Method for the preparation of ductile biomimetic structured ceramic materials for fused deposition 3d printing

Abstract

The application discloses a method for preparing a tough biomimetic structure ceramic material for fused deposition 3D printing, and belongs to the technical field of additive manufacturing. Graphene and an ionic polymer are modified on the surface of a flaky ceramic powder, so that the agglomeration and accumulation tendency of the flaky ceramic powder can be inhibited, the dispersibility of the flaky ceramic powder in an alkane printing binder can be improved, and the flaky ceramic powder is beneficial to be oriented under the action of an external field. Meanwhile, the in-situ introduced graphene is helpful to improve the strength and toughness of the flaky ceramic powder, improve the structural integrity of the raw material in the processing process and the strength and toughness of the finally sintered ceramic, and the problem that complex components are not easy to be prepared in the existing ceramic fused deposition 3D printing is solved.

Description

Technical Field

[0001] This invention belongs to the technical field of additive manufacturing and relates to a method for preparing tough biomimetic structural ceramic materials for fused deposition modeling (FDM) 3D printing. Background Technology

[0002] Ceramics possess excellent properties such as high hardness, high strength, and high modulus, and are widely used in energy, medical, and aerospace fields. However, their inherent brittleness and crack sensitivity limit their service environment and lifespan. In recent years, due to the development of biomimetic technology, various biomimetic materials based on the microstructure of organisms have emerged. By studying the "brick-and-mortar" multi-level microstructure of shellfish and crustaceans in nature, which have good impact resistance, layered composite ceramics with similar interface structure designs have been prepared using biomimetic technology. Their microstructure consists of alternating hard and soft layers, which prolongs the crack propagation path and significantly improves the fracture toughness and energy absorption level of the material. Unlike traditional toughening mechanisms, the toughening mechanism of layered composite ceramics is an energy absorption and dissipation mechanism. This structural design reduces the sensitivity of the material's mechanical properties to defects, making it a defect-resistant material and greatly improving its fracture toughness. Compared to traditional toughening mechanisms, layered composite ceramic designs avoid the limitations of working environment on toughening effects and the need for uniform dispersion of the first phase. Moreover, their toughening effect is far superior to traditional mechanisms, with fracture energy potentially increasing by 2-3 orders of magnitude. Currently, layered composite ceramics typically employ processes such as tape casting, gel casting, and roll forming to prepare the hard and soft interlayers. After drying, the hard and soft interlayers are stacked together and sintered to prepare the layered ceramic composite material. While these methods produce layered composite ceramics with high toughness, their structures are usually relatively simple, making it difficult to fabricate ceramic components with complex structures, thus significantly limiting their applications.

[0003] In recent years, emerging additive manufacturing technologies, such as 3D printing, are based on the principle of discrete deposition, using automated control to deposit materials layer by layer to achieve rapid manufacturing of complex parts. They offer advantages such as flexible structural design, integrated processing and molding, high precision, and short production cycles, providing a new approach for fabricating high-performance ceramic parts with complex structures. Among these, fused deposition modeling (FDM) 3D printing is a method that involves heating and melting various fusible filaments or granules, solidifying them layer by layer on a printing table to obtain a three-dimensional ceramic preform, followed by high-temperature debinding and sintering to obtain the final ceramic part.

[0004] In the additive manufacturing process of ceramic fused deposition modeling (FDM) 3D printing, spherical ceramic powders with higher flowability are typically selected as raw materials. However, this often overlooks the crushing effect of ball milling and other processing methods on the spherical raw materials, as well as the large packing gaps between the spherical particles. Therefore, the resulting ceramics are usually low in density and brittle. Furthermore, the preparation of high-toughness ceramic materials using traditional methods is often complex and not suitable for producing ceramic materials with complex and fine structures, thus limiting its practical applications.

[0005] Therefore, in view of the above-mentioned defects of existing ceramic fused deposition modeling 3D printing technology, this invention discloses a method for preparing tough biomimetic structural ceramic materials for fused deposition modeling 3D printing. Summary of the Invention

[0006] The purpose of this invention is to provide a method for preparing tough biomimetic structural ceramic materials for fused deposition modeling (FDM) printing. Based on an in-situ covalent grafting method, a modification strategy of graphene and ionic polymers is introduced to modify the surface of sheet ceramics. Through the high in-plane toughness of graphene and the repulsion between ionic polymers, the orientation degree and toughness of sheet ceramics are further improved, overcoming the difficulty in preparing complex components in existing ceramic FDM printing.

[0007] This invention is achieved through the following technical solution: A method for preparing tough biomimetic structural ceramic materials for fused deposition modeling (FDM) 3D printing includes the following steps: Step 1: Introduce graphene and ionomer on the surface of sheet-like ceramic powder by in-situ covalent grafting to modify the sheet-like ceramic powder. Step 2: Mix the modified sheet ceramic powder, sintering aid, printing adhesive and plasticizer to obtain filament raw material. Disperse the filament raw material evenly by solution dispersion and extrude the filament raw material to form printing filament. Step 3: Using a fused deposition modeling (FDM) 3D printing device, the printing filament is melted and printed onto the surface of the part to obtain a preliminary blank. During the fused printing process, the molten printing filament is rolled to make the sheet-like ceramic material in the molten printing filament oriented and aligned along the rolling direction. Step 4: Degrease the preform to remove the ionic polymers used to assist molding, and obtain the brown body; Step 5: Sinter the brown body to densify it and form a ceramic material.

[0008] To better implement the present invention, step 1 further includes: Step 1.1: A condensation reaction is carried out between a silane coupling agent and the hydroxyl groups on the surface of the sheet-like ceramic powder, so that the silane coupling agent is grafted onto the surface of the sheet-like ceramic powder. Step 1.2: Add the sheet-like ceramic powder to the uniformly dispersed graphene oxide solution to graft the graphene oxide onto the surface of the sheet-like ceramic powder. Step 1.3: React the sheet-like ceramic powder with a silane coupling agent to introduce vinyl groups onto the surface of the sheet-like ceramic powder, thereby grafting bivalent bonds onto the surface of the sheet-like ceramic powder; Step 1.4: Add the sheet-like ceramic powder grafted with bicovalent bonds to a solution containing ionic polymer monomers for free radical copolymerization; Step 1.5: Reduce the graphene oxide on the surface of the sheet ceramic powder to graphene, and dissociate the sheet ceramic powder in an acidic or alkaline environment to form a polyelectrolyte with positive or negative charge on the surface of the sheet ceramic powder, thereby completing the modification of the sheet ceramic powder.

[0009] To better realize the present invention, step 2 further includes: Step 2.1: Dissolve the printing adhesive using an organic solvent; Step 2.2: Mix the modified flake ceramic powder, sintering aid, printing adhesive, and plasticizer to obtain a raw material solution, and then ultrasonically disperse the raw material solution; Step 2.3: Filter, dry, and pulverize the dispersed raw material solution to obtain the silk raw material, and then perform internal mixing on the silk raw material; Step 2.4: Use a screw extruder to extrude the mixed filament material to prepare printing filament.

[0010] To better realize the present invention, the volume fraction of the flake ceramic powder in the raw material solution is 10 vol%-70 vol%, and the ratio of the sintering aid, printing adhesive and plasticizer is 2:1:1; the thickness of the flake ceramic powder is 10 nm-1000 nm, the width is 5 μm-100 μm and the length is 5 μm-100 μm.

[0011] To better realize the present invention, the volume fraction of the flake ceramic powder in the raw material solution is 50 vol.

[0012] To better realize the present invention, the printing adhesive further includes any one monomer or a mixture of any two of polyethylene, polyvinyl acetate, polyethylene glycol, and polyethylene oxide.

[0013] To better realize the present invention, step 3 further includes: Step 3.1: Use a laser beam as a heating source, so that half of the laser beam acts on the printing filament until the printing filament is in a semi-molten state; the other half of the laser beam acts on the surface of the part, and then use a fused deposition modeling 3D printing device to print the semi-molten printing filament onto the surface of the part; Step 3.2: During the process of laying the printing filament on the surface of the part, a roller pressing device is used to roll the semi-molten printing filament to roll it into a flat strip, so that the printing filament is oriented and arranged along the rolling direction to obtain a preliminary blank.

[0014] To better realize the present invention, step 4 further includes: Step 4.1: Place the initial blank in the air and fire it for a time of 2 hours or more. The heating rate during the firing process is 0.5℃ / min, and the final firing temperature is 600℃ or more. Step 4.2: Continue heating at a rate of 2℃ / min until the firing temperature is greater than or equal to 1000℃ and the firing time is greater than or equal to 2h.

[0015] To better realize the present invention, in step 5, the temperature is further increased at a rate of 4°C / min until the sintering temperature is greater than or equal to 1600°C and the sintering time is greater than or equal to 2h.

[0016] Compared with the prior art, the present invention has the following advantages and beneficial effects: (1) The present invention modifies the surface of sheet ceramic powder with graphene and ion polymer, which can not only suppress the agglomeration and stacking tendency between sheet ceramic powder, but also improve the dispersibility of sheet ceramic powder between alkane printing binders, thereby facilitating the orientation of sheet ceramic powder under the action of external field; at the same time, the in-situ introduction of graphene helps to improve the strength and toughness of sheet ceramic powder, and improve the structural integrity of raw materials during processing and the strength and toughness of the final sintered ceramic. (2) The present invention uses a laser beam as a heating source. Half of the laser beam spot acts on the printing filament to make it reach a semi-molten state, and the other half acts on the surface of the formed part, which promotes the penetration of the resin molecular chain ends of the formed part between adjacent layers and increases the fluidity of the printing filament. (3) The present invention adds a roller pressing device during the melt printing process, which can flatten the semi-molten printing filament into a strip under the pressure of the roller and bond it to the formed part. The pressure of the roller pressing enhances the bonding effect between adjacent filaments, and at the same time, it is beneficial for the sheet ceramics in the molten printing raw material to be oriented along the roller pressing direction, reducing the shrinkage rate in subsequent sintering, and thus improving the density of the component. (4) Layered composite ceramic materials prepared by the principle of fused 3D additive printing not only have higher toughness, but can also be designed with various complex structures according to service requirements, thereby achieving flexible and efficient customization of target components. Attached Figure Description

[0017] Figure 1 This is a schematic diagram of the steps of the present invention; Figure 2 This is a schematic diagram of the processing flow for sheet ceramics. Detailed Implementation

[0018] The following detailed description is illustrative and intended to provide further explanation of the invention. Unless otherwise specified, all technical and scientific terms used in this invention have the same meaning as commonly understood by one of ordinary skill in the art to which this invention pertains.

[0019] It should be noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the scope of exemplary embodiments according to the invention. As used herein, unless otherwise expressly indicated by the invention, the singular form is intended to include the plural form as well. Furthermore, it should be understood that when the terms "comprising" and / or "including" are used in this specification, they indicate the presence of features, steps, operations, devices, components, and / or combinations thereof.

[0020] For ease of description, the words "up," "down," "left," and "right" appearing in this invention only indicate that they are consistent with the up, down, left, and right directions of the accompanying drawings themselves, and do not limit the structure. They are merely for the purpose of facilitating the description of this invention and simplifying the description, and do not indicate or imply that the device or component referred to must have a specific orientation, or be constructed and operated in a specific orientation. Therefore, they should not be construed as limitations on this invention.

[0021] Terminology Explanation: The terms "installation," "connection," "linking," and "fixing" in this invention should be interpreted broadly. For example, they can refer to a fixed connection, a detachable connection, or an integral part; they can refer to a mechanical connection or an electrical connection; they can refer to a direct connection or an indirect connection through an intermediate medium; they can refer to the internal connection of two components or the interaction relationship between two components. Those skilled in the art can understand the specific meaning of the above terms in this invention according to the specific circumstances.

[0022] Example 1: The method for preparing tough biomimetic structural ceramic materials for fused deposition modeling (FDM) 3D printing in this embodiment is as follows: Figure 1 As shown, it includes the following steps: Step 1: Introduce graphene and ionomer on the surface of sheet-like ceramic powder by in-situ covalent grafting to modify the sheet-like ceramic powder. Step 2: Mix the modified sheet ceramic powder, sintering aid, printing adhesive and plasticizer to obtain filament raw material. Disperse the filament raw material evenly by solution dispersion and extrude the filament raw material to form printing filament. Step 3: Using a fused deposition modeling (FDM) 3D printing device, the printing filament is melted and printed onto the surface of the part to obtain a preliminary blank. During the fused printing process, the molten printing filament is rolled to make the sheet-like ceramic material in the molten printing filament oriented and aligned along the rolling direction. Step 4: Degrease the preform to remove the ionic polymers used to assist molding, and obtain the brown body; Step 5: Sinter the brown body to densify it and form a ceramic material.

[0023] Example 2: A method for preparing tough biomimetic structural ceramic materials for fused deposition modeling (FDM) is improved based on Example 1, wherein step 1 specifically includes: Step 1.1: A condensation reaction is carried out between a silane coupling agent and the hydroxyl groups on the surface of the sheet-like ceramic powder, so that the silane coupling agent is grafted onto the surface of the sheet-like ceramic powder. Step 1.2: Add the sheet-like ceramic powder to the uniformly dispersed graphene oxide solution to graft the graphene oxide onto the surface of the sheet-like ceramic powder. Step 1.3: React the sheet-like ceramic powder with a silane coupling agent to introduce vinyl groups onto the surface of the sheet-like ceramic powder, thereby grafting bivalent bonds onto the surface of the sheet-like ceramic powder; Step 1.4: Add the sheet-like ceramic powder grafted with bicovalent bonds to a solution containing ionic polymer monomers for free radical copolymerization; Step 1.5: Reduce the graphene oxide on the surface of the sheet ceramic powder to graphene, and dissociate the sheet ceramic powder in an acidic or alkaline environment to form a polyelectrolyte with positive or negative charge on the surface of the sheet ceramic powder, thereby completing the modification of the sheet ceramic powder.

[0024] The other parts of this embodiment are the same as those in Embodiment 1, so they will not be described again.

[0025] Example 3: A method for preparing tough biomimetic structural ceramic materials for fused deposition modeling, improved based on Example 1 or 2, wherein step 2 specifically includes: Step 2.1: Dissolve the printing adhesive using an organic solvent; Step 2.2: Mix the modified flake ceramic powder, sintering aid, printing adhesive, and plasticizer to obtain a raw material solution, and then ultrasonically disperse the raw material solution; Step 2.3: Filter, dry, and pulverize the dispersed raw material solution to obtain the silk raw material, and then perform internal mixing on the silk raw material; Step 2.4: Use a screw extruder to extrude the mixed filament material to prepare printing filament.

[0026] Furthermore, the volume fraction of the flake ceramic powder in the raw material solution is 10 vol%-70 vol%, and the ratio of the sintering aid, printing binder, and plasticizer is 2:1:1; the thickness of the flake ceramic powder is 10 nm-1000 nm, the width is 5 μm-100 μm, and the length is 5 μm-100 μm.

[0027] Furthermore, the volume fraction of the flake-shaped ceramic powder in the raw material solution is 50 vol.

[0028] Furthermore, the printing adhesive includes any one monomer or a mixture of any two of polyethylene, polyvinyl acetate, polyethylene glycol, and polyethylene oxide.

[0029] The other parts of this embodiment are the same as those in Embodiment 1 or 2, so they will not be described again.

[0030] Example 4: A method for preparing tough biomimetic structural ceramic materials for fused deposition modeling, improved based on any one of Examples 1-3, wherein step 3 specifically includes: Step 3.1: Use a laser beam as a heating source, so that half of the laser beam acts on the printing filament until the printing filament is in a semi-molten state; the other half of the laser beam acts on the surface of the part, and then use a fused deposition modeling 3D printing device to print the semi-molten printing filament onto the surface of the part; Step 3.2: During the process of laying the printing filament on the surface of the part, a roller pressing device is used to roll the semi-molten printing filament to flatten it into a strip shape, so that the printing filament is aligned along the rolling direction to obtain a preliminary blank. The rolling direction is set along the 3D printing direction, and the rolling particle size is determined by the relative distance between the roller and the printed part. The relative distance is determined by the printing layer height in the path planning.

[0031] The other parts of this embodiment are the same as any one of embodiments 1-3, so they will not be described again.

[0032] Example 5: A method for preparing tough biomimetic structural ceramic materials for fused deposition modeling, improved based on any one of Examples 1-4, wherein step 4 specifically includes: Step 4.1: Place the initial blank in the air and fire it for a time of 2 hours or more. The heating rate during the firing process is 0.5℃ / min, and the final firing temperature is 600℃ or more. Step 4.2: Continue heating at a rate of 2℃ / min until the firing temperature is greater than or equal to 1000℃ and the firing time is greater than or equal to 2h.

[0033] In step 5, the temperature continues to rise at a rate of 4℃ / min until the sintering temperature is greater than or equal to 1600℃ and the sintering time is greater than or equal to 2h.

[0034] The other parts of this embodiment are the same as any one of embodiments 1-4, so they will not be described again.

[0035] Example 6: Methods for preparing tough biomimetic structural ceramic materials for fused deposition modeling (FDM) 3D printing, such as Figure 2 As shown: Modified flake ceramic powder: The flake-shaped ceramic powder uses flake-shaped alumina. A condensation reaction is performed between a silane coupling agent (KH550) and the hydroxyl groups on the surface of the flake-shaped alumina (FC), followed by ultrasonic solvent cleaning to remove ungrafted silane coupling agent. The silane-coated flake-shaped alumina (FC-KH550) is then added to a uniformly dispersed graphene oxide solution to graft graphene oxide onto the surface of the flake-shaped alumina, achieving graphene grafting onto the flake-shaped alumina surface. The graphene-grafted flake-shaped alumina (FC-G) is then reacted with a silane coupling agent (KH570) to introduce reactive vinyl groups onto the surface of the graphene-grafted flake-shaped alumina (FC-G). Finally, the flake-shaped alumina grafted with bivalent bonds is added to a solution containing ethyleneimine for free radical copolymerization, thereby introducing a large amount of polyethyleneimine onto the surface of the flake-shaped alumina to obtain flake-shaped alumina with ionomer-bound polymers on the surface (FC-G-PEI). The graphene oxide on the surface of sheet-like alumina with ionomers is partially ionized and reduced to graphene, and polyethyleneimine is ionized to polyethyleneimine salt using an acidic solution, finally obtaining the modified sheet-like ceramic powder (FC-G-PEI+).

[0036] The solution for preparing the filament raw material includes paraffin, polyethylene, and polyvinyl acetate, with the ratio of paraffin:polyethylene:polyvinyl acetate = 2:1:1; the volume fraction of flake alumina in the raw material solution is 50 vol.

[0037] Flake alumina can also refer to a mixture, in which the ratio of flake alumina, nano-magnesium oxide, nano-titanium oxide, nano-zirconium oxide, and nano-silicon oxide in the above mixture is 1:1:1:1:1. 10% polyvinyl acetate was dissolved in acetone, and the flake alumina was added to the raw material solution and ultrasonically dispersed for 1 hour. The dispersion was then filtered, dried, and pulverized. Finally, the above raw materials were thoroughly mixed at 190°C for 2 hours to ensure uniformity. A 1.75 mm diameter printing filament was then prepared using a twin-screw extruder.

[0038] Fused deposition modeling (FDM) 3D printing equipment is used to transform the prepared printing filament into a preform. The model to be printed is drawn using MaterialiseMagics software, and then sliced ​​using Cura software. Before printing, the printability of the filament is tested to determine the appropriate laser beam power and slice thickness. During layup, a laser beam is used as the heating source. Half of the laser beam spot acts on the printing filament, bringing it to a semi-molten state, while the other half acts on the surface of the already formed part. This promotes the penetration of resin molecular chain ends between adjacent layers, increasing fluidity. Simultaneously, an added roller pressing device flattens the semi-molten printing filament into a strip under the pressure of the rollers, bonding it to the already formed part. The pressure of the rollers also enhances the bonding effect between adjacent filaments, thus facilitating the orientation of the sheet-like alumina along the roller pressing direction, reducing shrinkage during subsequent sintering, and increasing the density of the component.

[0039] The initial embryo is degreased: preferably by solvent degreasing followed by high-temperature degreasing. First, it is fired in air at 600°C for 2 hours at a heating rate of 0.5°C / min; then, it is heated to 1000°C at a rate of 2°C / min and held at 1000°C for 2 hours.

[0040] The degreased preform is sintered by heating to 1600℃ at a rate of 4℃ / min and holding for 2 hours. After cooling in the furnace, the target layered alumina ceramic is obtained.

[0041] The flexural strength and fracture toughness of the obtained alumina ceramics are shown in Table 1 below: Table 1. Bending Strength and Fracture Toughness The above are merely preferred embodiments of the present invention and are not intended to limit the present invention in any way. Any simple modifications or equivalent changes made to the above embodiments based on the technical essence of the present invention shall fall within the protection scope of the present invention.

Claims

1. A method for the preparation of tough biomimetic structured ceramic materials for fused deposition 3D printing, characterized in that, Includes the following steps: Step 1: Introduce graphene and ionomer on the surface of sheet-like ceramic powder by in-situ covalent grafting to modify the sheet-like ceramic powder. Step 2: Mix the modified sheet ceramic powder, sintering aid, printing adhesive and plasticizer to obtain filament raw material. Disperse the filament raw material evenly by solution dispersion and extrude the filament raw material to form printing filament. Step 3: Using a fused deposition modeling (FDM) 3D printer, the molten filament is melted and printed onto the surface of the part to obtain a preliminary blank. During the molten printing process, the molten filament is rolled to orient the sheet-like ceramic material within the molten filament along the rolling direction; specifically including: Step 3.1: Use a laser beam as a heating source, so that half of the laser beam acts on the printing filament until the printing filament is in a semi-molten state; the other half of the laser beam acts on the surface of the part, and then use a fused deposition modeling 3D printing device to print the semi-molten printing filament onto the surface of the part; Step 3.2: During the process of laying the printing filament on the surface of the part, a rolling device is used to roll the semi-molten printing filament to roll it into a flat strip and make the printing filament oriented along the rolling direction to obtain a preliminary blank. Step 4: Degrease the preform to remove the ionic polymers used to assist molding, and obtain the brown body; Step 5: Sinter the brown body to densify it and form a ceramic material.

2. The method for preparing tough biomimetic structured ceramic materials for fused deposition 3D printing according to claim 1, characterized in that, Step 1 specifically includes: Step 1.1: A condensation reaction is carried out between a silane coupling agent and the hydroxyl groups on the surface of the sheet-like ceramic powder, so that the silane coupling agent is grafted onto the surface of the sheet-like ceramic powder. Step 1.2: Add the sheet-like ceramic powder to the uniformly dispersed graphene oxide solution to graft the graphene oxide onto the surface of the sheet-like ceramic powder. Step 1.3: React the sheet-like ceramic powder with a silane coupling agent to introduce vinyl groups onto the surface of the sheet-like ceramic powder, thereby grafting bivalent bonds onto the surface of the sheet-like ceramic powder; Step 1.4: Add the sheet-like ceramic powder grafted with bicovalent bonds to a solution containing ionic polymer monomers for free radical copolymerization; Step 1.5: Reduce the graphene oxide on the surface of the sheet ceramic powder to graphene, and dissociate the sheet ceramic powder in an acidic or alkaline environment to form a polyelectrolyte with positive or negative charge on the surface of the sheet ceramic powder, thereby completing the modification of the sheet ceramic powder.

3. The method for preparing tough biomimetic structural ceramic materials for fused deposition modeling (FDM) 3D printing according to claim 2, characterized in that, Step 2 specifically includes: Step 2.1: Dissolve the printing adhesive using an organic solvent; Step 2.2: Mix the modified flake ceramic powder, sintering aid, printing adhesive, and plasticizer to obtain a raw material solution, and then ultrasonically disperse the raw material solution; Step 2.3: Filter, dry, and pulverize the dispersed raw material solution to obtain the silk raw material, and then perform internal mixing on the silk raw material; Step 2.4: Use a screw extruder to extrude the mixed filament material to prepare printing filament.

4. The method for preparing tough biomimetic structural ceramic materials for fused deposition modeling (FDM) 3D printing according to claim 3, characterized in that, The volume fraction of the flake ceramic powder in the raw material solution is 10 vol%-70 vol, and the ratio of the sintering aid, printing adhesive, and plasticizer is 2:1:1; the thickness of the flake ceramic powder is 10 nm-1000 nm, the width is 5 μm-100 μm, and the length is 5 μm-100 μm.

5. The method for preparing tough biomimetic structural ceramic materials for fused deposition modeling (FDM) 3D printing according to claim 4, characterized in that, The volume fraction of the flake-shaped ceramic powder in the raw material solution is 50 vol.

6. The method for preparing tough biomimetic structural ceramic materials for fused deposition modeling (FDM) 3D printing according to claim 5, characterized in that, The printing adhesive includes any one monomer or a mixture of any two of polyethylene, polyvinyl acetate, polyethylene glycol, and polyethylene oxide.

7. The method for preparing tough biomimetic structural ceramic materials for fused deposition modeling (FDM) 3D printing according to any one of claims 1-6, characterized in that, Step 4 specifically includes: Step 4.1: Place the initial blank in the air and fire it for a time of 2 hours or more. The heating rate during the firing process is 0.5℃ / min, and the final firing temperature is 600℃ or more. Step 4.2: Continue heating at a rate of 2℃ / min until the firing temperature is greater than or equal to 1000℃ and the firing time is greater than or equal to 2h.

8. The method for preparing tough biomimetic structural ceramic materials for fused deposition modeling (FDM) 3D printing according to claim 7, characterized in that, In step 5, the temperature continues to rise at a rate of 4℃ / min until the sintering temperature is greater than or equal to 1600℃ and the sintering time is greater than or equal to 2h.

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