Photocuring-based bionic layered ceramic and preparation method thereof

Abstract

The invention provides bionic layered ceramic based on photocuring and a preparation method of the bionic layered ceramic, and belongs to the technical field of ceramic manufacturing. The preparation method comprises the following steps: mixing first ceramic mixed powder and a first liquid-phase composition to prepare matrix layer slurry; mixing the second ceramic mixed powder and the second liquid phase composition to prepare interface layer slurry; then carrying out 3D photocuring printing on the matrix layer slurry and the interface layer slurry to prepare a layered ceramic biscuit; finally, the layered ceramic biscuit is dried, degreased and sintered, and the bionic layered ceramic is prepared. The first liquid phase composition and the second liquid phase composition independently include a photosensitive resin, a dispersant, and a photoinitiator. The bionic layered ceramic prepared by the method is low in layer thickness, high in layer precision, obvious in toughening phenomena such as crack deflection and crack bifurcation in the fracture process, and relatively high in fracture property and reliability.

Description

Technical Field

[0001] The present invention relates to the technical field of ceramic manufacturing, and in particular to a bionic layered ceramic based on photocuring and a preparation method thereof. Background Art

[0002] With the rapid development of the semiconductor industry, the demand for high-performance ceramic materials is increasing in many industrial fields such as electronics, optoelectronics, and energy. Layered ceramics, by strengthening crack deflection and crack bifurcation mechanisms, give ceramic materials excellent mechanical properties, thermal stability, and multifunctionality. Therefore, they are widely used in precision mechanical engineering, energy, electronic devices, environmental protection, and biomedicine. However, traditional methods such as stacking pressing, spraying, and chemical vapor deposition often face problems such as complex processes, high costs, and unstable material properties. Therefore, seeking new preparation methods to overcome these limitations and improve the performance and controllability of layered ceramic materials is one of the current research hotspots.

[0003] Currently, methods for preparing ceramic materials based on photocuring technology are gradually attracting attention. By using photosensitive materials and irradiating them with ultraviolet light, materials can be cured layer by layer at specific spatial locations to form the desired layered structure. This method can provide higher preparation precision and complexity, and can achieve special requirements such as microstructures and internal channels, with the characteristics of rapidity, efficiency, and controllability. Therefore, the present invention proposes a biomimetic layered ceramic based on photocuring and its preparation method, aiming to overcome the shortcomings of traditional preparation methods and provide layered ceramic materials with excellent properties. Summary of the Invention

[0004] The purpose of the present invention is to provide a bionic layered ceramic based on photocuring and a preparation method thereof, so as to solve the problems of low layer precision, poor fracture toughness and long preparation cycle of traditional bionic layered ceramics in the prior art.

[0005] In order to achieve the above-mentioned object of the invention, the present invention provides the following technical solutions:

[0006] The present invention provides a method for preparing biomimetic layered ceramics based on photocuring, comprising the following steps:

[0007] (1) mixing a first ceramic mixed powder and a first liquid composition to prepare a matrix layer slurry;

[0008] (2) mixing the second ceramic mixed powder and the second liquid phase composition to prepare an interface layer slurry;

[0009] (3) 3D photocuring printing is performed on the base layer slurry and the interface layer slurry to obtain a layered ceramic blank;

[0010] (4) drying, degreasing and sintering the layered ceramic green body to obtain a bionic layered ceramic;

[0011] The first liquid composition and the second liquid composition independently contain a photosensitive resin, a dispersant and a photoinitiator.

[0012] Preferably, the photosensitive resin comprises 1,6-hexanediol diacrylate and trimethylolpropane triacrylate.

[0013] Preferably, the mass ratio of the 1,6-hexanediol diacrylate to the trimethylolpropane triacrylate is 5-8:1-4.

[0014] Preferably, the first ceramic mixed powder comprises a skeleton proppant and a sintering aid, wherein the mass ratio of the skeleton proppant to the sintering aid is 100:10-30.

[0015] Preferably, in the base layer slurry, the content of the first ceramic mixed powder is 40-50 wt %, the content of the photosensitive resin is 46-59 wt %, the content of the dispersant is 0.5-3 wt %, and the content of the photoinitiator is 0.1-1 wt %.

[0016] Preferably, the second ceramic mixed powder comprises a skeleton support, a sintering aid and a reinforcing agent, wherein the mass ratio of the skeleton support, the sintering aid and the reinforcing agent is 100:20-40:10-30.

[0017] Preferably, in the interface layer slurry, the content of the second ceramic mixed powder is 30-40 wt %, the content of the photosensitive resin is 57-69.4 wt %, the content of the dispersant is 0.5-2 wt %, and the content of the photoinitiator is 0.1-1 wt %.

[0018] Preferably, during the 3D light curing printing, the UV light source intensity used for the base layer slurry is 10-30 mw / cm 2 The single layer curing time is 5 to 15 seconds, and the single layer curing thickness is 30 to 50 μm. The UV light source intensity used for the interface layer slurry is 15 to 25 mw / cm 2 The single layer curing time is 4 to 6 seconds, and the single layer curing thickness is 30 to 50 μm.

[0019] Preferably, the sintering temperature is 1400-1800° C., and the sintering time is 1-4 hours.

[0020] The present invention also provides a bionic layered ceramic prepared by the above-mentioned preparation method of bionic layered ceramic based on light curing, wherein the fracture toughness of the bionic layered ceramic is 6 to 10 MPa·m 1 / 2 .

[0021] Beneficial effects of the present invention:

[0022] (1) The present invention adds photosensitive resin to the base layer slurry and the interface layer slurry, utilizes the high resolution and precise control capability of 3D light-curing printing technology, and improves the dimensional stability and structural consistency of the parts by adjusting the exposure intensity and exposure time, so that the layer-by-layer curing and material deposition process can be completed in a short time, significantly shortening the preparation cycle and reducing the preparation cost.

[0023] (2) The bionic layered ceramics prepared by the present invention have low layer thickness and high layer precision. During the fracture process, the toughening phenomena such as crack deflection and crack bifurcation are obvious, and the ceramics have high fracture resistance and reliability. BRIEF DESCRIPTION OF THE DRAWINGS

[0024] Figure 1 Schematic diagram of the structure of the bionic layered ceramic of the present invention;

[0025] Figure 2 This is a microscopic morphology of the cross section of the bionic layered ceramic body prepared in Example 1. DETAILED DESCRIPTION

[0026] The present invention provides a method for preparing biomimetic layered ceramics based on photocuring, comprising the following steps:

[0027] (1) mixing a first ceramic mixed powder and a first liquid composition to prepare a matrix layer slurry;

[0028] (2) mixing the second ceramic mixed powder and the second liquid phase composition to prepare an interface layer slurry;

[0029] (3) 3D photocuring printing is performed on the base layer slurry and the interface layer slurry to obtain a layered ceramic blank;

[0030] (4) drying, degreasing and sintering the layered ceramic green body to obtain a bionic layered ceramic;

[0031] The first liquid composition and the second liquid composition independently contain a photosensitive resin, a dispersant and a photoinitiator.

[0032] In the present invention, the photosensitive resin comprises 1,6-hexanediol diacrylate and trimethylolpropane triacrylate.

[0033] In the present invention, the mass ratio of the 1,6-hexanediol diacrylate to the trimethylolpropane triacrylate is 5-8:1-4, preferably 6-7:2-3, and more preferably 7:3.

[0034] In the present invention, the dispersant is polypropylene glycol; and the photoinitiator is diphenyl (2,4,6-trimethylbenzoyl) phosphine oxide.

[0035] In the present invention, the first ceramic mixed powder comprises a skeleton proppant and a sintering aid, wherein the mass ratio of the skeleton proppant to the sintering aid is 100:10 to 30, preferably 100:20.

[0036] In the present invention, in the base layer slurry, the content of the first ceramic mixed powder is 40-50 wt %, the content of the photosensitive resin is 46-59 wt %, the content of the dispersant is 0.5-3 wt %, and the content of the photoinitiator is 0.1-1 wt %.

[0037] In the present invention, the second ceramic mixed powder comprises a skeleton support, a sintering aid and a reinforcing agent, wherein the mass ratio of the skeleton support, the sintering aid and the reinforcing agent is 100:20 to 40:10 to 30, preferably 100:30:20.

[0038] In the present invention, in the interface layer slurry, the content of the second ceramic mixed powder is 30-40 wt %, the content of the photosensitive resin is 57-69.4 wt %, the content of the dispersant is 0.5-2 wt %, and the content of the photoinitiator is 0.1-1 wt %.

[0039] In the present invention, the skeleton proppant independently comprises one or more of silicon carbide, silicon nitride, aluminum oxide, boron carbide and mullite, and the average particle size of the skeleton proppant is 1 to 30 μm; the sintering aid independently comprises one or more of kaolin, talc, aluminum oxide, yttrium oxide and silicon oxide; and the reinforcing agent comprises one or more of silicon carbide whiskers, silicon nitride whiskers, flaky boron nitride, plate-like corundum and graphene.

[0040] In the present invention, in the step (1), the first ceramic mixed powder and the first liquid composition are preferably mixed by ball milling.

[0041] In the present invention, in the step (2), the second ceramic mixed powder and the second liquid composition are preferably mixed by ball milling.

[0042] In the present invention, during the 3D light curing printing, the UV light source intensity used for the base layer slurry is 10-30 mw / cm 2 , preferably 15 to 25 mw / cm 2 , more preferably 20mw / cm 2 The single layer curing time is 5 to 15 seconds, preferably 8 to 12 seconds, more preferably 10 seconds, and the single layer curing thickness is 30 to 50 μm, preferably 35 to 45 μm, more preferably 40 μm; the ultraviolet light source intensity used for the interface layer slurry is 15 to 25 mw / cm 2 , preferably 18 to 22 mw / cm 2, more preferably 20mw / cm 2 The single-layer curing time is 4 to 6 s, preferably 5 s, and the single-layer curing thickness is 30 to 50 μm, preferably 35 to 45 μm, and more preferably 40 μm.

[0043] In the present invention, the sintering temperature is 1400-1800° C., preferably 1500-1700° C., and more preferably 1600° C.; the sintering time is 1-4 hours, preferably 2-3 hours.

[0044] The present invention also provides a bionic layered ceramic prepared by the above-mentioned preparation method of bionic layered ceramic based on light curing, wherein the fracture toughness of the bionic layered ceramic is 6 to 10 MPa·m 1 / 2 .

[0045] The technical solutions provided by the present invention are described in detail below with reference to the embodiments, but they should not be construed as limiting the scope of protection of the present invention.

[0046] Example 1

[0047] Prepare the base layer slurry: 100 parts of silicon nitride powder (average particle size of 20 μm), 8 parts of alumina powder, and 12 parts of yttrium oxide, mix them evenly to obtain a first ceramic mixed powder, add a photosensitive resin (mixed by 1,6-hexanediol diacrylate and trimethylolpropane triacrylate, wherein the mass ratio of 1,6-hexanediol diacrylate and trimethylolpropane triacrylate is 7:3), a dispersant polypropylene glycol, and a photoinitiator diphenyl (2,4,6-trimethylbenzoyl) phosphine oxide to prepare a base layer slurry, wherein the content of the first ceramic mixed powder is 45wt%, the content of the photosensitive resin is 52wt%, the content of polypropylene glycol is 2.5wt%, and the content of the photoinitiator diphenyl (2,4,6-trimethylbenzoyl) phosphine oxide is 0.5wt%, and the above raw materials are placed in a ball mill and ball milled at a speed of 150 rpm for 3 hours to obtain a base layer slurry.

[0048] Prepare an interface layer slurry: 100 parts of silicon nitride powder, 12 parts of aluminum oxide powder, 18 parts of yttrium oxide, and 20 parts of silicon carbide whiskers are mixed uniformly to obtain a second ceramic mixed powder, and a photosensitive resin (mixed by 1,6-hexanediol diacrylate and trimethylolpropane triacrylate, wherein the molar ratio of 1,6-hexanediol diacrylate to trimethylolpropane triacrylate is 7:3), a dispersant polypropylene glycol, and a photoinitiator diphenyl (2,4,6-trimethylbenzoyl) phosphine oxide are added to prepare an interface layer slurry, wherein the content of the second ceramic mixed powder is 35wt%, the content of the photosensitive resin is 63wt%, the content of the polypropylene glycol is 1.5wt%, and the content of the photoinitiator diphenyl (2,4,6-trimethylbenzoyl) phosphine oxide is 0.5wt%. The above raw materials are placed in a ball mill and ball milled at a speed of 200 rpm for 2.5 hours to obtain an interface layer slurry.

[0049] A 3D CAD model of biomimetic layered ceramics was created, and then the layering parameters and scanning path data were set. The base layer slurry and the interface layer slurry were poured into the liquid tanks on both sides of the DLP printer, respectively. The 3D model data was imported, and the UV light source intensity used for the base layer slurry was set to 20 mW / cm 2 The single layer curing time is 10s, the single layer curing thickness is 40μm, and the UV light source intensity used for the interface layer slurry is 20mw / cm 2 The single-layer curing time is 5s, the single-layer curing thickness is 40μm, and the layered ceramic green body is obtained by printing layer by layer.

[0050] The obtained layered ceramic green body was dried at 110°C for 12 hours, then heated to 1000°C at a heating rate of 0.3°C / min, and then heated to 1400°C at a heating rate of 1.5°C / min for degreasing. The green body was sintered at 1400°C for 4 hours to obtain a biomimetic layered silicon nitride ceramic with a fracture toughness of 8.5 MPa·m 1 / 2 .

[0051] Example 2

[0052] Prepare the base layer slurry: 100 parts of silicon carbide powder (average particle size of 20 μm) and 20 parts of silicon oxide, mix them evenly to obtain a first ceramic mixed powder, add photosensitive resin (mixed by 1,6-hexanediol diacrylate and trimethylolpropane triacrylate, wherein the molar ratio of 1,6-hexanediol diacrylate and trimethylolpropane triacrylate is 7:3), dispersant polypropylene glycol, and photoinitiator diphenyl (2,4,6-trimethylbenzoyl) phosphine oxide to make a base layer slurry, wherein the content of the first ceramic mixed powder is 50wt%, the content of the photosensitive resin is 46wt%, the content of polypropylene glycol is 3wt%, and the content of the photoinitiator diphenyl (2,4,6-trimethylbenzoyl) phosphine oxide is 1wt%, and the above raw materials are placed in a ball mill and ball milled at a speed of 150 rpm for 3 hours to obtain a base layer slurry.

[0053] Prepare an interface layer slurry: 100 parts of silicon carbide powder, 30 parts of silicon oxide, and 20 parts of silicon carbide whiskers are mixed evenly to obtain a second ceramic mixed powder, and a photosensitive resin (mixed from 1,6-hexanediol diacrylate and trimethylolpropane triacrylate, wherein the molar ratio of 1,6-hexanediol diacrylate to trimethylolpropane triacrylate is 7:3), a dispersant polypropylene glycol, and a photoinitiator diphenyl (2,4,6-trimethylbenzoyl) phosphine oxide are added to prepare an interface layer slurry, wherein the content of the second ceramic mixed powder is 40wt%, the content of the photosensitive resin is 58wt%, the content of polypropylene glycol is 1wt%, and the content of the photoinitiator diphenyl (2,4,6-trimethylbenzoyl) phosphine oxide is 1wt%. The above raw materials are placed in a ball mill and ball milled at a speed of 180 rpm for 2.5 hours to obtain an interface layer slurry.

[0054] A 3D CAD model of biomimetic layered ceramics was created, and then the layering parameters and scanning path data were set. The base layer slurry and the interface layer slurry were poured into the liquid tanks on both sides of the DLP printer respectively. The 3D model data was imported, and the UV light source intensity used for the base layer slurry was set to 30mw / cm 2 The single layer curing time is 15s, the single layer curing thickness is 50μm, and the UV light source intensity used for the interface layer slurry is 25mw / cm 2 The single-layer curing time is 6s, the single-layer curing thickness is 50μm, and the layered ceramic green body is obtained by printing layer by layer.

[0055] The obtained layered ceramic green body was dried at 110°C for 12 hours, then heated to 1000°C at a heating rate of 0.2°C / min, and then heated to 1600°C at a heating rate of 1.5°C / min for degreasing. The green body was sintered at 1600°C for 2 hours to obtain a biomimetic layered silicon carbide ceramic with a fracture toughness of 7.5 MPa·m 1 / 2 .

[0056] Example 3

[0057] Prepare the base layer slurry: 100 parts of silicon nitride powder (average particle size of 20 μm), 8 parts of aluminum oxide powder, and 12 parts of silicon oxide, mix them evenly to obtain a first ceramic mixed powder, add a photosensitive resin (mixed by 1,6-hexanediol diacrylate and trimethylolpropane triacrylate, wherein the molar ratio of 1,6-hexanediol diacrylate to trimethylolpropane triacrylate is 7:3), a dispersant polypropylene glycol, and a photoinitiator diphenyl (2,4,6-trimethylbenzoyl) phosphine oxide to prepare a base layer slurry, wherein the content of the first ceramic mixed powder is 40wt%, the content of the photosensitive resin is 58wt%, the content of polypropylene glycol is 1.5wt%, and the content of the photoinitiator diphenyl (2,4,6-trimethylbenzoyl) phosphine oxide is 0.5wt%, and the above raw materials are placed in a ball mill and ball milled at a speed of 180 rpm for 2.5 hours to obtain a base layer slurry.

[0058] Prepare an interface layer slurry: 100 parts of silicon nitride powder, 12 parts of aluminum oxide powder, 18 parts of silicon oxide, and 20 parts of silicon carbide whiskers are mixed evenly to obtain a second ceramic mixed powder, and a photosensitive resin (mixed from 1,6-hexanediol diacrylate and trimethylolpropane triacrylate, wherein the molar ratio of 1,6-hexanediol diacrylate to trimethylolpropane triacrylate is 7:3), a dispersant polypropylene glycol, and a photoinitiator diphenyl (2,4,6-trimethylbenzoyl) phosphine oxide are added to prepare an interface layer slurry, wherein the content of the second ceramic mixed powder is 30wt%, the content of the photosensitive resin is 68wt%, the content of the polypropylene glycol is 1.3wt%, and the content of the photoinitiator diphenyl (2,4,6-trimethylbenzoyl) phosphine oxide is 0.7wt%. The above raw materials are placed in a ball mill and ball milled at a speed of 150 rpm for 3 hours to obtain an interface layer slurry.

[0059] A 3D CAD model of biomimetic layered ceramics was created, and then the layering parameters and scanning path data were set. The base layer slurry and the interface layer slurry were poured into the liquid tanks on both sides of the DLP printer respectively. The 3D model data was imported, and the UV light source intensity used for the base layer slurry was set to 10mw / cm 2 The single layer curing time is 15s, the single layer curing thickness is 50μm, and the UV light source intensity used for the interface layer slurry is 15mw / cm 2 The single-layer curing time is 4s, the single-layer curing thickness is 30μm, and the layered ceramic green body is obtained by printing layer by layer.

[0060] The layered ceramic green body prepared above is dried at a temperature of 110°C for 12h, then heated to 1000°C at a heating rate of 0.2°C / min, and then heated to 1800°C at a heating rate of 1.5°C / min for defatting treatment, and sintered at 1800°C for 1h for sintering treatment, to obtain a biomimetic layered silicon nitride ceramic, which has a fracture toughness of 9.3MPa·m 1 / 2 .

[0061] From Figure 2 It can be seen that the photocured biomimetic layered ceramic matrix layer and interface layer have uniform thickness and are tightly combined.

[0062] The biomimetic layered ceramics prepared in Examples 1-3 are tested for fracture toughness by the single edge pre-cracked beam (SEPB) method in GB / T23806-2009, wherein the sample size is 2x4x20mm, the span is 16mm, and the loading speed is 0.05mm / min.

[0063] The above only describes the preferred embodiments of the present application, and it should be noted that those skilled in the art can make several improvements and refinements without departing from the principles of the present application, and these improvements and refinements should also be considered within the protection scope of the present application.

Claims

1. A method for preparing biomimetic layered ceramics based on photocuring, characterized in that: The steps include: (1) mixing a first ceramic mixed powder and a first liquid composition to prepare a matrix layer slurry; (2) mixing the second ceramic mixed powder and the second liquid phase composition to prepare an interface layer slurry; (3) 3D photocuring printing is performed on the base layer slurry and the interface layer slurry to obtain a layered ceramic blank; (4) drying, degreasing and sintering the layered ceramic green body to obtain a bionic layered ceramic; The first liquid composition and the second liquid composition independently contain a photosensitive resin, a dispersant and a photoinitiator.

2. The method for preparing biomimetic layered ceramics based on photocuring according to claim 1, characterized in that: The photosensitive resin includes 1,6-hexanediol diacrylate and trimethylolpropane triacrylate.

3. The method for preparing biomimetic layered ceramics based on photocuring according to claim 2, characterized in that: The mass ratio of the 1,6-hexanediol diacrylate to the trimethylolpropane triacrylate is 5-8:1-4.

4. The method for preparing biomimetic layered ceramics based on photocuring according to any one of claims 1 to 3, characterized in that: The first ceramic mixed powder comprises a skeleton proppant and a sintering aid, wherein the mass ratio of the skeleton proppant to the sintering aid is 100:10-30.

5. The method for preparing biomimetic layered ceramics based on photocuring according to claim 4, characterized in that: In the base layer slurry, the content of the first ceramic mixed powder is 40-50 wt %, the content of the photosensitive resin is 46-59 wt %, the content of the dispersant is 0.5-3 wt %, and the content of the photoinitiator is 0.1-1 wt %.

6. The method for preparing biomimetic layered ceramics based on photocuring according to claim 2 or 5, characterized in that: The second ceramic mixed powder comprises a skeleton support, a sintering aid and a reinforcing agent, wherein the mass ratio of the skeleton support, the sintering aid and the reinforcing agent is 100:20-40:10-30.

7. The method for preparing biomimetic layered ceramics based on photocuring according to claim 6, characterized in that: In the interface layer slurry, the content of the second ceramic mixed powder is 30-40 wt %, the content of the photosensitive resin is 57-69.4 wt %, the content of the dispersant is 0.5-2 wt %, and the content of the photoinitiator is 0.1-1 wt %.

8. The method for preparing biomimetic layered ceramics based on photocuring according to claim 5 or 7, characterized in that: During the 3D light-curing printing, the UV light source intensity used for the base layer slurry is 10-30 mw / cm 2 The single layer curing time is 5 to 15 seconds, and the single layer curing thickness is 30 to 50 μm. The UV light source intensity used for the interface layer slurry is 15 to 25 mw / cm 2 The single layer curing time is 4 to 6 seconds, and the single layer curing thickness is 30 to 50 μm.

9. The method for preparing biomimetic layered ceramics based on photocuring according to claim 9, characterized in that: The sintering temperature is 1400-1800° C., and the sintering time is 1-4 hours.

10. The bionic layered ceramics prepared by the method for preparing bionic layered ceramics based on light curing according to any one of claims 1 to 9, characterized in that: The fracture toughness of the bionic layered ceramic is 6 to 10 MPa·m 1 / 2 .

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