A photocurable 3D printing zirconium diboride-based ultra-high temperature ceramic slurry and its preparation method and application

Abstract

The present invention discloses a photocurable 3D printing slurry for zirconium diboride-based ultrahigh-temperature ceramics, a printing method, and applications thereof. The photocurable printing slurry is formulated using a zirconium diboride-based ultrahigh-temperature ceramic sol-gel precursor xerogel powder. This significantly improves the curing depth of the photocurable 3D printing slurry. This facilitates the printing of high-precision, defect-free zirconium diboride-based ultrahigh-temperature ceramic green bodies. Furthermore, by optimizing the sintering temperature, the present invention can produce porous zirconium diboride-based ultrahigh-temperature ceramics.

Description

Technical Field

[0001] The present invention belongs to the technical field of ceramic additive manufacturing, and specifically relates to a photocuring 3D printing zirconium diboride-based ultra-high temperature ceramic slurry and a printing method thereof. Background Art

[0002] Ultrahigh-temperature ceramics (UHT ceramics) are a class of ceramic materials that maintain stable physical and chemical properties in harsh environments such as ultrahigh temperatures (≥2000°C) and reactive atmospheres. These materials primarily include refractory metal carbides, borides, and nitrides. Compared to conventional high-temperature structural materials, zirconium diboride (ZrB2)-based UHT ceramics exhibit properties such as ultrahigh temperature resistance, ablation resistance, high strength, thermal shock resistance, and chemical stability. These ceramics are capable of withstanding extreme environments such as hypersonic long-duration flight, transatmospheric flight, and atmospheric reentry. Their high melting point and resistance to high-temperature oxidation and thermal stress make them suitable for use in extreme environments such as ballistic missile nose cones, hypersonic vehicle fronts, rocket engines, and aerospace reentry vehicles. Zirconium diboride-based UHT ceramics are typically manufactured using traditional sintering processes, such as hot pressing, pressureless sintering, and spark plasma sintering. However, achieving complex shapes is extremely difficult due to the geometric limitations of the mold or cavity. With the development of stereolithography (SLI) technology, fabricating ceramic structures with complex shapes has become much easier.

[0003] Due to the high absorbance of zirconium diboride-based ultrahigh-temperature ceramic powder in the UV-visible light band, the curing depth of photocurable slurries is low, making it difficult to form complex components using photocurable 3D printing technology. This patent proposes a method for preparing zirconium diboride-based ultrahigh-temperature ceramics using photocurable 3D printing. The photocurable slurry, prepared using xerogel powder, a zirconium diboride-based ultrahigh-temperature ceramic sol-gel precursor, significantly increases the curing depth of the photocurable slurry, enabling rapid photocuring of zirconium diboride-based ultrahigh-temperature ceramic components. Summary of the Invention

[0004] The purpose of this section is to summarize some aspects of the embodiments of the present invention and briefly introduce some preferred embodiments. Some simplifications or omissions may be made in this section and the abstract and title of this application to avoid obscuring the purpose of this section, the abstract and the title of the invention, and such simplifications or omissions should not be used to limit the scope of the present invention.

[0005] In view of the above problems and / or the problems existing in the prior art, the present invention is proposed.

[0006] Therefore, the purpose of the present invention is to overcome the deficiencies in the prior art and provide a photocurable 3D printing zirconium diboride-based ultra-high temperature ceramic slurry.

[0007] In order to solve the above technical problems, the present invention provides the following technical solutions: a photocurable 3D printing zirconium diboride-based ultra-high temperature ceramic slurry, characterized by comprising:

[0008] Zirconium diboride-based ultrahigh temperature ceramic sol-gel precursor xerogel powder, photosensitive resin active diluent, dispersant, photoinitiator and light absorber;

[0009] Among them, the zirconium diboride-based ultra-high temperature ceramic sol-gel precursor dry gel powder has a particle size of 0.1 to 200 μm and an absorbance of <0.7 in the 250-600 nm light wave band; and its mass fraction in the zirconium diboride-based ultra-high temperature ceramic slurry is 40 to 90 wt.%.

[0010] The purpose of the present invention is to overcome the deficiencies in the prior art and provide a method for preparing a zirconium diboride-based ultrahigh temperature ceramic slurry for photocuring 3D printing.

[0011] As a preferred embodiment of the preparation method of the present invention, wherein:

[0012] Stirring the zirconium source and ethanol to obtain a zirconium source solution;

[0013] The boron source, the carbon source and the ethanol are stirred to obtain a mixed solution of the boron source and the carbon source;

[0014] adding the zirconium source solution to the mixed solution of the boron source and the carbon source and stirring to obtain a mixed solution of the zirconium source, the boron source and the carbon source;

[0015] The mixed solution of the zirconium source, the boron source and the carbon source is dried, ground and sieved to obtain a zirconium diboride-based ultrahigh temperature ceramic sol-gel precursor xerogel powder;

[0016] adding zirconium diboride-based ultrahigh temperature ceramic sol-gel precursor xerogel powder into a polytetrafluoroethylene ball milling jar and milling the xerogel powder to obtain zirconium diboride-based ultrahigh temperature ceramic sol-gel precursor xerogel powder;

[0017] Zirconium diboride-based ultrahigh temperature ceramic sol-gel precursor dry gel powder, photosensitive resin active diluent, dispersant, photoinitiator and light absorber are mixed to form zirconium diboride-based ultrahigh temperature ceramic slurry.

[0018] As a preferred embodiment of the photocurable 3D printing zirconium diboride-based ultra-high temperature ceramic slurry of the present invention, the zirconium source and ethanol are stirred to obtain a zirconium source solution, wherein the stirring temperature is 60-70°C, the time is 1-2 hours, and the ratio of the zirconium source to the ethanol is 1g zirconium source: 5-10mL ethanol.

[0019] As a preferred embodiment of the light-cured 3D printing zirconium diboride-based ultra-high temperature ceramic slurry of the present invention, the boron source, the carbon source and ethanol are stirred to obtain a mixed solution of the boron source and the carbon source, wherein the stirring temperature is 60-70°C, the stirring time is 1-2h, the volume ratio of the total mass of the boron source and the carbon source to the ethanol is 1g boron source and carbon source: 2-5mL ethanol; the molar ratio of zirconium and boron elements in the zirconium source, the boron source and the carbon source is 1:2-1:3, and the molar ratio of zirconium and carbon is 1:5-1:9.

[0020] As a preferred embodiment of the photocurable 3D printing zirconium diboride-based ultra-high temperature ceramic slurry of the present invention, the mixed solution of the zirconium source, the boron source and the carbon source is dried, ground and sieved to obtain a zirconium diboride-based ultra-high temperature ceramic sol-gel precursor dry gel powder, wherein the drying temperature is 80-90°C and the drying time is 24-48 hours.

[0021] As a preferred embodiment of the photocurable 3D printing zirconium diboride-based ultra-high temperature ceramic slurry of the present invention, the zirconium diboride-based ultra-high temperature ceramic sol-gel precursor dry gel powder is added to a polytetrafluoroethylene ball mill and ball milled. The mass ratio of the zirconium diboride-based ultra-high temperature ceramic sol-gel precursor dry gel powder to the zirconium oxide ball milling beads in the ball mill is 1:10. The total volume of the zirconium diboride-based ultra-high temperature ceramic sol-gel precursor dry gel powder and the zirconium oxide ball milling beads accounts for 1 / 3-1 / 2 of the volume of the polytetrafluoroethylene ball mill. The rotation speed is 300-450 rpm and the ball milling time is 2-12 h.

[0022] As a preferred embodiment of the photocurable 3D printing zirconium diboride-based ultra-high temperature ceramic slurry of the present invention, the photosensitive resin active diluent is 1,6-hexanediol diacrylate, accounting for 8-60% of the total mass of the slurry, the dispersant is SP-769Z, accounting for 0-10% of the total mass of the slurry, the photoinitiator is bis(2,4,6-trimethylbenzoyl)diphenylphosphine oxide, accounting for 0.1-1% of the total mass of the slurry, and the light absorber is Sudan I, accounting for 0.01-0.5% of the total mass of the slurry.

[0023] The purpose of the present invention is to overcome the deficiencies in the prior art and provide an application of a zirconium diboride-based ultrahigh temperature ceramic slurry in photocuring 3D printing of zirconium diboride-based ultrahigh temperature ceramics.

[0024] As a preferred embodiment of the application of the present invention, a zirconium diboride-based ultrahigh temperature ceramic slurry is printed using a photocuring printer to form a zirconium diboride-based ultrahigh temperature ceramic printed body; the printed body is sequentially cleaned, degreased, and subjected to high-temperature sintering to obtain the zirconium diboride-based ultrahigh temperature ceramic. The degreasing process comprises a two-step degreasing process for degreasing the printed body, wherein the printed sample is placed in an alumina crucible and embedded in zirconium diboride ceramic powder, and the crucible is placed in a tube furnace for degreasing. The first step is low-temperature degreasing, wherein the temperature is first increased from room temperature to 280°C at a heating rate of 0.05-2°C / min in an argon atmosphere, and then maintained at 100, 125, 180, and 280°C for 2-4 hours, followed by cooling to room temperature. The second step is high-temperature degreasing, heating the temperature to 280℃ at a heating rate of 2-10℃ and keeping it warm for 1-2h, then heating it to 600℃ at a heating rate of 0.05-2℃ / min, keeping it warm at 300, 325, 350, 415 and 600℃ for 2-4h respectively, and then cooling to room temperature.

[0025] As a preferred solution of the application of the present invention, the high-temperature sintering is pressureless sintering or gas pressure sintering, and the sintering temperature is not lower than 1500°C.

[0026] Beneficial effects of the present invention:

[0027] The present invention uses zirconium diboride-based ultrahigh-temperature ceramic sol-gel precursor xerogel powder instead of zirconium diboride ceramic powder as the raw material for preparing a photocurable printing slurry. This significantly reduces the powder's light absorptivity within the 250-600nm wavelength range, increasing the curing depth of the photocurable 3D printing zirconium diboride-based ultrahigh-temperature ceramic slurry. This facilitates the rapid printing of high-precision, defect-free zirconium diboride-based ultrahigh-temperature ceramic green bodies. Furthermore, combined with the appropriate selection of the sintering temperature, the present invention can produce zirconium diboride-based ultrahigh-temperature ceramics with complex shapes. BRIEF DESCRIPTION OF THE DRAWINGS

[0028] In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the following briefly introduces the drawings required for describing the embodiments and comparative examples. Obviously, the drawings described below are only some embodiments and comparative examples of the present invention. Those skilled in the art can also derive other drawings based on these drawings without inventive effort. Among them:

[0029] Figure 1 This is the UV-visible absorbance spectrum of the zirconium diboride-based ultrahigh temperature ceramic sol-gel precursor xerogel powder and the zirconium diboride ceramic powder for photocuring 3D printing in Example 1 of the present invention.

[0030] Figure 2The exposure dose-curing depth relationship of the slurry prepared from the zirconium diboride-based ultrahigh temperature ceramic sol-gel precursor xerogel powder and the zirconium diboride ceramic powder in Example 1 of the present invention and Comparative Example 1.

[0031] Figure 3 This is the morphology of the sample after degreasing obtained by photocuring printing using a slurry prepared with zirconium diboride-based ultra-high temperature ceramic sol-gel precursor xerogel powder in Example 1 of the present invention.

[0032] Figure 4 This is the XRD image of the sample after sintering at 1500℃ in Example 1.

[0033] Figure 5 This is the microscopic morphology of the sample after sintering at 1500℃ in Example 1.

[0034] Figure 6 This is the morphology of the sample in Comparative Example 2 that was not embedded with zirconium diboride ceramic powder after degreasing.

[0035] Figure 7 This is the XRD pattern of Comparative Example 3 after sintering at 1400°C. DETAILED DESCRIPTION

[0036] In order to make the above-mentioned objects, features and advantages of the present invention more obvious and easy to understand, the specific implementation methods of the present invention are described in detail below in conjunction with the embodiments of the specification.

[0037] In the following description, many specific details are set forth to facilitate a full understanding of the present invention. However, the present invention may also be implemented in other ways different from those described herein. Those skilled in the art may make similar generalizations without violating the connotation of the present invention. Therefore, the present invention is not limited to the specific embodiments disclosed below.

[0038] Secondly, the term "one embodiment" or "embodiment" herein refers to a specific feature, structure, or characteristic that may be included in at least one implementation of the present invention. The phrase "in one embodiment" appearing in various places throughout this specification does not necessarily refer to the same embodiment, nor does it refer to a separate or selective embodiment that is mutually exclusive of other embodiments.

[0039] Unless otherwise specified, the raw materials used in the present invention are commonly available in the market.

[0040] The 3D printer used in the present invention is a CeraStation 160 ceramic 3D printer developed by Jiangsu Qiandu Intelligent Manufacturing High-Tech Co., Ltd. The thickness of the ceramic printing layer used for testing is 100 μm, the exposure intensity is 70, and the exposure time is 10 s.

[0041] Example 1

[0042] This embodiment provides a photocurable 3D printing zirconium diboride precursor slurry and a photocurable printing and post-processing method thereof, specifically:

[0043] 1) Preparation of zirconium diboride-based ultrahigh temperature ceramic sol-gel precursor xerogel powder:

[0044] A zirconium source solution was prepared using zirconyl nitrate as the zirconium source and ethanol as the solvent. A mixed solution of the boron source and carbon source was prepared using boric acid as the boron source, sorbitol as the carbon source and ethanol as the solvent. The molar ratio of zirconium, boron and carbon elements in the zirconium source, boron source and carbon source is 1:3:9. Weigh 0.0723 mol (16.80 g) of zirconyl nitrate into a beaker, add 85 mL of ethanol, and stir at 60°C for 1 hour to obtain a clear and transparent solution, which is the zirconium source solution. At the same time, weigh 0.217 mol (13.48 g) of boric acid and 0.108 mol (20.16 g) of sorbitol into a beaker, add 67 mL of ethanol, and stir at 60°C for 1 hour to obtain a clear and transparent solution, which is the mixed solution of the boron source and carbon source;

[0045] The mixed solution of the boron source and the carbon source was continuously stirred at 60° C., and the zirconium source solution was added dropwise to the boron source and carbon source solutions. After the addition was completed, the mixture was continuously stirred at 60° C. for 2 h to obtain a mixed solution of the zirconium source, the boron source, and the carbon source;

[0046] The mixed solution was placed in an 80°C oven for 48 hours to obtain a zirconium diboride-based ultrahigh temperature ceramic sol-gel precursor xerogel block. The precursor xerogel block was collected, ground into a powder using an agate mortar and pestle, and sieved through a 300-mesh sieve. The ground zirconium diboride-based ultrahigh temperature ceramic sol-gel precursor xerogel powder was collected;

[0047] The zirconium diboride-based ultrahigh temperature ceramic sol-gel precursor xerogel powder after ball milling is obtained to obtain the zirconium diboride-based ultrahigh temperature ceramic sol-gel precursor xerogel powder after ball milling:

[0048] 36 g of zirconium diboride-based ultra-high temperature ceramic sol-gel precursor dry gel powder was weighed and placed in a polytetrafluoroethylene ball mill with a volume of 275 mL. 360 g of zirconium dioxide ball milling beads with a diameter of 3 mm were added. The mixture was ball milled at a speed of 450 rpm for 8 h to obtain zirconium diboride-based ultra-high temperature ceramic sol-gel precursor dry gel powder.

[0049] like Figure 1As shown, the obtained zirconium diboride-based ultra-high temperature ceramic sol-gel precursor dry gel powder was subjected to an ultraviolet-visible absorbance test, and the test wavelength range was 200-800nm. In the ultraviolet-visible absorbance spectrum, the horizontal axis is the wavelength of the light wave, and the vertical axis is the absorptivity of the powder to light. The wavelength of the light wave used in the photocuring 3D printing equipment is 405nm. At 405nm, the absorptivity of the zirconium diboride-based ultra-high temperature ceramic sol-gel precursor dry gel powder is 0.16, while that of the zirconium diboride ceramic powder is 0.83. The lower the powder's absorptivity to light waves, the more conducive it is to photocuring 3D printing. The zirconium diboride-based ultra-high temperature ceramic sol-gel precursor dry gel powder used in the present invention has significant advantages as a raw material for photocuring printing.

[0050] 2) Preparation of light-curing slurry:

[0051] Weigh 14.49 g of bifunctional photosensitive resin active diluent 1,6-hexanediol diacrylate, 0.15 g of photoinitiator phenyl bis(2,4,6-trimethylbenzoyl)phosphine oxide, 0.08 g of light absorber Sudan I, 23 g of zirconium diboride-based ultra-high temperature ceramic sol-gel precursor dry gel powder, and 1.15 g of dispersant SP-769Z into a plastic jar, add 20 g of zirconium oxide ball milling beads, and ball mill at 300 rpm for 8 h to prepare a light-curing slurry.

[0052] The slurry was tested for curing depth, and the results are shown in Figure 2 . In the exposure dose-curing depth relationship diagram, the horizontal axis is the exposure dose (incident energy per unit area) and the vertical axis is the curing depth. At the same exposure dose, a higher curing depth indicates that the slurry has better photocuring properties; at the same curing depth, the lower the required exposure dose, the better the photocuring properties. The photocuring properties of the slurry prepared with zirconium diboride-based ultra-high temperature ceramic sol-gel precursor dry gel powder are significantly better than those prepared with zirconium diboride ceramics.

[0053] 3) Perform light-curing 3D printing:

[0054] A 1-cm cube was printed using an industrial-grade CeraStation 160 ceramic printer (Jiangsu Qiandu Intelligent Manufacturing High-Tech Co., Ltd.) at an exposure intensity of 70, a single exposure time of 10 seconds, and a layer thickness of 100 μm. The printed part was ultrasonically cleaned with isopropyl alcohol three times for 10 minutes each.

[0055] 4) Degreasing:

[0056] A two-step degreasing process was used to degrease the printed parts. The specific steps are as follows: the printed sample was placed in an alumina crucible and embedded in zirconium diboride ceramic powder. The crucible was then placed in a tube furnace for degreasing. The first step was low-temperature degreasing. First, the temperature was increased from room temperature to 280°C at a heating rate of 0.15°C / min under an argon atmosphere. The temperature was then held at 100, 125, 180, and 280°C for 2 hours before cooling to room temperature. The second step was high-temperature degreasing. The temperature was increased to 280°C at a heating rate of 2°C and held for 1 hour. The temperature was then increased to 600°C at a heating rate of 0.15°C / min. The temperature was then held at 300, 325, 350, 415, and 600°C for 2 hours before cooling to room temperature.

[0057] See the sample photo after degreasing Figure 3 There are no defects such as cracks or delamination on the surface, indicating that the degreasing results are good.

[0058] 5) Sintering

[0059] After debinding, sintering is carried out in an argon atmosphere at a sintering temperature of 1500°C and a holding time of 2h.

[0060] Figure 4 The XRD pattern of the sintered sample is plotted on the horizontal axis, with the angle (2θ) and the intensity (Y). XRD refinement results indicate that the primary phase after sintering is zirconium diboride, with a small amount of zirconium carbide present. The mass ratio of zirconium diboride to zirconium carbide is approximately 98:2.

[0061] like Figure 5 As shown, a microporous structure is obtained after sintering.

[0062] Example 2

[0063] This example differs from Example 1 in that the ratios of the zirconium source, carbon source, and boron source during the preparation of the zirconium diboride-based ultrahigh-temperature ceramic sol-gel precursor xerogel powder are changed. The molar ratio of zirconium, boron, and carbon in the zirconium source, boron source, and carbon source is 1:3:6.

[0064] In this example, zirconium oxynitrate was used as the zirconium source and ethanol was used as the solvent to prepare a zirconium source solution. Boric acid was used as the boron source, sorbitol was used as the carbon source, and ethanol was used as the solvent to prepare a mixed solution of the boron source and the carbon source. Weigh 0.0723 mol (16.80 g) of zirconium oxynitrate in a beaker, add 85 mL of ethanol, and stir at 50 ° C for 1 hour to obtain a clear and transparent solution, which is the zirconium source solution. At the same time, weigh 0.217 mol (13.48 g) of boric acid and 0.0723 mol (13.44 g) of sorbitol in a beaker, add 54 mL of ethanol, and stir at 60 ° C for 1 hour to obtain a clear and transparent solution, which is the mixed solution of the boron source and the carbon source.

[0065] Example 3

[0066] This example differs from Examples 1 and 2 in that the ratios of the zirconium source, carbon source, and boron source used in the preparation of the zirconium diboride-based ultrahigh-temperature ceramic sol-gel precursor xerogel powder are modified. The molar ratio of zirconium, boron, and carbon in the zirconium source, boron source, and carbon source is 1:3:7.5.

[0067] In this example, zirconium oxynitrate is used as the zirconium source and ethanol is used as the solvent to prepare a zirconium source solution. Boric acid is used as the boron source, sorbitol is used as the carbon source, and ethanol is used as the solvent to prepare a mixed solution of the boron source and the carbon source. Weigh 0.0723 mol (16.80 g) of zirconium oxynitrate in a beaker, add 85 mL of ethanol, and stir at 50 ° C for 1 hour to obtain a clear and transparent solution, which is the zirconium source solution. At the same time, weigh 0.217 mol (13.48 g) of boric acid and 0.090 mol (16.80 g) of sorbitol in a beaker, add 60 mL of ethanol, and stir at 60 ° C for 1 hour to obtain a clear and transparent solution, which is the mixed solution of the boron source and the carbon source.

[0068] Comparative Example 1

[0069] The difference from Example 1 is that zirconium diboride ceramic powder is used to prepare the photocurable slurry, and the relationship between the curing depth and the exposure energy is tested. Slurries with a mass fraction of zirconium diboride ceramic powder of 30% and 50% are prepared, and the proportions of other additives are the same as in Example 1. Figure 2 As shown, the photocurable slurry prepared with zirconium diboride ceramic powder is difficult to achieve high curing depth under low exposure intensity compared to the slurry prepared with zirconium diboride-based ultra-high temperature ceramic sol-gel precursor dry gel powder, and it is difficult to achieve effective photocuring.

[0070] Comparative Example 2

[0071] The difference from Example 1 is that in step (4), the zirconium diboride ceramic powder is not used for embedding in the degreasing process, and the degreasing process is to heat the sample to 600°C at a heating rate of 0.15°C / min under an argon atmosphere and keep the temperature at 600°C for 2 hours. Figure 6 As shown in the figure, the sample showed obvious cracking after degreasing. Figure 3 This forms a sharp contrast, highlighting the superiority of the degreasing process adopted by the present invention.

[0072] Comparative Example 3

[0073] The difference from Example 1 is that the sintering temperature in step (5) is set to 1400°C. Figure 7 The XRD test results show that the main phase is zirconium oxide, with a small amount of zirconium diboride and zirconium carbide. Figure 4 contrast, Figure 7 No ultra-high temperature ceramic phase dominated by zirconium diboride was obtained, highlighting the importance of controlling the sintering temperature.

[0074] Comparative Example 4

[0075] The difference from Example 1 is that in step (1), ethanol is replaced with acetic acid and the inorganic zirconium source is replaced with an organic zirconium source in the preparation of the zirconium diboride-based ultrahigh-temperature ceramic sol-gel precursor xerogel powder. It is difficult to obtain crack-free debinding and sintered samples using a slurry prepared using this powder.

[0076] In summary, the present invention uses zirconium diboride-based ultrahigh-temperature ceramic sol-gel precursor xerogel powder to formulate a photocurable printing slurry, which can significantly improve the curing depth of photocurable 3D printed zirconium diboride-based ultrahigh-temperature ceramic slurry. This is conducive to printing high-precision, defect-free zirconium diboride-based ultrahigh-temperature ceramic green bodies. Furthermore, the present invention flexibly controls the particle size of the powder system through processes such as crushing and screening, combined with the rational selection of the sintering temperature, to obtain porous zirconium diboride-based ultrahigh-temperature ceramics.

[0077] It should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention and are not intended to limit the present invention. Although the present invention has been described in detail with reference to the preferred embodiments, those skilled in the art should understand that the technical solutions of the present invention may be modified or replaced by equivalents without departing from the spirit and scope of the technical solutions of the present invention, which should all be included in the scope of the claims of the present invention.

Claims

1. A photocurable 3D printing zirconium diboride-based ultra-high temperature ceramic slurry, characterized by: include, Zirconium diboride-based ultrahigh temperature ceramic sol-gel precursor xerogel powder, photosensitive resin active diluent, dispersant, photoinitiator and light absorber; Among them, the particle size of the zirconium diboride-based ultra-high temperature ceramic sol-gel precursor dry gel powder is 0.1~200μm, and the absorbance in the 250~600nm light wave band is <0.7; the mass fraction in the zirconium diboride-based ultra-high temperature ceramic slurry is 40~90wt.%.

2. The method for preparing a photocurable 3D printing zirconium diboride-based ultrahigh temperature ceramic slurry according to claim 1, wherein: include, Stirring the zirconium source and ethanol to obtain a zirconium source solution; The boron source, the carbon source and the ethanol are stirred to obtain a mixed solution of the boron source and the carbon source; adding the zirconium source solution to the mixed solution of the boron source and the carbon source and stirring to obtain a mixed solution of the zirconium source, the boron source and the carbon source; The mixed solution of the zirconium source, the boron source and the carbon source is dried, ground and sieved to obtain a zirconium diboride-based ultrahigh temperature ceramic sol-gel precursor xerogel powder; adding zirconium diboride-based ultrahigh temperature ceramic sol-gel precursor xerogel powder into a polytetrafluoroethylene ball milling jar and milling the xerogel powder to obtain zirconium diboride-based ultrahigh temperature ceramic sol-gel precursor xerogel powder; Zirconium diboride-based ultrahigh temperature ceramic sol-gel precursor dry gel powder, photosensitive resin active diluent, dispersant, photoinitiator and light absorber are mixed to form zirconium diboride-based ultrahigh temperature ceramic slurry.

3. The preparation method according to claim 2, wherein: The zirconium source and ethanol are stirred to obtain a zirconium source solution, wherein the stirring temperature is 60-70° C., the stirring time is 1-2 h, and the ratio of the zirconium source to the ethanol is 1 g of zirconium source: 5-10 mL of ethanol.

4. The preparation method according to claim 2, wherein: The boron source, the carbon source and ethanol are stirred to obtain a mixed solution of the boron source and the carbon source, wherein the stirring temperature is 60-70°C, the stirring time is 1-2 hours, the volume ratio of the total mass of the boron source and the carbon source to the ethanol is 1g of boron source and carbon source: 2-5mL of ethanol; the molar ratio of zirconium and boron elements in the zirconium source, the boron source and the carbon source is 1:2-1:3, and the molar ratio of zirconium and carbon is 1:5-1:

9.

5. The preparation method according to claim 2, wherein: The mixed solution of the zirconium source, the boron source and the carbon source is dried, ground and sieved to obtain zirconium diboride-based ultrahigh temperature ceramic sol-gel precursor xerogel powder, wherein the drying temperature is 80-90° C. and the drying time is 24-48 h.

6. The preparation method according to claim 2, wherein: The zirconium diboride-based ultrahigh temperature ceramic sol-gel precursor dry gel powder is added to a polytetrafluoroethylene ball mill and ball milled. The mass ratio of the zirconium diboride-based ultrahigh temperature ceramic sol-gel precursor dry gel powder to the zirconium oxide ball milling beads in the ball mill is 1:

10. The total volume of the zirconium diboride-based ultrahigh temperature ceramic sol-gel precursor dry gel powder and the zirconium oxide ball milling beads accounts for 1 / 3-1 / 2 of the volume of the polytetrafluoroethylene ball mill. The rotation speed is 300-450 rpm, and the ball milling time is 2-12 h.

7. The light-curing 3D printing zirconium diboride-based ultrahigh temperature ceramic slurry according to claim 1, characterized in that: The photosensitive resin active diluent is 1,6-hexanediol diacrylate, the dispersant is SP-769Z, the photoinitiator is phenyl bis (2, 4, 6-trimethylbenzoyl) phosphine oxide, and the light absorber is Sudan I.

8. Use of the photocurable 3D printing zirconium diboride-based ultrahigh temperature ceramic slurry according to claim 1 in photocurable 3D printing of zirconium diboride-based ultrahigh temperature ceramics.

9. The use according to claim 8, characterized in that: The method comprises printing zirconium diboride-based ultrahigh temperature ceramic slurry by a light-curing printer to form a zirconium diboride-based ultrahigh temperature ceramic printed body; and sequentially cleaning, degreasing, and high-temperature sintering the printed body to obtain the zirconium diboride-based ultrahigh temperature ceramic. The degreasing process comprises the following steps: degreasing the printed body by a two-step degreasing method, placing the printed sample in an alumina crucible and embedding it in zirconium diboride ceramic powder, and placing the crucible in a tube furnace for degreasing; the first step is low-temperature degreasing, firstly, heating from room temperature to 280°C at a heating rate of 0.05-2°C / min under an argon atmosphere, during which the temperature is kept at 100, 125, 180 and 280°C for 2-4 hours, and then cooling to room temperature; the second step is high-temperature degreasing, heating to 280°C at a heating rate of 2-10°C and keeping it for 1-2 hours, then heating to 600°C at a heating rate of 0.05-2°C / min, during which the temperature is kept at 300, 325, 350, 415 and 600°C for 2-4 hours, and then cooling to room temperature.

10. The use according to claim 9, characterized in that: The high-temperature sintering is pressureless sintering or gas pressure sintering, and the sintering temperature is not lower than 1500°C.

Images