物包括：含巯基光敏树脂单体、含乙烯基光敏树脂单体、光引发剂以及任选的无机陶瓷填料；其中,至少一种光敏树脂单体中含硅元素。(2)步骤(1)得到的变形后制件经过两次热处理,得到所述陶瓷制件。本发明利用具有可变形的柔软聚合物基陶瓷前驱体,并进一步变形、通过两次热处理,得到结构更为复杂且多样化的陶瓷制件,赋予了3D打印陶瓷材料变形能力,能够制备出单纯光固化3D打印难以实现的更加复杂的结构。(The invention discloses a 3D printing ceramic part with a complex structure and a preparation method and application thereof. The preparation method comprises the following steps: (1) carrying out deformation operation on the flexible polymer-based ceramic precursor workpiece, and fixing the deformed shape of the flexible polymer-based ceramic precursor workpiece; the composition for preparing the flexible polymer-based ceramic precursor comprises: a mercapto group-containing photosensitive resin monomer, a vinyl group-containing photosensitive resin monomer, a photoinitiator and an optional inorganic ceramic filler; wherein at least one photosensitive resin monomer contains silicon element. (2) And (2) carrying out heat treatment twice on the deformed workpiece obtained in the step (1) to obtain the ceramic workpiece. According to the invention, the deformable soft polymer-based ceramic precursor is further deformed and subjected to two times of heat treatment to obtain ceramic parts with more complex and diversified structures, the deformation capability of the 3D printing ceramic material is endowed, and the more complex structure which is difficult to realize by the simplex photocuring 3D printing can be prepared.)

1. A method for preparing a ceramic article, comprising the steps of:

(1) carrying out deformation operation on the flexible polymer-based ceramic precursor workpiece, and fixing the deformed shape of the flexible polymer-based ceramic precursor workpiece;

(2) and (2) carrying out heat treatment twice on the deformed workpiece obtained in the step (1) to obtain the ceramic workpiece.

2. The method of claim 1, wherein preparing the composition of the flexible polymer-based ceramic precursor comprises: a mercapto group-containing photosensitive resin monomer, a vinyl group-containing photosensitive resin monomer, a photoinitiator and an optional inorganic ceramic filler; wherein at least one photosensitive resin monomer contains silicon element.

3. The production method according to claim 2, wherein the mercapto group-containing photosensitive resin monomer is selected from at least one of the following compounds: mercaptosilazane or an oligomer thereof, mercaptosiloxane or an oligomer thereof, and mercaptoacrylate or an oligomer thereof, and the like. Preferably, the oligomer of mercaptosiloxane is selected from mercaptopolydimethylsiloxane; the oligomer of the mercapto acrylate is selected from at least one of mercapto polyether acrylate and mercapto polyester acrylate; the mercapto acrylate is at least one selected from mercapto epoxy acrylate and trihydroxy methyl propane tri (3-mercapto acrylate). Preferably, the mercapto group-containing photosensitive resin monomer is mercapto acrylate and/or an oligomer thereof; exemplary is at least one of trihydroxymethyl propane tris (3-mercapto acrylate), mercapto epoxy acrylate, mercapto polyether acrylate.

Preferably, the vinyl-containing photosensitive resin monomer is selected from at least one of the following compounds: vinylsilane or an oligomer thereof (e.g., vinylpolysiloxane), vinylsilazane or an oligomer thereof (e.g., vinylpolysilazane), (meth) acrylate (e.g., at least one of 1,6, hexanediol diacrylate, isocyanatoethyl methacrylate, and isobornyl acrylate), urethane (meth) acrylate, and the like, preferably 2,4, 6-trimethyl-2, 4, 6-trivinylcyclonitrogensilane, vinylpolysilazane, and/or vinylpolysiloxane.

Preferably, the photoinitiator is selected from at least one of the following materials: bibenzoyl, diphenylethanedione, dialkoxyacetophenone, camphorquinone, α -hydroxyalkylbenzone, α -aminoalkylbenzophenone, acylphosphine oxide, benzophenone-based compound (e.g., at least one of benzophenone, 4-methylbenzophenone, and 2,4, 6-trimethylbenzophenone), ethanolamine-based compound, quinone-based compound, titanocene-based compound, iodonium salt-based compound, sulfonium salt-based compound, and triazine-based compound.

Preferably, the inorganic ceramic filler is selected from at least one of the following materials: structural ceramics (for example, at least one of silicon dioxide, silicon nitride, zirconium oxide, calcium phosphate, and silicon nitride), piezoelectric ceramics (at least one of the binary systems of barium titanate and lead zirconate titanate), dielectric ceramics (at least one of aluminum oxide, silicon carbide, and beryllium oxide), and the like, preferably at least one of silicon dioxide, barium titanate, aluminum oxide, and zirconium oxide.

4. The production method according to any one of claims 2 to 3, wherein the molar ratio of the mercapto group-containing photosensitive resin monomer to the vinyl group-containing photosensitive resin monomer is (1-100): (1-100).

Preferably, the mass ratio of the photoinitiator to the total mass of the photosensitive resin monomers is (0.01-5): 100.

Preferably, the mass ratio of the inorganic ceramic filler to the total mass of the photosensitive resin monomers is (0.01-50): 100.

5. The method of any one of claims 1-4, wherein the method of making the flexible polymer-based ceramic precursor article comprises the steps of:

a) blending a mercapto-containing photosensitive resin monomer, a vinyl-containing photosensitive resin monomer and a photoinitiator to obtain a resin solution;

b) optionally, adding the inorganic ceramic filler into the resin solution to obtain a mixed dispersion liquid;

c) and (c) carrying out photocuring 3D printing on the resin solution obtained in the step a) or the mixed dispersion obtained in the step b) to obtain the flexible polymer-based ceramic precursor part.

Preferably, in step a) and/or b), the materials are mixed under stirring.

Preferably, in step c), the laser used for the photocuring 3D printing is visible light or ultraviolet light.

6. The production method according to any one of claims 1 to 5, wherein in the step (1), the manner of deformation is selected from at least one of: stretching, bending, folding, twisting, and compressing.

7. The method according to any one of claims 1 to 6, wherein in the step (2), both heat treatments comprise a complete process of raising the temperature, keeping the temperature and lowering the temperature to room temperature.

Preferably, in the step (2), the temperature of the first heat treatment is lower than that of the second heat treatment.

Preferably, the temperature of the first heat treatment is 100-.

Preferably, the temperature of the second heat treatment is 600-.

Preferably, in step (2), the first heat treatment and the second heat treatment have the same or different temperature rise rates, for example, 1 to 30 ℃/min.

Preferably, in step (2), the time of the first heat treatment and the time of the second heat treatment are the same or different, for example, the time of the heat treatment is 0.5 to 24 hours, preferably 1 to 10 hours.

Preferably, in the step (2), the process of cooling to room temperature is natural cooling along with the furnace.

Preferably, in step (2), the atmosphere of the two heat treatments is the same or different, and is, for example, an inert atmosphere such as nitrogen, air, or the like.

8. The method for the production according to claim 1 or 2, characterized in that it comprises the following steps:

1-1) performing at least one deformation operation of stretching, bending, folding, twisting and the like on the flexible polymer-based ceramic precursor workpiece, and fixing the shape of the flexible polymer-based ceramic precursor workpiece by using a metal wire;

the flexible polymer-based ceramic precursor part is prepared from the following composition through 3D photocuring printing: a mercapto group-containing photosensitive resin monomer, a vinyl group-containing photosensitive resin monomer, a photoinitiator and an optional inorganic ceramic filler; wherein at least one photosensitive resin monomer contains silicon element;

2-1) carrying out first heat treatment on the deformed workpiece obtained in the step 1-1) to shape the polymer-based ceramic precursor and remove the metal wire for fixing;

3-1) carrying out secondary heat treatment on the polymer-based ceramic precursor workpiece shaped in the step 2-1) to obtain the ceramic workpiece;

wherein the temperature of the first heat treatment is lower than that of the second heat treatment.

9. A ceramic article produced by the production method according to any one of claims 1 to 8.

10. Use of a flexible polymer-based ceramic precursor according to any one of claims 1 to 5 for the preparation of a ceramic article according to claim 9, or use of a ceramic article according to claim 9 in a piezoelectric material, a dielectric material, a wave-absorbing material, a ceramic solid cell, a semiconductor material or an energy storage material.

Preferably, the ceramic part is a piezoelectric ceramic part, a dielectric ceramic part, a wave-absorbing ceramic part, a ceramic solid battery, a semiconductor ceramic part or an energy-storage ceramic part.

Technical Field

The invention belongs to the technical field of 3D printing, and particularly relates to a 3D printing ceramic part with a complex structure, and a preparation method and application thereof.

Background

Compared with metal materials and high polymer materials, ceramic materials are difficult to machine and form, and ceramic materials with complex shapes are more difficult to prepare. The ceramic material is difficult to obtain by casting and machining, is mainly prepared by powder sintering and film deposition, and can generate defects such as gaps, nonuniformity and the like in the machining process, thereby seriously influencing the high-temperature performance, weather resistance, mechanical property and the like of the ceramic material and limiting the use of the ceramic material.

3D prints, is a emerging quick forming technique, and 3D prints the one shot forming that can realize complex construction, obtains the complex construction that traditional processing mode is difficult to realize, also need not the loaded down with trivial details process flow of traditional processing simultaneously. Photocuring 3D prints advantages such as having high shaping precision, high printing efficiency, can realize the printing of micron, submicron even nanometer scale structure. However, the existing photocuring 3D printing ceramic material is directly sintered and shaped after a printed part is finished, and has no possibility of re-molding, so that the diversity and complexity of the structure of the photocuring 3D ceramic material are limited.

Disclosure of Invention

The invention provides a preparation method of a ceramic product, which comprises the following steps:

(1) carrying out deformation operation on the flexible polymer-based ceramic precursor workpiece, and fixing the deformed shape of the flexible polymer-based ceramic precursor workpiece;

(2) and (2) carrying out heat treatment twice on the deformed workpiece obtained in the step (1) to obtain the ceramic workpiece.

According to an embodiment of the present invention, a composition for preparing the flexible polymer-based ceramic precursor includes: a mercapto group-containing photosensitive resin monomer, a vinyl group-containing photosensitive resin monomer, a photoinitiator and an optional inorganic ceramic filler; wherein at least one photosensitive resin monomer contains silicon element.

According to an embodiment of the present invention, the mercapto group-containing photosensitive resin monomer may be selected from at least one of the following compounds: mercaptosilazane or an oligomer thereof, mercaptosiloxane or an oligomer thereof, and mercaptoacrylate or an oligomer thereof, and the like. For example, the oligomer of mercaptosiloxane may be selected from mercaptopolydimethylsiloxane; the oligomer of the mercapto acrylate can be selected from at least one of mercapto polyether acrylate and mercapto polyester acrylate; the mercapto acrylate may be at least one selected from mercapto epoxy acrylate and trihydroxy methyl propane tri (3-mercapto acrylate). Preferably, the mercapto group-containing photosensitive resin monomer is mercapto acrylate and/or an oligomer thereof; exemplary is at least one of trihydroxymethyl propane tris (3-mercapto acrylate), mercapto epoxy acrylate, mercapto polyether acrylate.

According to an embodiment of the present invention, the vinyl-containing photosensitive resin monomer may be selected from at least one of the following compounds: vinylsilane or an oligomer thereof (e.g., vinylpolysiloxane), vinylsilazane or an oligomer thereof (e.g., vinylpolysilazane), (meth) acrylate (e.g., at least one of 1,6, hexanediol diacrylate, isocyanatoethyl methacrylate, and isobornyl acrylate), urethane (meth) acrylate, and the like, preferably 2,4, 6-trimethyl-2, 4, 6-trivinylcyclonitrogensilane, vinylpolysilazane, and/or vinylpolysiloxane.

According to an embodiment of the present invention, the photoinitiator may be selected from at least one of the following materials: bibenzoyl, diphenylethanedione, dialkoxyacetophenone, camphorquinone, α -hydroxyalkylbenzones (e.g., at least one of HMPP, HHMP, and HCPK), α -aminoalkylbenzones (e.g., at least one of Irgacure907 and Irgacure 369), acylphosphine oxides (e.g., at least one of TPO, TEPO, and BAPO), benzophenones (e.g., at least one of benzophenone, 4-methylbenzophenone, and 2,4, 6-trimethylbenzophenone), ethanolamines (e.g., at least one of triethanolamine, N-methylethanolamine, N-dimethylethanolamine, and N, N-diethylethanolamine), quinones, titanocenes, iodonium salts, sulfonium salts, and triazines.

According to an embodiment of the present invention, the inorganic ceramic filler may be selected from at least one of the following materials: structural ceramics (for example, at least one of silicon dioxide, silicon nitride, zirconium oxide, calcium phosphate, and silicon nitride), piezoelectric ceramics (for example, a binary system piezoelectric ceramic selected from barium titanate and lead zirconate titanate), dielectric ceramics (at least one of aluminum oxide, silicon carbide, and beryllium oxide), and the like, and preferably at least one of silicon dioxide, barium titanate, aluminum oxide, and zirconium oxide.

According to an embodiment of the present invention, the molar ratio of the mercapto group-containing photosensitive resin monomer to the vinyl group-containing photosensitive resin monomer is (1-100): (1-100), preferably the molar ratio is (1-10): (1-10), more preferably (1-5): (1-5), for example the molar ratio is 1:1, 2:1, 1:2, 1:3, 3: 1.

According to an embodiment of the invention, the mass ratio of the photoinitiator to the total mass of the photosensitive resin monomers is (0.01-5):100, preferably (0.1-3):100, more preferably (0.5-2):100, for example 0.5:100, 0.55:100, 0.61:100, 1:100, 1.5: 100.

According to an embodiment of the present invention, the mass ratio of the inorganic ceramic filler to the total mass of the photosensitive resin monomers is (0.01-50):100, preferably (5-30):100, more preferably (10-20):100, for example, the mass ratio is 10:100, 15:100, 20: 100.

According to an embodiment of the present invention, the method of making the flexible polymer-based ceramic precursor article comprises the steps of:

a) blending a mercapto-containing photosensitive resin monomer, a vinyl-containing photosensitive resin monomer and a photoinitiator to obtain a resin solution;

b) optionally, adding the inorganic ceramic filler into the resin solution to obtain a mixed dispersion liquid;

c) and (c) carrying out photocuring 3D printing on the resin solution obtained in the step a) or the mixed dispersion obtained in the step b) to obtain the flexible polymer-based ceramic precursor part.

According to an embodiment of the invention, in step a) and/or b) the materials are mixed under stirring.

According to an embodiment of the present invention, in step c), the laser used for the photocuring 3D printing is visible light or ultraviolet light. The wavelength range of the visible light is 425-780nm, for example, the wavelength is 430-600nm, and is typically 445 nm. Wherein the wavelength range of the ultraviolet light is 265-420nm, such as 300-410nm, and exemplary is 405 nm. Wherein the curing time of each layer is 1-600 seconds, and illustratively, the curing time of each layer is 10 seconds, 15 seconds, 20 seconds, or 60 seconds. Wherein each layer has a thickness of 5-100 μm, for example 20-80 μm, exemplarily 80 μm, 100 μm.

According to an embodiment of the invention, in step (1), the manner of deformation is selected from at least one of the following: stretching, bending, folding, twisting, compressing, etc.; for example, the elongation is more than 0 and not more than 1000%; for example, the bend angle is greater than 0 and not more than 180 degrees; for example, the twist angle is greater than 0 and not more than 360 degrees. Illustratively, the stretch ratio is 100%, 110%, 200%.

According to an embodiment of the present invention, in step (1), the shape fixing means may fix the shape of the article by a wire (e.g., iron wire) or a clamp.

According to an embodiment of the present invention, in step (2), both heat treatments comprise a complete process of raising the temperature, keeping the temperature and lowering the temperature to room temperature.

According to an embodiment of the present invention, in the step (2), the temperature of the first heat treatment is lower than that of the second heat treatment.

For example, the temperature of the first heat treatment is 100-.

For example, the temperature of the second heat treatment is 600-.

According to an embodiment of the present invention, in step (2), the temperature increase rate of the first heat treatment and the second heat treatment may be the same or different, for example, 1 to 30 ℃/min, preferably 3 to 10 ℃/min, and exemplified by 3 ℃/min, 4 ℃/min, 5 ℃/min, 6 ℃/min. As an example, the first heat treatment and the second heat treatment are different in temperature, for example, the temperature increase rate of the first heat treatment is 3 deg.C/min, 4 deg.C/min or 5 deg.C/min, and the temperature increase rate of the second heat treatment is 5 deg.C/min.

According to an embodiment of the invention, in step (2), the time of the first heat treatment and the second heat treatment is the same or different, for example the time of the heat treatment is 0.5 to 24h, preferably 1 to 10h, exemplary 1h, 2h, 3h, 4h, 5h, 10 h. As an example, the first heat treatment and the second heat treatment are different in time, for example, the first heat treatment time is 3 hours, and the second heat treatment time is 4 hours and 6 hours.

According to the embodiment of the present invention, in the step (2), the cooling to room temperature is natural cooling along with the furnace.

According to an embodiment of the present invention, in the step (2), the atmosphere of the two heat treatments may be the same or different, and for example, may be an inert atmosphere such as nitrogen, air, or the like. When nitrogen is selected as the heat treatment atmosphere, a black ceramic product can be obtained; when air is selected as the heat treatment atmosphere, a white ceramic product can be obtained.

According to an embodiment of the present invention, in the step (2), the heat treatment is performed in a tube furnace.

According to an embodiment of the present invention, in the step (2), after the first heat treatment is completed, the jig or the wire for fixation is removed.

According to an exemplary aspect of the present invention, the method for preparing the ceramic article comprises the steps of:

1-1) performing at least one deformation operation of stretching, bending, folding, twisting and the like on the flexible polymer-based ceramic precursor workpiece, and fixing the shape of the flexible polymer-based ceramic precursor workpiece by using a metal wire;

the flexible polymer-based ceramic precursor part is prepared from the following composition through 3D photocuring printing: a mercapto group-containing photosensitive resin monomer, a vinyl group-containing photosensitive resin monomer, a photoinitiator and an optional inorganic ceramic filler; wherein at least one photosensitive resin monomer contains silicon element;

2-1) carrying out first heat treatment on the deformed workpiece obtained in the step 1-1) to shape the polymer-based ceramic precursor and remove the metal wire for fixing;

3-1) carrying out secondary heat treatment on the polymer-based ceramic precursor workpiece shaped in the step 2-1) to obtain the ceramic workpiece;

wherein the temperature of the first heat treatment is lower than that of the second heat treatment.

The invention also provides a ceramic product prepared by the preparation method.

Preferably, the ceramic article has structural versatility and complexity.

The invention also provides application of the flexible polymer-based ceramic precursor in preparing ceramic products with diverse and complex structures. Preferably, the ceramic part can be a piezoelectric ceramic part, a dielectric ceramic part, a wave-absorbing ceramic part, a ceramic solid battery, a semiconductor ceramic part or an energy-storage ceramic part.

The invention also provides the application of the ceramic part in the aspects of piezoelectric materials, dielectric materials, wave-absorbing materials, ceramic solid batteries, semiconductor materials or energy storage materials and the like.

The invention has the beneficial effects that:

according to the invention, the deformable soft polymer-based ceramic precursor is further deformed and subjected to two times of heat treatment to obtain ceramic parts with more complex and diversified structures, the deformation capability of the 3D printing ceramic material is endowed, and the more complex structure which is difficult to realize by the simplex photocuring 3D printing can be prepared. The obtained ceramic part can be applied to the fields of dielectric materials, piezoelectric materials, energy storage devices and the like.

Drawings

FIG. 1 is a photograph of a resin mixed dispersion in step 1) of example 1.

FIG. 2 is a scanning electron microscope image of a cross section of the photocured 3D printed article obtained in step 2) of example 1.

FIG. 3 is a photograph of a deformed ceramic article obtained after sintering.

FIG. 4 is a scanning electron micrograph of a cross section of a deformed ceramic article according to example 1.

Fig. 5 is a photograph of the photocured 3D printed article obtained in step 2) of example 2.

FIG. 6 is a photograph of the final sample in example 2.

Detailed Description

The technical solution of the present invention will be further described in detail with reference to specific embodiments. It is to be understood that the following examples are only illustrative and explanatory of the present invention and should not be construed as limiting the scope of the present invention. All the technologies realized based on the above-mentioned contents of the present invention are covered in the protection scope of the present invention.

Unless otherwise indicated, the raw materials and reagents used in the following examples are all commercially available products or can be prepared by known methods.

Example 1

1) 51g of 2,4, 6-trimethyl-2, 4, 6-trivinylcyclo-azosilane, 47g of trihydroxymethylpropanetris (3-mercaptoacrylate), 0.5g of camphorquinone and 10g of zirconia powder were blended, and the molar ratio of the two resins, 2,4, 6-trimethyl-2, 4, 6-trivinylcyclo-azosilane and trihydroxymethylpropanetris (3-mercaptoacrylate), was about 2: 1. Magnetically stirring for 30min at normal temperature during blending at the rotating speed of 600rpm to obtain a resin mixed dispersion liquid;

2) carrying out photocuring 3D printing on the resin mixed dispersion liquid obtained in the step 1), wherein the laser wavelength is 445nm, the layer thickness of each layer is controlled to be 100 microns, the curing time of each layer is controlled to be 10s, and a photocuring 3D printing part can be obtained after printing is finished and is used as a flexible polymer-based ceramic precursor part;

3) twisting the workpiece obtained in the step 2), and fixing the shape of the workpiece by using a clamp to obtain a deformed workpiece;

4) placing the deformed workpiece obtained in the step 3) in a tubular furnace protected by nitrogen to raise the temperature to 600 ℃ at the heating rate of 4 ℃/min, then preserving the heat for 3h, cooling the workpiece to room temperature along with the furnace, and taking down the workpiece from a clamp to obtain a sample subjected to primary heat treatment;

5) and (3) placing the sample subjected to the primary heat treatment obtained in the step 4) in a tubular furnace in an air atmosphere, heating to 1500 ℃ at a heating rate of 5 ℃/min, then preserving heat for 4h, and cooling to room temperature along with the furnace to obtain a sample subjected to secondary heat treatment, namely the final sample, namely the deformed ceramic workpiece.

Fig. 1 is a photograph of the resin mixed dispersion liquid obtained in step 1), and it can be seen that zirconium dioxide powder is stably dispersed in the resin mixed dispersion liquid.

Fig. 2 is a scanning electron microscope image of the cross section of the photocuring 3D printed part obtained in step 2), and it can be seen that the zirconium dioxide powder is uniformly distributed and does not have an obvious agglomeration phenomenon.

Fig. 3 is a photograph of a deformed ceramic article obtained after sintering, after deformation a distorted ceramic article is obtained, the structure remaining intact.

FIG. 4 is a scanning electron microscope image of a cross section of a deformed ceramic article, showing that the polymer precursor is transformed into a dense mass after sintering, and zirconium dioxide powder is uniformly distributed therein.

Example 2

1) Blending 51g of 2,4, 6-trimethyl-2, 4, 6-trivinylcyclo-azosilane, 47g of trihydroxy methyl propane tri (3-mercapto acrylate) and 0.5g of camphorquinone, wherein the molar ratio of the 2,4, 6-trimethyl-2, 4, 6-trivinylcyclo-azosilane to the trihydroxy methyl propane tri (3-mercapto acrylate) is about 2:1, magnetically stirring at normal temperature for 30min, and rotating at 600rpm to obtain a resin mixed dispersion liquid;

2) carrying out photocuring 3D printing on the resin mixed dispersion liquid obtained in the step 1), wherein the laser wavelength is 445nm, the layer thickness of each layer is controlled to be 100 microns, the curing time of each layer is controlled to be 15s, and after printing is finished, obtaining a photocuring 3D printing part, namely a flexible polymer-based ceramic precursor part;

3) compressing the workpiece obtained in the step 2) by 5%, and fixing the shape of the workpiece by using a clamp to obtain a deformed workpiece;

4) placing the deformed workpiece obtained in the step 3) in a tubular furnace protected by nitrogen to raise the temperature to 600 ℃ at the heating rate of 5 ℃/min, then preserving the heat for 3h, cooling the workpiece to room temperature along with the furnace, and taking down the workpiece from a clamp to obtain a sample subjected to primary heat treatment;

5) and (3) placing the sample subjected to the primary heat treatment obtained in the step 4) in a tubular furnace protected by nitrogen to rise to 1500 ℃ at the heating rate of 5 ℃/min, then preserving heat for 6h, and cooling to room temperature along with the furnace to obtain a sample subjected to the secondary heat treatment, namely the final sample.

Fig. 5 is a photograph of the photocuring 3D printed article in step 2). Fig. 6 is a photograph of the final sample.

Example 3

1) Blending 51g of 2,4, 6-trimethyl-2, 4, 6-trivinylcyclo-azosilane, 47g of trihydroxymethyl propane tri (3-mercaptoacrylate) and 0.5g of TPO, wherein the molar ratio of the 2,4, 6-trimethyl-2, 4, 6-trivinylcyclo-azosilane to the trihydroxymethyl propane tri (3-mercaptoacrylate) is about 2:1, magnetically stirring at normal temperature for 30min, and rotating at 600rpm to obtain a resin mixed dispersion liquid;

2) carrying out photocuring 3D printing on the resin mixed dispersion liquid obtained in the step 1), wherein the laser wavelength is 445nm, the layer thickness of each layer is controlled to be 100 microns, the curing time of each layer is controlled to be 15s, and a photocuring 3D printing part can be obtained after printing is finished;

3) the part obtained in the step 2) is pressed and stretched to 1.1 times of the original length, and the shape of the part is fixed by a clamp, so that a deformed part can be obtained;

4) placing the deformed workpiece obtained in the step 3) in a tubular furnace protected by nitrogen to raise the temperature to 600 ℃ at the heating rate of 5 ℃/min, then preserving the heat for 3h, cooling the workpiece to room temperature along with the furnace, and taking down the workpiece from a clamp to obtain a sample subjected to primary heat treatment;

5) and (3) placing the sample subjected to the primary heat treatment obtained in the step 4) in a tubular furnace protected by nitrogen to rise to 1500 ℃ at the heating rate of 5 ℃/min, then preserving heat for 6h, and cooling to room temperature along with the furnace to obtain a sample subjected to the secondary heat treatment, namely the final sample.

Example 4

1) Blending 51g of 2,4, 6-trimethyl-2, 4, 6-trivinylcyclo-azosilane, 31g of trihydroxy-methyl propane tri (3-mercapto acrylate) and 0.5g of camphorquinone, wherein the molar ratio of the two resins of the 2,4, 6-trimethyl-2, 4, 6-trivinylcyclo-azosilane and the trihydroxy-methyl propane tri (3-mercapto acrylate) is about 3:1, magnetically stirring at normal temperature for 30min, and rotating speed is 600rpm to obtain a resin solution;

2) carrying out photocuring 3D printing on the resin solution obtained in the step 1), wherein the laser wavelength is 445nm, the layer thickness of each layer is controlled to be 100 microns, the curing time of each layer is controlled to be 10s, and a photocuring 3D printing part can be obtained after printing is finished;

3) stretching the workpiece obtained in the step 2) to 1 time of the initial length of the workpiece, and fixing the shape of the workpiece by using an iron wire to obtain a deformed workpiece;

4) placing the deformed workpiece obtained in the step 3) in a tubular furnace protected by nitrogen to be heated to 600 ℃ at the heating rate of 4 ℃/min, then preserving heat for 3h, and cooling to room temperature along with the furnace to obtain a sample after primary heat treatment;

5) putting the sample subjected to the primary heat treatment obtained in the step 4) into a tubular furnace protected by nitrogen, heating to 1500 ℃ at the heating rate of 5 ℃/min, then preserving heat for 4h, and cooling to room temperature along with the furnace. And obtaining a sample after the secondary heat treatment, namely the final sample.

Example 5

1) 51g of vinyl polysiloxane, 31g of trihydroxy methyl propane tri (3-mercapto acrylate) and 0.5g of TPO are blended, and are magnetically stirred for 30min at normal temperature at the rotating speed of 600rpm to obtain a resin solution;

2) carrying out photocuring 3D printing on the resin solution obtained in the step 1), wherein the laser wavelength is 445nm, the layer thickness of each layer is controlled to be 100 microns, the curing time of each layer is controlled to be 10s, and a photocuring 3D printing part can be obtained after printing is finished;

3) bending the workpiece obtained in the step 2), controlling the bending angle to be 90 degrees, and fixing the shape of the workpiece by using an iron wire to obtain a deformed workpiece;

4) placing the deformed workpiece obtained in the step 3) in a tubular furnace protected by nitrogen to be heated to 600 ℃ at the heating rate of 4 ℃/min, then preserving heat for 3h, and cooling to room temperature along with the furnace to obtain a sample after primary heat treatment;

5) and (3) placing the sample subjected to the primary heat treatment obtained in the step 4) in a tubular furnace protected by nitrogen, heating to 1500 ℃ at the heating rate of 5 ℃/min, then preserving heat for 4h, and cooling to room temperature along with the furnace to obtain a sample subjected to secondary heat treatment, namely the final sample.

Example 6

1) Mixing 51g of vinyl polysilazane, 31g of trihydroxy methyl propane tris (3-mercaptoacrylate), 0.5g of TPO and 10g of silicon dioxide, and magnetically stirring at normal temperature for 30min at the rotating speed of 600rpm to obtain a resin solution;

2) carrying out photocuring 3D printing on the resin solution obtained in the step 1), wherein the laser wavelength is 445nm, the layer thickness of each layer is controlled to be 80 microns, the curing time of each layer is controlled to be 10s, and a photocuring 3D printing part can be obtained after printing is finished;

3) bending the workpiece obtained in the step 2), controlling the bending angle to be 120 degrees, and fixing the shape of the workpiece by using a clamp to obtain a deformed workpiece;

4) placing the deformed workpiece obtained in the step 3) in a tubular furnace protected by nitrogen to be heated to 600 ℃ at the heating rate of 3 ℃/min, then preserving heat for 3h, and cooling to room temperature along with the furnace to obtain a sample after primary heat treatment;

5) and (3) placing the sample subjected to the primary heat treatment obtained in the step 4) in a tubular furnace protected by nitrogen, heating to 1500 ℃ at the heating rate of 5 ℃/min, then preserving heat for 4h, and cooling to room temperature along with the furnace to obtain a sample subjected to secondary heat treatment, namely the final sample.

Example 7

1) 50g of mercapto polyether acrylate, 50g of vinyl polysiloxane, 0.5g of benzophenone and 5g of zirconium dioxide are blended, and are magnetically stirred for 30min at normal temperature at the rotating speed of 800rpm to obtain a resin mixed dispersion liquid;

2) carrying out photocuring 3D printing on the resin mixed dispersion liquid obtained in the step 1), wherein the laser wavelength is 445nm, the layer thickness of each layer is controlled to be 100 microns, the curing time of each layer is controlled to be 15s, and a photocuring 3D printing part can be obtained after printing is finished;

3) stretching the workpiece obtained in the step 2) to 2 times of the original length, and fixing the shape of the workpiece by using a clamp to obtain a deformed workpiece;

4) placing the deformed workpiece obtained in the step 3) in a tubular furnace protected by nitrogen to raise the temperature to 600 ℃ at the heating rate of 5 ℃/min, then preserving the heat for 3h, cooling the workpiece to room temperature along with the furnace, and taking down the workpiece from a clamp to obtain a sample subjected to primary heat treatment;

5) and (3) placing the sample subjected to the primary heat treatment obtained in the step 4) in a tubular furnace protected by nitrogen to rise to 1500 ℃ at the heating rate of 5 ℃/min, then preserving heat for 6h, and cooling to room temperature along with the furnace to obtain a sample subjected to the secondary heat treatment, namely the final sample.

Example 8

1) Blending 40g of mercapto epoxy acrylate, 50g of vinyl polysilazane, 0.5g of 4-methylbenzophenone and 5g of barium titanate, and magnetically stirring at normal temperature for 30min at the rotating speed of 600rpm to obtain a resin mixed dispersion liquid;

2) carrying out photocuring 3D printing on the resin mixed dispersion liquid obtained in the step 1), wherein the laser wavelength is 405nm, the layer thickness of each layer is controlled to be 100 microns, the curing time of each layer is controlled to be 15s, and a photocuring 3D printing part can be obtained after printing is finished;

3) bending the workpiece obtained in the step 2) by 180 degrees, and fixing the shape of the workpiece by using a clamp to obtain a deformed workpiece;

4) placing the deformed workpiece obtained in the step 3) in a tubular furnace protected by nitrogen to raise the temperature to 600 ℃ at the heating rate of 5 ℃/min, then preserving the heat for 3h, cooling the workpiece to room temperature along with the furnace, and taking down the workpiece from a clamp to obtain a sample subjected to primary heat treatment;

5) and (3) placing the sample subjected to the primary heat treatment obtained in the step 4) in a tubular furnace protected by nitrogen to raise the temperature to 1400 ℃ at the heating rate of 5 ℃/min, then preserving the heat for 6h, and cooling the sample to room temperature along with the furnace to obtain a sample subjected to the secondary heat treatment, namely the final sample.

The embodiments of the present invention have been described above. However, the present invention is not limited to the above embodiment. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.