A photothermal dual-curing ZrB2-ZrC-SiC ceramic precursor composition, its preparation method and application
By combining a photothermal dual-curing ZrB2-ZrC-SiC ceramic precursor composition with photosensitive resin and thermal initiator, the problem of photocuring 3D printing of ZrB2-ZrC-SiC ceramics has been solved, achieving efficient and dense ceramic printing, which is suitable for aerospace and other fields.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- WUHAN UNIV OF TECH
- Filing Date
- 2026-03-26
- Publication Date
- 2026-05-26
AI Technical Summary
In the existing technology, there is no reported method for photopolymerization 3D printing of ZrB2-ZrC-SiC ceramics, which leads to limitations in photopolymerization performance. The conversion rate of active groups such as double bonds in the precursor is not high, and the curing depth is insufficient, making it difficult to meet the manufacturing requirements of complex structural parts.
A photothermal dual-curing ZrB2-ZrC-SiC ceramic precursor composition is adopted. Through the synergistic effect of photosensitive resin, ZrB2-ZrC-SiC ceramic precursor and photo and thermal initiators, photocuring and thermal curing are combined to improve crosslinking density, avoid phase separation, and form a dense ZrB2-ZrC-SiC multiphase ceramic.
It has achieved efficient photopolymerization printing of ZrB2-ZrC-SiC ceramics with a curing depth of over 150 micrometers, improving the density and yield of ceramics and meeting the needs for rapid printing of complex structural parts.
Smart Images
Figure CN122079641A_ABST
Abstract
Description
Technical Field
[0001] This invention relates to the field of 3D printing materials technology, and in particular to a photothermal dual-curing ZrB2-ZrC-SiC ceramic precursor composition, its preparation method, and its application. Background Technology
[0002] Ultra-high temperature ceramics, especially ZrB2 and ZrC-based materials, possess crucial application value in aerospace, hypersonic vehicles, and propulsion systems due to their excellent physical and chemical stability at ultra-high temperatures and reactive atmospheres reaching 2000℃ or even 3000℃ (Jyoti et al., 2025). However, the insufficient oxidation resistance of single ultra-high temperature ceramic materials at high temperatures limits their widespread application. ZrB2-ZrC-SiC ternary composites exhibit excellent oxidation and ablation resistance over a wide temperature range, overcoming the shortcomings of single materials. Furthermore, by optimizing the ZrB2 content, the mechanical properties of ZrC-SiC-ZrB2 ceramics can be significantly improved. Traditional ceramic preparation methods struggle to meet the manufacturing requirements of complex geometric parts, while photopolymerization 3D printing, as a rapid prototyping technology, can manufacture complex structural parts with high precision, effectively solving the problems of difficult ceramic material processing and long preparation cycles, making it an important development direction in the field of ultra-high temperature ceramics.
[0003] Currently, there are no reports on the research of precursors used in photopolymerization 3D printing of ZrB2-ZrC-SiC ceramics. A possible approach is to combine polymer-converted ceramics technology with photopolymerization 3D printing technology. Polymer-converted ceramics technology leverages the chemical designability of organic polymer precursors to customize ceramic materials according to actual application requirements, and then transforms them into the target ceramic through a subsequent pyrolysis process. For example, research has successfully prepared high-purity spherical ZrC nanoparticles using Zr-MOF-derived ZrC nanoparticles as precursors, which were then converted into ZrC ceramics through thermal decomposition. C / C-ZrC-SiC composite materials have been successfully prepared through processes such as polymerization impregnation, pyrolysis, and reactive melt infiltration, significantly improving the flexural and tensile strength of the materials. However, due to limitations in photopolymerization performance, such as low conversion rates and insufficient curing depth of active groups like double bonds in the precursors when using only photopolymerization, there are no reports on using ZrB2-ZrC-SiC ceramic precursors for photopolymerization 3D printing.
[0004] Therefore, there is an urgent need for a photopolymerization 3D printing method for ZrB2-ZrC-SiC ceramics to meet practical application requirements. Summary of the Invention
[0005] In view of this, the present invention proposes a photothermal dual-curing ZrB2-ZrC-SiC ceramic precursor composition, its preparation method, and its application. Through the synergistic effect of the ZrB2-ZrC-SiC ceramic precursor, photosensitive resin, and thermal initiator, photocuring printing of ZrB2-ZrC-SiC multiphase ceramics is achieved, providing a new solution for the efficient 3D printing preparation of ZrB2-ZrC-SiC ceramics.
[0006] The technical solution of this invention is implemented as follows: In a first aspect, the present invention provides a photothermal dual-curing ZrB2-ZrC-SiC ceramic precursor composition, the components of which include a photosensitive resin, a ZrB2-ZrC-SiC ceramic precursor, a photoinitiator, and a thermal initiator; the molecule of the photosensitive resin contains an acryloyloxy group, and the molecule of the ZrB2-ZrC-SiC ceramic precursor contains a vinyl double bond in an acrylate ligand coordinated with Zr, and a vinyl group directly connected to Si.
[0007] Acryloyloxy groups in the photosensitive resin possess extremely high photoinitiation polymerization activity, responsible for establishing a "rigid framework" of three-dimensional spatial structure upon light exposure. Meanwhile, the acrylate ligands linked to Zr in the ZrB2-ZrC-SiC precursor provide crosslinking sites similar to the resin structure, ensuring that the inorganic source molecules are anchored at the polymer network. Although the vinyl groups linked to Si have slightly weaker photoactivity, they can undergo supplementary polymerization with unreacted acryloyloxy groups during the thermal initiation stage, eliminating light dead zones and greatly increasing the final crosslinking density of the system. In this invention, the photosensitive resin mainly plays a crosslinking role and will not transform into ZrB2-ZrC-SiC ceramics after pyrolysis. Utilizing the homogeneity of the acrylic functional groups in the ZrB2-ZrC-SiC precursor and the photosensitive resin, phase separation between the inorganic precursor and the organic resin during the curing process can be avoided. Thermal initiators can initiate the free radical polymerization reaction of photosensitive resins and ZrB2-ZrC-SiC ceramic precursors, and during the photocuring process, they can further promote the full curing of unsaturated groups such as double bonds.
[0008] Based on the above technical solutions, preferably, the photosensitive resin is an acrylate resin monomer and / or oligomer, and a single resin molecule contains not less than 2 acryloyloxy groups.
[0009] Based on the above technical solutions, preferably, the photosensitive resin is selected from one or more of 1,6-hexanediol diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, ditrimethylolpropane tetraacrylate, dipentaerythritol pentaacrylate, or dipentaerythritol hexaacrylate; more preferably, the photosensitive resin is pentaerythritol tetraacrylate.
[0010] Based on the above technical solutions, preferably, the ZrB2-ZrC-SiC ceramic precursor comprises zirconium source, silicon source, carbon source and acrylic acid.
[0011] Based on the above technical solutions, preferably, the zirconium source includes zirconium n-propoxide, the silicon source includes vinyltriethoxysilane, and the carbon source includes divinylbenzene.
[0012] Based on the above technical solutions, preferably, the mass ratio of the photosensitive resin to the ZrB2-ZrC-SiC ceramic precursor is 0.5~4:1.
[0013] Based on the above technical solution, a further preferred embodiment is that the mass ratio of the photosensitive resin to the ZrB2-ZrC-SiC ceramic precursor is 2:1.
[0014] Secondly, a method for preparing the photothermal dual-curing ZrB2-ZrC-SiC ceramic precursor composition as described above is provided, comprising the following steps: S1, mix the ZrB2-ZrC-SiC ceramic precursor with the photosensitive resin to obtain mixture A; S2, dissolve the photoinitiator completely in mixture A to obtain mixture B; S3, the thermal initiator is fully dissolved in mixture B to obtain the precursor composition.
[0015] Based on the above technical solutions, preferably, in step S2, the photoinitiator is selected from one or more of bis(2,4,6-trimethylbenzoyl)diphenylphosphine oxide, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, or ethyl 2,4,6-trimethylbenzoylphenylphosphonate; in step S3, the thermal initiator is selected from one or more of tert-butyl peroxide, azobisisobutyronitrile, dicumyl peroxide, or dibenzoyl peroxide; both the photoinitiator and the thermal initiator are free radical initiators; more preferably, the photoinitiator is bis(2,4,6-trimethylbenzoyl)diphenylphosphine oxide; and the thermal initiator is tert-butyl peroxide.
[0016] Based on the above technical solutions, preferably, the mass of the photoinitiator is 3-5% of the mass of mixture A, and the mass of the thermal initiator is 2-5% of the mass of mixture A.
[0017] Based on the above technical solutions, a further preferred embodiment is that the mass of the photoinitiator is 3.3% of the mass of mixture A; and the mass of the thermal initiator is 2% of the mass of mixture A.
[0018] Thirdly, a method for preparing ZrB2-ZrC-SiC ceramics is provided, comprising the following steps: photocuring and printing a photothermal dual-curing ZrB2-ZrC-SiC ceramic precursor composition to obtain a printed green body; sequentially cleaning, thermal curing, degreasing, and high-temperature sintering the printed green body to obtain ZrB2-ZrC-SiC ceramics.
[0019] Based on the above technical solutions, preferably, the photopolymerization printing involves pouring the precursor composition into the material tank of the 3D printer, adjusting the exposure time to 3~60s, and the exposure intensity to 10~200mW / cm. 2 The printed layer thickness is 25-100 micrometers, and 3D printing is completed layer by layer to obtain a printed blank; further optimized, the exposure time is adjusted to 30 seconds and the exposure intensity is 100 mW / cm. 2 The printing layer thickness is 50 micrometers, and 3D printing is completed layer by layer to obtain the printed blank.
[0020] Based on the above technical solutions, preferably, the thermosetting includes placing the printed preform in an oven, heating it to 80~150℃, and holding it at that temperature for 1~10 hours to obtain a thermosetting preform; more preferably, the temperature is raised to 120℃ and held for 2 hours to obtain a thermosetting preform.
[0021] Based on the above technical solutions, preferably, the degreasing includes heating the thermosetting preform obtained by thermosetting treatment to 500~700℃ at a rate of 0.25~4℃ / min, holding it at that temperature for 1~5h, and then cooling it in the furnace to obtain a carbonized preform; during the heating process, holding it at the temperature corresponding to each weight loss peak of the DTG curve obtained by thermogravimetric analysis for 1~2 hours respectively.
[0022] Based on the above technical solutions, a further preferred method is to heat the thermosetting preform obtained after thermosetting treatment to 600℃ at a rate of 0.5℃ / min, hold it at that temperature for 3 hours, and then cool it in the furnace to obtain a carbonized preform; during the heating process, according to the temperature corresponding to each weight loss peak of the DTG curve obtained by thermogravimetric analysis, the preform is held at that temperature for 1.5 hours respectively.
[0023] Based on the above technical solutions, preferably, the high-temperature sintering includes heating the carbonized green body to 1500-2000℃ at a rate of 2-10℃ / min, holding it at that temperature for 1-5 hours, and then cooling it in the furnace to obtain a ZrB2-ZrC-SiC multiphase ceramic sample.
[0024] Based on the above technical solution, a further preferred embodiment is that the high-temperature sintering includes heating the carbonized green body to 1600℃ at a rate of 10℃ / min, holding it at that temperature for 1 hour, and then cooling it in the furnace to obtain a ZrB2-ZrC-SiC multiphase ceramic sample.
[0025] The photothermal dual-curing ZrB2-ZrC-SiC ceramic precursor composition of the present invention has the following advantages over the prior art: 1. The ZrB2-ZrC-SiC ceramic precursor composition proposed in this invention can achieve both photocuring and thermal curing. Exposure time is 10 seconds, and exposure intensity is 50 mW / cm². 2 The curing depth reaches over 150 micrometers, which is beneficial for the rapid printing of ZrB2-ZrC-SiC ceramic precursor preforms. The preforms printed by photopolymerization can be transformed into ZrB2-ZrC-SiC ceramics through thermal curing, debinding, and high-temperature sintering, thereby realizing the photopolymerization printing of ZrB2-ZrC-SiC multiphase ceramics.
[0026] 2. By utilizing the double bonds and vinyl groups in the ZrB2-ZrC-SiC ceramic precursor, and the acryloyloxy groups in the photosensitive resin, a synergistic effect is achieved, which increases the final crosslinking density of the system. At the same time, by utilizing the homogeneity of the acrylic functional groups of the precursor and the resin, phase separation between the inorganic precursor and the organic resin during the curing process is avoided.
[0027] 3. Thermal initiators not only compensate for the shortcomings of photocuring, but also induce further cross-linking of residual double bonds in the early stage of thermal decomposition, forming a denser pre-ceramic network, thereby further improving the yield and density of the final ZrB2-ZrC-SiC ceramic. Attached Figure Description
[0028] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.
[0029] Figure 1 The image shows the morphology of the ZrB2-ZrC-SiC ceramic precursor composition prepared in Example 1 of this invention. Figure 2 This is a graph showing the relationship between the curing depth and incident light energy of the ZrB2-ZrC-SiC ceramic precursor composition prepared in Example 1 of the present invention. Figure 3 The thermogravimetric analysis spectrum, including TG curve and DTG curve, is obtained by thermogravimetric analysis after the photocuring printed sample of the ZrB2-ZrC-SiC ceramic precursor composition prepared in Example 1 of the present invention is cured by thermogravimetric analysis. Figure 4 The image shows the XRD pattern of the ZrB2-ZrC-SiC ceramic precursor sample prepared in Example 1 of this invention after high-temperature sintering. Detailed Implementation
[0030] The technical solutions of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of the present invention.
[0031] The raw materials used in this invention are all commercially available products.
[0032] Example 1 This embodiment provides a method for preparing and applying a photothermal dual-curing ZrB2-ZrC-SiC ceramic precursor composition.
[0033] Preparation of liquid ZrB2-ZrC-SiC ceramic precursor: 8.85 mL of zirconium propoxide solution (70% purity) was placed in a flask, and 0.04 mol (2.93 g) of acrylic acid (99% purity) was added. The mixture was magnetically stirred at 500 rpm for 24 h in an oil bath at 25 °C to obtain a pale yellow, clear, and transparent solution. Then, 0.02 mol (3.92 g) of vinyltriethoxysilane (97% purity) and 0.02 mol (2.51 g) of phenylboronic acid (97% purity) were added. The oil bath was heated to 60 °C, and the mixture was magnetically stirred at 500 rpm for 2 h to obtain a yellow, clear solution. Using a rotary evaporator, the solvent and unreacted substances were removed by evacuating to -0.10 to -0.05 kPa at 85 °C to obtain a yellow, transparent liquid. The obtained yellow, transparent liquid was then reacted with 0.04... 6.50 g of divinylbenzene (80% purity) was mixed and stirred at room temperature for 2 h to obtain liquid ZrB2-ZrC-SiC ceramic precursor.
[0034] Take 6.5 g of the above liquid ZrB2-ZrC-SiC ceramic precursor, add 13.0 g of pentaerythritol tetraacrylate, and stir magnetically at 300 rpm until completely dissolved. Add 0.65 g of bis(2,4,6-trimethylbenzoyl)diphenylphosphine oxide, and stir magnetically at 300 rpm until completely dissolved. Finally, add 0.40 g of tert-butyl peroxide, and stir magnetically at 300 rpm until completely dissolved, to obtain the following... Figure 1 The photothermal dual-curing ZrB2-ZrC-SiC ceramic precursor composition shown is illustrated.
[0035] The ceramic precursor composition was poured into the material tank of the 3D printer, and the exposure time was adjusted to 30 seconds with an exposure intensity of 100 mW / cm². 2 The curing depth was tested, and the results were as follows: Figure 2 As shown.
[0036] The layer thickness was set to 50 micrometers, and 3D printing was completed layer by layer to obtain a printed blank. The printed blank was placed in an oven, heated to 120°C, and held at that temperature for 2 hours to obtain a thermosetting blank.
[0037] like Figure 3 As shown, the TG and DTG curves of the thermosetting preform were tested using a thermogravimetric analyzer. The remaining mass after pyrolysis at 1000℃ under argon atmosphere was 28.8%, and the DTG curve showed weight loss peaks at 240℃ and 445℃.
[0038] The thermosetting preform was placed in a tube furnace and heated to 600℃ at a rate of 0.5℃ / min under an argon atmosphere, and held for 3 hours. During the heating process, it was held at 240℃ and 445℃ for 1.5 hours each. Finally, it was cooled to room temperature with the furnace to obtain a carbonized preform. The carbonized preform was then placed in a high-temperature furnace and heated to 1600℃ at a rate of 10℃ / min under a vacuum or argon atmosphere, and held for 1 hour. Finally, it was cooled to room temperature with the furnace to obtain a sintered ceramic sample. Figure 4 The XRD refinement results of the sintered sample show that the relative contents of ZrB2, ZrC and SiC are 78.5%, 6.7% and 14.8%, respectively.
[0039] Example 2 This embodiment provides a method for preparing and applying a photothermal dual-curing ZrB2-ZrC-SiC ceramic precursor composition.
[0040] Preparation of liquid ZrB2-ZrC-SiC ceramic precursor: Same as in Example 1.
[0041] Take 6.5 g of the above liquid ZrB2-ZrC-SiC ceramic precursor, add 3.25 g of pentaerythritol tetraacrylate, and stir magnetically at 300 rpm until completely dissolved. Add 0.29 g of 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, and stir magnetically at 300 rpm until completely dissolved. Finally, add 0.20 g of azobisisobutyronitrile, and stir magnetically at 300 rpm until completely dissolved.
[0042] The ceramic precursor composition was poured into the material tank of the 3D printer, and the exposure time was adjusted to 30 seconds with an exposure intensity of 100 mW / cm². 2 Test the curing depth.
[0043] The layer thickness was set to 50 micrometers, and 3D printing was completed layer by layer to obtain a printed blank. The printed blank was placed in an oven, heated to 80°C, and held at that temperature for 10 hours to obtain a thermosetting blank.
[0044] The thermogravimetric analysis (TG) and thermogravimetric analysis (DTG) curves of the thermosetting preform were tested. The remaining mass after pyrolysis at 1000℃ under argon atmosphere was 41.6%, and the DTG curve showed weight loss peaks at 245℃ and 440℃.
[0045] The thermosetting preform was placed in a tube furnace and heated to 500℃ at a rate of 0.25℃ / min under an argon atmosphere, and held at that temperature for 5 hours. During the heating process, it was held at 245℃ and 440℃ for 1 hour each. Finally, it was cooled to room temperature with the furnace to obtain a carbonized preform. The carbonized preform was then placed in a high-temperature furnace and heated to 1500℃ at a rate of 2℃ / min under a vacuum or argon atmosphere, and held at that temperature for 1 hour. Finally, it was cooled to room temperature with the furnace to obtain a sintered ceramic sample.
[0046] Example 3 This embodiment provides a method for preparing and applying a photothermal dual-curing ZrB2-ZrC-SiC ceramic precursor composition.
[0047] Preparation of liquid ZrB2-ZrC-SiC ceramic precursor: Same as in Example 1.
[0048] Take 6.5g of the above liquid ZrB2-ZrC-SiC ceramic precursor, add 26g of pentaerythritol tetraacrylate, and stir magnetically at 300rpm until completely dissolved. Add 1.63g of ethyl 2,4,6-trimethylbenzoylphenylphosphonate, and stir magnetically at 300rpm until completely dissolved. Finally, add 1.63g of dicumyl peroxide, and stir magnetically at 300rpm until completely dissolved.
[0049] The ceramic precursor composition was poured into the material tank of the 3D printer, and the exposure time was adjusted to 30 seconds with an exposure intensity of 100 mW / cm². 2 Test the curing depth.
[0050] The layer thickness was set to 50 micrometers, and 3D printing was completed layer by layer to obtain a printed blank. The printed blank was placed in an oven, heated to 150°C, and held at that temperature for 1 hour to obtain a thermosetting blank.
[0051] The thermogravimetric analysis (TG) and thermogravimetric analysis (DTG) curves of the thermosetting preform were tested. The remaining mass after pyrolysis at 1000℃ under argon atmosphere was 22.4%, and the DTG curve showed weight loss peaks at 240℃ and 435℃.
[0052] The thermosetting preform was placed in a tube furnace and heated to 700℃ at a rate of 4℃ / min under an argon atmosphere, and held for 1 hour. During the heating process, it was held at 240℃ and 435℃ for 2 hours each, and finally cooled to room temperature with the furnace to obtain a carbonized preform. The carbonized preform was then placed in a high-temperature furnace and heated to 2000℃ at a rate of 5℃ / min under a vacuum or argon atmosphere, and held for 5 hours. Finally, it was cooled to room temperature with the furnace to obtain a sintered ceramic sample.
[0053] Example 4 The preparation method of this embodiment is basically the same as that of Example 1, except that pentaerythritol tetraacrylate is replaced with equal amounts of 1,6-hexanediol diacrylate (Group 1), trimethylolpropane triacrylate (Group 2), pentaerythritol triacrylate (Group 3), pentaerythritol tetraacrylate (Group 4), dimethylolpropane tetraacrylate (Group 5), dipentaerythritol pentaacrylate (Group 6), dipentaerythritol hexaacrylate (Group 7), and a combination of pentaerythritol tetraacrylate and trimethylolpropane triacrylate in an equal mass ratio (Group 8). The results show that the precursor compositions of Groups 1 to 8 can still achieve photocuring after changing the type of acrylate resin monomer. Furthermore, the curing depth tends to increase with the increase in the number of acrylate functional groups in a single molecule.
[0054] Example 5 The preparation method of this embodiment is basically the same as that of Example 1, except that 3.25 g of pentaerythritol tetraacrylate is added, that is, the mass of pentaerythritol tetraacrylate is 0.5 times the mass of the precursor. As a result, although the curing depth is lower than that of Example 1, it can still cure normally.
[0055] Comparative Example 1 The preparation method of this comparative example is basically the same as that of Example 1, except that 2.6 g of pentaerythritol tetraacrylate was added, that is, the mass of pentaerythritol tetraacrylate is 0.4 times the mass of the precursor. As a result, this precursor composition could not withstand an exposure time of 15 s and an exposure intensity of 100 mW / cm. 2 Under certain conditions, the film could not be cured by photopolymerization printing with a single-layer printing time of 10 seconds. This indicates that when the content of pentaerythritol tetraacrylate is reduced to a certain level, the curing depth of the precursor composition is too low, making efficient photopolymerization impossible.
[0056] Example 6 The preparation method of this embodiment is basically the same as that of Example 1, except that 26 g of pentaerythritol tetraacrylate is added, that is, the mass of pentaerythritol tetraacrylate is 4 times the mass of the precursor. As a result, the curing depth is significantly improved compared with Example 1, indicating that the curing depth of the precursor composition can be increased by increasing the content of pentaerythritol tetraacrylate.
[0057] Comparative Example 2 The preparation method of this comparative example is basically the same as that of Example 1, except that 32g of pentaerythritol tetraacrylate is added, that is, the mass of pentaerythritol tetraacrylate is 4.9 times the mass of the precursor.
[0058] Comparative Example 3 The preparation method of this comparative example is basically the same as that of Example 1, except that pentaerythritol tetraacrylate is replaced with an equal amount of vinyl ether resin monomer, specifically triethylene glycol divinyl ether.
[0059] Comparative Example 4 The preparation method of this comparative example is basically the same as that of Example 1, except that pentaerythritol tetraacrylate is replaced with an equal amount of epoxy resin monomer, specifically phenyl glycidyl ether.
[0060] As a result, during the preparation processes of Comparative Examples 3 and 4, it was found that the precursor compositions prepared using monomers without acryloyloxy groups could not withstand exposure times of 15 s and exposure intensities of 100 mW / cm². 2 Under certain conditions, the film cannot be cured by photopolymerization printing with a single-layer printing time of 10 seconds. This comparative example demonstrates the necessity of using photosensitive resin monomers containing acryloyl groups.
[0061] Comparative Example 5 The preparation method of this comparative example is basically the same as that of Example 1, except that the heating rate in the degreasing step is 5°C / min. As a result, the carbonized green body obtained was severely cracked.
[0062] Comparative Example 6 The preparation method of this comparative example is basically the same as that of Example 1, except that the sintering temperature in the high-temperature sintering step is 1400℃. As a result, the product contains a large amount of unreacted ZrO2 phase.
[0063] Comparative Example 7 The preparation method of this comparative example is basically the same as that of Example 1, except that in the preparation of the ZrB2-ZrC-SiC ceramic precursor, acrylic acid is replaced with an equal amount of acetylacetone, so that the ligands linked to Zr do not contain double bonds, and only the vinyl groups in the branches linked to Si are retained. The results show that this precursor composition cannot withstand exposure at an exposure time of 15 s and an exposure intensity of 100 mW / cm². 2 Under certain conditions, the ZrB2-ZrC-SiC ceramic precursor cannot be photopolymerized and printed with a single-layer printing time of 10 seconds. This comparative example demonstrates the importance of simultaneously containing double bonds and vinyl groups in the ZrB2-ZrC-SiC ceramic precursor.
[0064] In summary, this invention provides a method for preparing and applying a photothermal dual-curing ZrB2-ZrC-SiC ceramic precursor composition. The ZrB2-ZrC-SiC ceramic precursor composition proposed in this invention can achieve both photocuring and thermal curing. The exposure time is 10 s, and the exposure intensity is 50 mW / cm². 2 The curing depth reaches over 150 micrometers, which is beneficial for the rapid printing of ZrB2-ZrC-SiC ceramic precursor preforms. The preforms printed by photopolymerization can be transformed into ZrB2-ZrC-SiC ceramics through thermal curing, debinding, and high-temperature sintering, thereby realizing the photopolymerization printing of ZrB2-ZrC-SiC multiphase ceramics.
[0065] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the protection scope of the present invention.
Claims
1. A photothermal dual-curing ZrB2-ZrC-SiC ceramic precursor composition, characterized in that: Its components include photosensitive resin, ZrB2-ZrC-SiC ceramic precursor, photoinitiator and thermal initiator; the molecule of the photosensitive resin contains an acryloyloxy group, and the molecule of the ZrB2-ZrC-SiC ceramic precursor contains a vinyl double bond in an acrylate ligand coordinated with Zr, as well as a vinyl group directly connected to Si.
2. The photothermal dual-curing ZrB2-ZrC-SiC ceramic precursor composition as described in claim 1, characterized in that: The photosensitive resin is selected from one or more of 1,6-hexanediol diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dimethylolpropane tetraacrylate, dipentaerythritol pentaacrylate, or dipentaerythritol hexaacrylate.
3. The photothermal dual-curing ZrB2-ZrC-SiC ceramic precursor composition as described in claim 1, characterized in that, The ZrB2-ZrC-SiC ceramic precursor comprises zirconium source, silicon source, carbon source and acrylic acid.
4. The photothermal dual-curing ZrB2-ZrC-SiC ceramic precursor composition as described in claim 1, characterized in that, The mass ratio of the photosensitive resin to the ZrB2-ZrC-SiC ceramic precursor is 0.5~4:
1.
5. A method for preparing the photothermal dual-curing ZrB2-ZrC-SiC ceramic precursor composition as described in any one of claims 1 to 4, characterized in that, Includes the following steps: S1, mix the ZrB2-ZrC-SiC ceramic precursor with the photosensitive resin to obtain mixture A; S2, dissolve the photoinitiator completely in mixture A to obtain mixture B; S3, the thermal initiator is fully dissolved in mixture B to obtain the precursor composition.
6. The method for preparing the photothermal dual-curing ZrB2-ZrC-SiC ceramic precursor composition as described in claim 5, characterized in that: In step S2, the photoinitiator is selected from one or more of bis(2,4,6-trimethylbenzoyl)diphenylphosphine oxide, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, or ethyl 2,4,6-trimethylbenzoylphenylphosphonate; in step S3, the thermal initiator is selected from one or more of tert-butyl peroxide, azobisisobutyronitrile, dicumyl peroxide, or dibenzoyl peroxide.
7. The method for preparing the photothermal dual-curing ZrB2-ZrC-SiC ceramic precursor composition as described in claim 6, characterized in that: The mass of the photoinitiator is 3-5% of the mass of mixture A, and the mass of the thermal initiator is 2-5% of the mass of mixture A.
8. A method for preparing ZrB2-ZrC-SiC ceramics, characterized in that, The process includes the following steps: photocuring and printing the photothermal dual-curing ZrB2-ZrC-SiC ceramic precursor composition as described in any one of claims 1 to 4 to obtain a printed green body; sequentially cleaning, thermal curing, degreasing, and high-temperature sintering the printed green body to obtain ZrB2-ZrC-SiC ceramic.
9. The method for preparing ZrB2-ZrC-SiC ceramics as described in claim 8, characterized in that: The degreasing process involves heating the thermosetting preform obtained after thermosetting treatment to 500-700°C at a rate of 0.25-5°C / min, holding it at that temperature for 1-5 hours, and then cooling it in the furnace to obtain a carbonized preform. During the heating process, the temperature corresponding to each weight loss peak of the DTG curve obtained from the thermogravimetric analysis was maintained for 1 to 2 hours.
10. The method for preparing ZrB2-ZrC-SiC ceramics as described in claim 9, characterized in that: The high-temperature sintering process involves heating the carbonized green body to 1500-2000℃ at a rate of 2-10℃ / min, holding it at that temperature for 1-5 hours, and then cooling it in the furnace to obtain a ZrB2-ZrC-SiC multiphase ceramic sample.