A preparation method of a multi-material photocuring 3D printing integration of a titanium nitride silicon carbide endothermic heat storage heterogeneous ceramic framework

Abstract

The application discloses a preparation method of a multi-material photocuring 3D printing integrated titanium nitride silicon carbide endothermic heat storage heterogeneous ceramic framework, which comprises the following steps: preparing silicon carbide ceramic slurry containing photocuring resin, dispersant, photoinitiator and sintering aid; preparing titanium nitride ceramic slurry containing photocuring resin, dispersant, photoinitiator and sintering aid; adding the silicon carbide ceramic slurry and the titanium nitride ceramic slurry into slurry cavities of a multi-material photocuring 3D printer respectively, inputting model information of the titanium nitride silicon carbide heterogeneous ceramic framework into the printer for photocuring printing, and obtaining the titanium nitride silicon carbide heterogeneous ceramic framework after defatting and sintering treatment. The titanium nitride silicon carbide heterogeneous ceramic framework prepared by the method has the functions of high-efficiency light-heat conversion endothermy, high-efficiency heat energy conduction, high-efficiency heat energy charging and discharging and high-density molten salt load heat storage, and has the effect of omnibearing improvement of the light-heat utilization efficiency of a solar thermal power station.

Description

Technical Field

[0001] This invention belongs to the technical field of ceramic 3D printing, specifically relating to a method for preparing a multi-material photopolymerization 3D printing integrated titanium nitride and silicon carbide heat-absorbing and heat-storing heterogeneous ceramic skeleton. Background Technology

[0002] Concentrating solar power (CSP), also known as solar thermal power generation, boasts advantages such as high spectral utilization and energy conversion efficiency, and strong dispatchability, making it a crucial component of the national new energy strategy. The key factors affecting the light utilization efficiency of a solar thermal power plant are the solar absorber and the solar storage unit. The solar absorber absorbs sunlight and converts light energy into heat energy, which is then transferred through pipes to the storage unit for storage. Since solar energy is limited by seasonal and weather factors, the solar storage unit ensures a stable output of heat energy from the solar thermal power plant to the generator. Because the operating temperature of solar thermal power plants is mostly between 800 and 1200 °C, the absorbers and storage units are often made of ceramic. Traditional solar thermal power plants separate the absorption and storage systems; the heat energy absorbed by the absorber must be transferred to the solar storage unit through pipes, resulting in significant heat loss during transmission and greatly reducing the light utilization efficiency of the solar thermal power plant. The new generation of integrated solar thermal power plants combines heat absorption and heat storage systems, greatly reducing heat transfer losses and effectively improving the solar thermal utilization efficiency of solar thermal power generation systems.

[0003] Solar thermal power generation integrated ceramic absorption / storage units typically consist of an internal ceramic storage frame and an external ceramic absorption frame. The external absorption ceramic frame requires high solar absorptivity and high photothermal conversion efficiency to effectively absorb solar energy and convert it into heat. The internal storage ceramic frame needs high thermal conductivity and high porosity to effectively transfer the converted heat energy to the phase change material for storage and to encapsulate a sufficient amount of phase change material. The entire integrated absorption / storage unit also requires excellent thermal shock resistance and mechanical properties. Furthermore, the interface layer between the absorption and storage ceramic frames needs strong compatibility to enhance heat transfer efficiency. The pore structure of both the absorption and storage ceramic frames is crucial to the mechanical / thermal performance and thermal cycling stability of the entire absorption / storage unit; precise pore structure design helps improve the photothermal conversion efficiency of the entire unit.

[0004] For example, the Chinese invention patent "An antioxidant, long-life corundum-mullite ceramic with integrated heat absorption and storage and its preparation method" (CN202110651773.6) describes an antioxidant, long-life corundum ceramic with integrated heat absorption and storage. Mullite ceramics and their preparation method are disclosed. The raw materials and modifiers used to prepare the ceramics are as follows: alumina 65-75 wt%, Suzhou clay 15-20 wt%, titanium oxide 3-5 wt%, molybdenum oxide 3-6 wt%, iron oxide 5-7%, and nickel oxide 2-3 wt%. The corundum-mullite heat-absorbing / heat-storing integrated ceramics are prepared from these raw materials. The crystal phase of this heat-absorbing / heat-storing ceramic is black corundum, which has weak heat absorption performance and lower thermal conductivity than non-oxide ceramics such as silicon carbide. Furthermore, no structural optimization has been performed to improve its photothermal utilization efficiency. For example, in the paper "Preparation and characterization of solar absorption and thermal storage integrated ceramics from calcium and iron-rich steel slag" (Ceramics International, 49(5) (2023) 8381-8389), a calcium magnesium olivine / magnesium iron spinel ceramic with integrated heat absorption and heat storage was synthesized using steel slag and limestone as raw materials. Although the ceramic has certain heat absorption and heat storage functions, its absorption rate and thermal conductivity are too low, and it has not undergone structural design.

[0005] For example, the Chinese invention patent "Bamboo-inspired Phase Change Thermal Storage Material and Preparation Method" (CN202111517549.4) uses bamboo joints as raw materials. A porous silicon carbide ceramic with a bamboo-like shape is generated through the reaction of molten silicon with a carbonized bamboo structure. Inorganic salts are then vacuum-impregnated into the silicon carbide framework to obtain a composite material with high thermal conductivity (35 W / m•K) and high energy storage density (309 kJ / kg). Additionally, titanium nitride is loaded onto the surface of silicon carbide and vacuum-impregnated with paraffin to obtain a composite photothermal storage material with a spectral absorption rate as high as 96%. This integrated heat absorption / storage device combines silicon carbide thermal storage units and titanium nitride heat absorption units, exhibiting high absorption rate and thermal conductivity. Furthermore, the bamboo joints utilize a biomimetic hierarchical structure, effectively improving heat exchange efficiency. The paper "Loofah-derived eco-friendly SiC ceramics for high-performance sunlight capture, thermal transport, and energy storage" (Solar Energy Materials, 45 (2022) 786-795) still uses bamboo joints as a template and employs reaction sintering to prepare biomimetic porous silicon carbide ceramics, coating the surface of the high thermal conductivity silicon carbide ceramic with a high-absorption titanium nitride layer. However, the interface bonding between the titanium nitride heat-absorbing layer and the silicon carbide heat-storage layer in the silicon carbide / titanium nitride heat-absorbing / heat-storage integrated ceramic prepared by the above method is poor, and the pore structure cannot be precisely controlled, which to some extent limits the application and development of heat-absorbing / heat-storage integrated ceramics for solar thermal power generation. Summary of the Invention

[0006] To address the aforementioned deficiencies or improvement needs of existing technologies, the present invention aims to provide a multi-material photopolymerization 3D printing integrated fabrication method for a titanium nitride / silicon carbide (TiN / SiC) heat-absorbing and heat-storing heterogeneous ceramic skeleton. By optimizing the composition suitable for the TiN / SiC heat-absorbing and heat-storing heterogeneous ceramic skeleton and combining it with a multi-material photopolymerization 3D printer, a TiN / SiC heat-absorbing and heat-storing heterogeneous ceramic skeleton can be fabricated in an integrated manner. The TiN / SiC heat-absorbing and heat-storing heterogeneous ceramic skeleton obtained by the method provided by this invention has an outer titanium nitride skeleton that can efficiently absorb light energy and convert it into heat energy, while the inner silicon carbide skeleton can encapsulate a sufficient amount of molten salt phase change material and efficiently transfer heat energy to the molten salt for storage, thereby improving the photothermal utilization efficiency of the integrated heat-absorbing / heat-storing unit.

[0007] To achieve the above objectives, according to a first aspect of the present invention, a method for preparing a multi-material photopolymerization 3D printing integrated titanium nitride and silicon carbide heat-absorbing and heat-storing heterogeneous ceramic skeleton is provided, comprising the following steps:

[0008] (1) Prepare silicon carbide ceramic slurry containing photocurable resin, dispersant, photoinitiator and sintering aid; prepare titanium nitride ceramic slurry containing photocurable resin, dispersant, photoinitiator and sintering aid;

[0009] (2) The silicon carbide ceramic slurry and the titanium nitride ceramic slurry are respectively added to the slurry cavity of the multi-material photopolymerization 3D printer, and the model information of the titanium nitride silicon carbide heterostructure ceramic skeleton is input into the printer for photopolymerization printing. After degreasing and sintering treatment, the titanium nitride silicon carbide heterostructure ceramic skeleton is obtained.

[0010] As a preferred embodiment of the present invention, in step (1);

[0011] The silicon carbide ceramic slurry also includes polymethyl methacrylate microspheres and camphene;

[0012] The polymethyl methacrylate microspheres have an average particle size of 2-10 μm, and the amount of polymethyl methacrylate microspheres added accounts for 5-10 wt% of the silicon carbide ceramic slurry.

[0013] The borneol accounts for 10 to 30% of the volume of the silicon carbide ceramic slurry.

[0014] As a preferred embodiment of the present invention, in step (1);

[0015] The silicon carbide powder in the silicon carbide ceramic slurry has an average particle size of 5-10 μm, and the amount of silicon carbide powder accounts for 40-50 vol% of the silicon carbide ceramic slurry.

[0016] The titanium nitride ceramic slurry contains titanium nitride powder with an average particle size of 0.5 to 5.0 μm, and the amount of titanium nitride powder accounts for 45 to 55 vol of the titanium nitride ceramic slurry.

[0017] As a preferred embodiment of the present invention, in step (1);

[0018] The photocurable resin is a mixture of monofunctional photocurable monomers, difunctional photocurable monomers, high-functionality photocurable monomers, and high-refractive-index photocurable monomers; wherein the volume ratio of the monofunctional photocurable monomers, difunctional photocurable monomers, high-functionality photocurable monomers, and high-refractive-index photocurable monomers is 2:2:3:3 to 2:2:1:5, and the total volume ratio of the monofunctional and difunctional photocurable monomers is 40 vol% of the photocurable resin.

[0019] The monofunctional photocurable monomer is one of lauryl acrylate, ethoxyethoxyethyl acrylate, isobornyl acrylate, and acrylomorpholine; the difunctional photocurable monomer is one of 1,6-hexanediol acrylate, tripropylene glycol diacrylate, dipropylene glycol acrylate, propionyl oxydipentyl glycol acrylate, and 1,9-nonanediol diacrylate; the high-functionality photocurable monomer is one of trimethylolpropane triacrylate, ethoxytrimethylolpropane triacrylate, and pentaerythritol triacrylate; the high refractive index photocurable monomer is one of o-phenylphenoxyethyl acrylate or 9,9-bis[4-(2-acryloyloxyethoxy)phenyl]fluorene bisphenol fluorene diacrylate.

[0020] The amount of the photocurable resin added corresponds to 50-60 vol% and 45-55 vol% of the silicon carbide ceramic slurry and the titanium nitride ceramic slurry, respectively.

[0021] As a preferred embodiment of the present invention, in step (1);

[0022] The dispersant is one of the polymer copolymer dispersants BYK111, BYK163, and BYK180, and the amount of the dispersant added corresponds to 2 to 4 wt% of the silicon carbide ceramic slurry or the titanium nitride ceramic slurry.

[0023] The photoinitiator is one of 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, 1-hydroxycyclohexylphenyl ketone, and phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide, and the amount of the photoinitiator added corresponds to 1 to 5 wt% of the silicon carbide ceramic slurry or the titanium nitride ceramic slurry.

[0024] As a preferred embodiment of the present invention, in step (1);

[0025] The sintering aid is one or more of yttrium oxide powder, aluminum oxide powder, and magnesium oxide powder;

[0026] The amount of the sintering aid added corresponds to 2 to 4 wt% of the silicon carbide ceramic slurry or the titanium nitride ceramic slurry.

[0027] As a preferred embodiment of the present invention, in step (2);

[0028] The laser power for the photopolymerization printing is 5 ~ 200 mW / cm. 2 The printing layer thickness is 20 ~ 50 μm;

[0029] The extrusion rate and direct writing rate of the silicon carbide ceramic slurry are 5~10 cm. 3 / s and 5 ~ 20 mm / s;

[0030] The extrusion rate and direct writing rate of the titanium nitride ceramic slurry are 10~20 cm⁻¹, respectively. 3 / s and 10 ~ 20 mm / s.

[0031] As a preferred embodiment of the present invention, in step (2);

[0032] The model information of the titanium nitride silicon carbide heteroceramic skeleton is set as follows: the outer layer of the titanium nitride silicon carbide heteroceramic skeleton is prepared by the titanium nitride ceramic slurry, and the inner layer of the titanium nitride silicon carbide heteroceramic skeleton is prepared by the silicon carbide ceramic slurry.

[0033] As a preferred embodiment of the present invention, in step (2);

[0034] The degreasing temperature was increased from 25 ℃ to 600 ℃ at a rate of 0.1 ~ 0.5 ℃ / min, and the temperature was maintained at 200 ℃, 340 ℃, 420 ℃, 500 ℃ and 550 ℃ for 100 ~ 120 min respectively.

[0035] The sintering is a two-step sintering process, specifically:

[0036] Under inert gas, the temperature was increased at 5 °C / min and held at 1800 °C for 2 to 4 h, followed by sintering at 5 °C / min in a spark plasma SPS furnace at 1800 °C for 1 to 2 h.

[0037] According to another aspect of the present invention, a titanium nitride silicon carbide hetero ceramic framework prepared by the preparation method described in the first aspect is provided.

[0038] In summary, compared with the prior art, the above-described technical solutions conceived by this invention mainly possess the following technical advantages:

[0039] (1) The material formulation of this invention has significant performance advantages. First, SiC is selected as the heat storage material. Compared with the oxide ceramics commonly used in traditional heat absorption / storage integrated units, SiC has a significantly improved thermal conductivity, which can significantly improve the heat transfer efficiency. In addition, TiN is selected as the heat absorption material, which has an extremely high solar light absorption rate. The combination of the two can greatly improve the photothermal utilization efficiency of the solar thermal power generation system.

[0040] (2) This invention uses photopolymerization 3D printing technology to prepare an integrated heat absorption / storage unit for solar thermal power plants, which is fabricated in one piece. It is especially suitable for the structure of TiN / SiC heterolithic ceramic skeleton. This technology can make the inner and outer layer interfaces of TiN / SiC heterolithic ceramic skeleton excellent and can precisely control the pore structure, which greatly improves the photothermal utilization efficiency of the integrated heat absorption / storage unit.

[0041] (3) The TiN / SiC heat-absorbing / heat-storing heterogeneous ceramic skeleton prepared by the method of the present invention has an outer titanium nitride skeleton that can efficiently absorb light energy and convert it into heat energy, and an inner silicon carbide skeleton that can encapsulate a sufficient amount of molten salt phase change material and efficiently transfer heat energy to the molten salt for storage, thereby improving the photothermal utilization efficiency of the heat-absorbing / heat-storing integrated unit. Attached Figure Description

[0042] Figure 1 This is a schematic flowchart illustrating the integrated fabrication method of multi-material photopolymerization 3D printing of a TiN / SiC endothermic / heat-storing heterogeneous ceramic skeleton, as exemplified by the present invention.

[0043] Figure 2 The morphology image shows the TiN / SiC heterostructure ceramic framework prepared by the multi-material photopolymerization 3D printing process in Example 1 of this invention; wherein, Figure 2 In the image, 'a' represents a SEM image of the outer layer of TiN. Figure 2 In the figure, b represents the EDS energy dispersive spectroscopy analysis of the outer layer of TiN. Figure 2 In the image, 'c' represents the SEM image of the inner layer of SiC.

[0044] Figure 3 Performance diagram of TiN / SiC heterostructure ceramic skeleton prepared by multi-material photopolymerization 3D printing process as an example of an embodiment of the present invention. Detailed Implementation

[0045] To make the objectives, technical solutions, and advantages of this invention clearer, the invention will be further described in detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative and not intended to limit the invention. Furthermore, the technical features involved in the various embodiments of this invention described below can be combined with each other as long as they do not conflict with each other.

[0046] like Figure 1 As shown, this invention provides a method for preparing a multi-material photopolymerization 3D printing integrated titanium nitride and silicon carbide heat-absorbing and heat-storing heterogeneous ceramic skeleton, comprising the following steps:

[0047] Step 1: Prepare SiC ceramic slurry by high-speed ball milling using photocurable resin, dispersant, photoinitiator, silicon carbide (SiC) powder and sintering aid as raw materials;

[0048] Step 2: Prepare TiN ceramic slurry by high-speed ball milling using photocurable resin, dispersant, photoinitiator, titanium nitride (TiN) powder, and sintering aid as raw materials;

[0049] Step 3: Add SiC and TiN ceramic slurries into the slurry chamber of the multi-material photopolymerization 3D printer respectively, and input the model information of the biomimetic grade silicon carbide titanium nitride (TiN / SiC) heterogeneous ceramic skeleton into the printer;

[0050] Step 4: Select appropriate printing layer thickness, slurry extrusion parameters, and exposure parameters to achieve the integral forming of heterogeneous ceramic skeleton;

[0051] Step 5: After degreasing and sintering, a biomimetic TiN / SiC heat-absorbing and heat-storing integrated heterogeneous ceramic skeleton is prepared.

[0052] In some embodiments, the SiC ceramic slurry further includes polymethyl methacrylate (PMMA) microspheres and camphene; the average particle size of the PMMA microspheres is 2 to 10 μm, and the amount of PMMA microspheres added accounts for 5 to 10 wt% of the SiC ceramic slurry; the volume ratio of camphene in the SiC ceramic slurry is 10% to 30%.

[0053] In some embodiments, in step one

[0054] The SiC powder has a particle size d50 of 5 ~ 10 μm, and the amount of SiC powder accounts for 40 ~ 50 vol of SiC ceramic slurry.

[0055] In some embodiments, in step two

[0056] The TiN powder has a particle size d50 of 0.5 ~ 5.0 μm, and the amount of TiN powder accounts for 45 ~ 55 vol of TiN ceramic slurry.

[0057] In some embodiments, the configuration details of the SiC ceramic slurry and TiN ceramic slurry involved in steps one and two, wherein the photocurable resin, polymer copolymer dispersant and photoinitiator are as follows:

[0058] The photocurable resin is a mixture of monofunctional photocurable monomers, difunctional photocurable monomers, high-functionality photocurable monomers and high-refractive-index photocurable monomers, with a volume ratio of 2:2:3:3 to 2:2:1:5, and the total volume ratio of monofunctional and difunctional photocurable monomers is 40 vol of the photocurable resin.

[0059] The monofunctional photocurable monomer is one of lauryl acrylate (LA), ethoxyethoxyethyl acrylate (EOEOEA), isobornyl acrylate (IBOA), and acrylmorpholine (ACMO); the difunctional photocurable monomer is 1,6-hexanediol acrylate (HDDA), tripropylene glycol diacrylate (TPGDA), dipropylene glycol acrylate (DPGDA), dipentylene glycol acrylate (NPG2PODA), and 1,9-nonanediol diacrylate (NDD). One of A); the high-functionality photocurable monomer is one of trimethylolpropane triacrylate (TMPTA), trimethylolpropane triacrylate ethoxylate (TMP3EOTA), or pentaerythritol triacrylate (PETA); the high-refractive-index photocurable monomer is one of o-phenylphenoxyethyl acrylate (OPPEA, refractive index 1.575) or 9,9-bis[4-(2-acryloyloxyethoxy)phenyl]fluorene bisphenol fluorene diacrylate (A-BPEF, refractive index 1.622). The amount of photocurable resin added accounts for 50-60 vol% and 45-55 vol% of SiC ceramic slurry and TiN ceramic slurry, respectively.

[0060] In the description of this invention, the multifunctional photocurable monomer is a photocurable monomer with a light energy greater than or equal to 3, as known in the art. It is a mixture of a high-functionality photocurable monomer and a high-refractive-index photocurable monomer; the high-refractive-index photocurable monomer is a ceramic powder with a refractive index greater than or equal to 2.0 and an absorptivity greater than or equal to 0.5.

[0061] The dispersant is one of the polymer copolymer dispersants BYK111, BYK163, and BYK180, and the amount added is 2 to 4 wt% of the SiC ceramic slurry or TiN ceramic slurry.

[0062] The photoinitiator is one of 2,4,6-trimethylbenzoyl-diphenylphosphine oxide (TPO), 1-hydroxycyclohexylphenyl methyl ketone (184), or phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide (819), and the amount added corresponds to 1 to 5 wt% of the SiC ceramic slurry or TiN ceramic slurry.

[0063] In some embodiments, the sintering aid is one or more of yttrium oxide powder (Y₂O₃ powder), aluminum oxide powder (Al₂O₃ powder), and magnesium oxide powder (MgO powder), and the amount added corresponds to 2 to 4 wt% of the SiC ceramic slurry or TiN ceramic slurry.

[0064] In some embodiments, in step four, the laser power is 5 ~ 200 mW / cm². 2 The printed layer thickness is 20~50μm, and the SiC slurry extrusion rate and direct writing rate are 5~10 cm.3 / s and 5 ~ 20 mm / s, the TiN slurry extrusion rate and direct writing rate are 10 ~ 20 cm / s, respectively. 3 / s and 10 ~ 20 mm / s, and the model information of the TiN / SiC heterostructure ceramic skeleton is set as follows: the outer layer of the TiN / SiC heterostructure ceramic skeleton is prepared by TiN ceramic slurry, and the inner layer of the TiN / SiC heterostructure ceramic skeleton is prepared by SiC ceramic slurry.

[0065] In some embodiments, in step five, the degreasing temperature is increased from 25 °C to 600 °C at a heating rate of 0.1 ~ 0.5 °C / min, and held at 200, 340, 400, 420, 500, 550 and 600 °C for 100 ~ 120 min respectively. Sintering is performed in two steps: first, under inert gas, the temperature is increased at 5 °C / min and held at 1800 °C for 2 ~ 4 h, followed by sintering at 5 °C / min in a spark plasma SPS furnace at 1800 °C for 1 ~ 2 h.

[0066] In another aspect of the present invention, the TiN / SiC heat-absorbing / heat-storing heterogeneous ceramic skeleton prepared by the above-mentioned multi-material photopolymerization 3D printing integrated fabrication method has an outer layer of titanium nitride skeleton for absorbing light energy and converting it into heat energy, and an inner layer of silicon carbide skeleton for encapsulating molten salt phase change material and efficiently transferring heat energy to the molten salt for storage. The heat-absorbing and heat-storing integrated devices prepared by the multi-material photopolymerization 3D printing integrated fabrication method of the TiN / SiC heat-absorbing / heat-storing heterogeneous ceramic skeleton of this patent all exhibit high photothermal utilization efficiency, i.e., high thermal conductivity and absorptivity.

[0067] Some specific embodiments will be given below, along with detailed descriptions in conjunction with the accompanying drawings.

[0068] Example 1

[0069] SiC ceramic slurry was prepared by high-speed ball milling using photocurable resin, dispersant, photoinitiator, PMMA microspheres, camphene, SiC powder, Y2O3 powder, and Al2O3 powder as raw materials.

[0070] In the SiC ceramic slurry, the photocurable resin is a mixture of isobornyl acrylate (IBOA), 1,6-hexanediol acrylate (HDDA), trimethylolpropane triacrylate (TMP3EOTA), and o-phenylphenoxyethyl acrylate (OPPEA) in a volume ratio of 2:4:2:2; the dispersant is 2 wt% BYK111, and the photoinitiator is 3 wt% TPO; the PMMA microspheres have a particle size of 2 μm, and the volume ratio of camphene to SiC ceramic slurry is 1:9; the SiC powder has a particle size d50 of 5 μm, and Y2O3 powder and Al2O3 powder are sintering aids, accounting for 5 wt% of the SiC powder mass. The TiN slurry has a solid content of 45 vol%, and the SiC slurry has a solid content of 40 vol%.

[0071] TiN ceramic slurry was prepared by high-speed ball milling using photocurable resin, dispersant, photoinitiator, TiN powder, and Y2O3 powder as raw materials.

[0072] In the TiN ceramic slurry, the photocurable resin is a mixture of isobornyl acrylate (IBOA), 1,6-hexanediol acrylate (HDDA), trimethylolpropane triacrylate (TMP3EOTA), o-phenylphenoxyethyl acrylate (OPPEA), and 15-functional aliphatic polyurethane acrylate RJ4219, with a volume ratio of 2:2:2:2; the dispersant is 4 wt% of the polymer copolymer dispersant BYK180; the photoinitiator is 5 wt% TPO; the TiN powder particle size d50 is 5.0 μm; and the Y2O3 powder is a sintering aid, accounting for 3 wt% of the SiC powder mass.

[0073] The SiC ceramic slurry and TiN ceramic slurry mentioned above are respectively added to the slurry chamber of the multi-material photopolymerization 3D printer, and the model information of the biomimetic TiN / SiC heterogeneous ceramic skeleton is input into the printer. Photopolymerization 3D printing is performed according to the model information and printing parameters in the above embodiment.

[0074] By selecting appropriate printing layer thickness, slurry extrusion parameters, and exposure parameters, the integral forming of heterogeneous ceramic skeletons can be achieved. The laser power is 200 mW / cm². 2 The printed layer thickness was 20 μm, and the SiC slurry extrusion rate and direct writing rate were 10 cm⁻¹ and 10 cm⁻¹, respectively. 3 The TiN slurry extrusion rate and direct writing rate were 20 cm / s and 10 mm / s, respectively. 3 / s and 10 mm / s.

[0075] After debinding and sintering, a biomimetic TiN / SiC heat-absorbing / heat-storing integrated heterogeneous ceramic framework was finally prepared. The debinding temperature was increased from 25 ℃ to 600 ℃ at a rate of 0.5 ℃ / min, with holding times of 120 min at 200 ℃, 340 ℃, 420 ℃, 500 ℃, 550 ℃, and 600 ℃ respectively. Sintering was performed in two steps: first, under inert gas, the temperature was increased to 1800 ℃ and held for 3 h at a rate of 5 ℃ / min; then, sintering was carried out at 1800 ℃ for 2 h in a spark plasma (SPS) furnace at a rate of 5 ℃ / min.

[0076] Example 2:

[0077] SiC ceramic slurry was prepared by high-speed ball milling using photocurable resin, dispersant, photoinitiator, PMMA microspheres, camphene, SiC powder, Y2O3 powder, and Al2O3 powder as raw materials.

[0078] In the SiC ceramic slurry, the photocurable resin is a mixture of isobornyl acrylate (IBOA), 1,6-hexanediol acrylate (HDDA), trimethylolpropane triacrylate (TMP3EOTA), and o-phenylphenoxyethyl acrylate (OPPEA) in a volume ratio of 2:4:2:2. The dispersant is 3 wt% BYK180, the photoinitiator is 2 wt% 819, the PMMA microspheres have a particle size of 10 μm, the volume ratio of camphene to SiC ceramic slurry is 3:7, the SiC powder particle size d50 is 10 μm, and Y2O3 powder and Al2O3 powder are sintering aids, accounting for 4 wt% of the SiC powder mass. The TiN slurry has a solid content of 55 vol%, and the SiC slurry has a solid content of 50 vol%.

[0079] TiN ceramic slurry was prepared by high-speed ball milling using photocurable resin, dispersant, photoinitiator, TiN powder, and Y2O3 powder as raw materials.

[0080] In the TiN ceramic slurry, the photocurable resin is a mixture of isobornyl acrylate (IBOA), 1,6-hexanediol acrylate (HDDA), trimethylolpropane triacrylate (TMP3EOTA), o-phenylphenoxyethyl acrylate (OPPEA), and 15-functional aliphatic polyurethane acrylate RJ4219, with a volume ratio of 2:2:2:2. The dispersant is 3 wt% of the polymer copolymer dispersant BYK180, and the photoinitiator is 2 wt% 819. The TiN powder particle size d50 is 3.0 μm, and the Y2O3 powder is a sintering aid, accounting for 4 wt% of the SiC powder mass.

[0081] SiC and TiN ceramic slurries are added to the slurry chamber of a multi-material photopolymerization 3D printer, and the model information of the biomimetic TiN / SiC heterogeneous ceramic skeleton is input into the printer. Photopolymerization 3D printing is performed according to the model information and printing parameters in the above embodiment.

[0082] By selecting appropriate printing layer thickness, slurry extrusion parameters, and exposure parameters, the integral forming of heterogeneous ceramic skeletons can be achieved. The laser power is 40 mW / cm². 2 The printed layer thickness was 25 μm, and the SiC slurry extrusion rate and direct writing rate were 10 cm⁻¹ and 10 cm⁻¹, respectively. 3 The TiN slurry extrusion rate and direct writing rate were 10 cm / s and 10 mm / s, respectively. 3 / s and 10 mm / s.

[0083] After debinding and sintering, a biomimetic TiN / SiC endothermic / heat storage heterogeneous ceramic framework was finally prepared. The debinding temperature was increased from 25 ℃ to 600 ℃ at a heating rate of 0.2 ℃ / min, and the holding times were 200, 340, 400, 420, 500, 550 and 600 ℃, with a holding time of 100 min. Sintering was carried out in two steps: first, the temperature was increased to 1800 ℃ and held for 3 h under inert gas at a heating rate of 5 ℃ / min, followed by sintering at 1800 ℃ for 1 h in a spark plasma SPS furnace at a heating rate of 5 ℃ / min.

[0084] Example 3:

[0085] SiC ceramic slurry was prepared by high-speed ball milling using photocurable resin, dispersant, photoinitiator, PMMA microspheres, camphene, SiC powder, Y2O3 powder, and Al2O3 powder as raw materials.

[0086] In the SiC ceramic slurry, the photocurable resin is a mixture of isobornyl acrylate (IBOA), 1,6-hexanediol acrylate (HDDA), trimethylolpropane triacrylate (TMP3EOTA), and o-phenylphenoxyethyl acrylate (OPPEA) in a volume ratio of 2:4:2:2. The dispersant is 4 wt% BYK163, the photoinitiator is 4 wt% 819, the PMMA microspheres have a particle size of 5 μm, the volume ratio of camphene to SiC ceramic slurry is 2:8, the SiC powder particle size d50 is 8 μm, and Y2O3 powder and Al2O3 powder are sintering aids, accounting for 3 wt% of the SiC powder mass. The TiN slurry has a solid content of 50 vol%, and the SiC slurry has a solid content of 45 vol%.

[0087] TiN ceramic slurry was prepared by high-speed ball milling using photocurable resin, dispersant, photoinitiator, TiN powder, and Y2O3 powder as raw materials.

[0088] In the TiN ceramic slurry, the photocurable resin is a mixture of isobornyl acrylate (IBOA), 1,6-hexanediol acrylate (HDDA), trimethylolpropane triacrylate (TMP3EOTA), o-phenylphenoxyethyl acrylate (OPPEA), and 15-functional aliphatic polyurethane acrylate RJ4219, with a volume ratio of 2:2:2:2. The dispersant is 4 wt% of polymer copolymer dispersant BYK163, 4 wt% of photoinitiator 819, the TiN powder particle size d50 is 5.0 μm, and the Y2O3 powder is a sintering aid, accounting for 3 wt% of the SiC powder mass.

[0089] SiC and TiN ceramic slurries are added to the slurry chamber of a multi-material photopolymerization 3D printer, and the model information of the biomimetic TiN / SiC heterogeneous ceramic skeleton is input into the printer. Photopolymerization 3D printing is performed according to the model information and printing parameters in the above embodiment.

[0090] By selecting appropriate printing layer thickness, slurry extrusion parameters, and exposure parameters, the integral forming of heterogeneous ceramic skeletons can be achieved; the laser power is 100 mW / cm². 2 The printed layer thickness was 40 μm, and the SiC slurry extrusion rate and direct writing rate were 10 cm⁻¹, respectively. 3 The TiN slurry extrusion rate and direct writing rate were 15 cm / s and 15 mm / s, respectively. 3 / s and 15 mm / s.

[0091] After debinding and sintering, a biomimetic TiN / SiC heat-absorbing / heat-storing integrated heterogeneous ceramic framework was finally prepared. The debinding temperature was increased from 25 ℃ to 600 ℃ at a heating rate of 0.25 ℃ / min, and the holding times were 200, 340, 400, 420, 500, 550 and 600 ℃, with a holding time of 120 min. Sintering was carried out in two steps: first, the temperature was increased to 1800 ℃ and held for 2 h under inert gas at a heating rate of 5 ℃ / min, followed by sintering at 1800 ℃ for 2.5 h in a spark plasma SPS furnace at a heating rate of 5 ℃ / min.

[0092] Those skilled in the art will readily understand that the above description is merely a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, and improvements made within the spirit and principles of the present invention should be included within the scope of protection of the present invention.

Claims

1. A method for fabricating a multi-material photopolymerization 3D printing integrated titanium nitride and silicon carbide heat-absorbing and heat-storing heterogeneous ceramic skeleton, characterized in that, Includes the following steps: (1) Prepare silicon carbide ceramic slurry containing photocurable resin, dispersant, photoinitiator, sintering aid, polymethyl methacrylate microspheres and camphene; prepare titanium nitride ceramic slurry containing photocurable resin, dispersant, photoinitiator and sintering aid; (2) The silicon carbide ceramic slurry and the titanium nitride ceramic slurry are respectively added to the slurry chamber of the multi-material photopolymerization 3D printer, and the model information of the titanium nitride silicon carbide heterostructure ceramic skeleton is input into the printer for photopolymerization printing. After degreasing and sintering, the titanium nitride silicon carbide heterostructure ceramic skeleton is obtained. The model information for the titanium nitride silicon carbide heteroceramic framework is set as follows: The outer layer of the titanium nitride-silicon carbide heteroceramic framework is prepared by the titanium nitride ceramic slurry, and the inner layer of the titanium nitride-silicon carbide heteroceramic framework is prepared by the silicon carbide ceramic slurry; the inner layer of the titanium nitride-silicon carbide heteroceramic framework is used to encapsulate molten salt phase change material.

2. The method for preparing a multi-material photopolymerization 3D printing integrated titanium nitride and silicon carbide heat-absorbing and heat-storing heterogeneous ceramic skeleton according to claim 1, characterized in that, In step (1); The polymethyl methacrylate microspheres have an average particle size of 2-10 μm, and the amount of polymethyl methacrylate microspheres added accounts for 5-10 wt% of the silicon carbide ceramic slurry. The borneol accounts for 10 to 30% of the volume of the silicon carbide ceramic slurry.

3. The method for preparing a multi-material photopolymerization 3D printing integrated titanium nitride and silicon carbide heat-absorbing and heat-storing heterogeneous ceramic skeleton according to claim 1, characterized in that, In step (1); The silicon carbide powder in the silicon carbide ceramic slurry has an average particle size of 5-10 μm, and the amount of silicon carbide powder accounts for 40-50 vol% of the silicon carbide ceramic slurry. The titanium nitride ceramic slurry contains titanium nitride powder with an average particle size of 0.5 to 5.0 μm, and the amount of titanium nitride powder accounts for 45 to 55 vol of the titanium nitride ceramic slurry.

4. The method for preparing a multi-material photopolymerization 3D printing integrated titanium nitride and silicon carbide heat-absorbing and heat-storing heterogeneous ceramic skeleton according to claim 1, characterized in that, In step (1); The photocurable resin is a mixture of monofunctional photocurable monomers, difunctional photocurable monomers, high-functionality photocurable monomers, and high-refractive-index photocurable monomers; wherein the volume ratio of the monofunctional photocurable monomers, difunctional photocurable monomers, high-functionality photocurable monomers, and high-refractive-index photocurable monomers is 2:2:3:3 to 2:2:1:5, and the total volume ratio of the monofunctional and difunctional photocurable monomers is 40 vol% of the photocurable resin. The monofunctional photocurable monomer is one of lauryl acrylate, ethoxyethoxyethyl acrylate, isobornyl acrylate, and acrylomorpholine; the difunctional photocurable monomer is one of 1,6-hexanediol acrylate, tripropylene glycol diacrylate, dipropylene glycol acrylate, propionyl oxydipentyl glycol acrylate, and 1,9-nonanediol diacrylate; the high-functionality photocurable monomer is one of trimethylolpropane triacrylate, ethoxytrimethylolpropane triacrylate, and pentaerythritol triacrylate; the high refractive index photocurable monomer is one of o-phenylphenoxyethyl acrylate or 9,9-bis[4-(2-acryloyloxyethoxy)phenyl]fluorene bisphenol fluorene diacrylate. The amount of the photocurable resin added corresponds to 50-60 vol% and 45-55 vol% of the silicon carbide ceramic slurry and the titanium nitride ceramic slurry, respectively.

5. The method for preparing a multi-material photopolymerization 3D printing integrated titanium nitride and silicon carbide heat-absorbing and heat-storing heterogeneous ceramic skeleton according to claim 1, characterized in that, In step (1); The dispersant is one of the polymer copolymer dispersants BYK111, BYK163, and BYK180, and the amount of the dispersant added corresponds to 2 to 4 wt% of the silicon carbide ceramic slurry or the titanium nitride ceramic slurry. The photoinitiator is one of 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, 1-hydroxycyclohexylphenyl ketone, and phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide, and the amount of the photoinitiator added corresponds to 1 to 5 wt% of the silicon carbide ceramic slurry or the titanium nitride ceramic slurry.

6. The method for preparing a multi-material photopolymerization 3D printing integrated titanium nitride and silicon carbide heat-absorbing and heat-storing heterogeneous ceramic skeleton according to claim 2, characterized in that, In step (1); The sintering aid is one or more of yttrium oxide powder, aluminum oxide powder, and magnesium oxide powder; The amount of the sintering aid added corresponds to 2 to 4 wt% of the silicon carbide ceramic slurry or the titanium nitride ceramic slurry.

7. The method for preparing a multi-material photopolymerization 3D printing integrated titanium nitride and silicon carbide heat-absorbing and heat-storing heterogeneous ceramic skeleton according to claim 1, characterized in that, In step (2); The laser power for the photopolymerization printing is 5 ~ 200 mW / cm. 2 The printing layer thickness is 20 ~ 50 μm; The extrusion rate and direct writing rate of the silicon carbide ceramic slurry are 5~10 cm. 3 / s and 5 ~ 20 mm / s; The extrusion rate and direct writing rate of the titanium nitride ceramic slurry are 10~20 cm⁻¹, respectively. 3 / s and 10 ~ 20 mm / s.

8. The method for preparing a multi-material photopolymerization 3D printing integrated titanium nitride and silicon carbide heat-absorbing and heat-storing heterogeneous ceramic skeleton according to claim 1, characterized in that, In step (2); The degreasing temperature was increased from 25 ℃ to 600 ℃ at a rate of 0.1 ~ 0.5 ℃ / min, and the temperature was maintained at 200 ℃, 340 ℃, 420 ℃, 500 ℃ and 550 ℃ for 100 ~ 120 min respectively. The sintering is a two-step sintering process, specifically: Under inert gas, the temperature was increased at 5 °C / min and held at 1800 °C for 2 to 4 h, followed by sintering at 5 °C / min in a spark plasma SPS furnace at 1800 °C for 1 to 2 h.

9. The titanium nitride silicon carbide heterostructure ceramic framework prepared by the preparation method according to any one of claims 1-8.

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