Enamel-imitated structure and component zirconia-based composite material and preparation method thereof

Abstract

The invention discloses a zirconia-based composite material imitating enamel structure and composition, and relates to the technical field of amorphous ceramic nanotube array / organic polymer composites.The preparation method comprises the following steps that 1, ammonium fluoride, glycerol and formamide are sequentially added into deionized water to prepare an electrolyte; (2) a zirconium sheet is soaked in the electrolyte for three-step anodic oxidation, and an amorphous zirconium oxide nanotube array is obtained; and (3) soaking the amorphous zirconia nanotube array in a PMMA (polymethyl methacrylate) solution, drying, dropwise adding the PMMA solution, and performing vacuum drying to obtain the zirconia-based composite material with the enamel-imitating structure and components. The preparation method is convenient to operate, mild in reaction condition, environmentally friendly and suitable for large-scale actual production, the composite material has the excellent performance of high rigidity and high hardness, the microstructure can be precisely regulated and controlled, and an innovative material technical scheme with practicability and reliability is provided for actual engineering application.

Description

Technical Field

[0001] This invention relates to the field of amorphous ceramic nanotube array / organic polymer composite materials technology, specifically to a zirconia-based composite material with a tooth enamel-like structure and composition and its preparation method. Background Technology

[0002] In nature, many biomaterials exhibit exceptional properties thanks to their intricate microstructures. Among them, the layered structure of seashells combines hardness and toughness, the molecular arrangement of spider silk achieves a balance between high strength and ductility, and tooth enamel, as the hardest tissue in the human body, is mainly composed of hydroxyapatite crystals. These crystals are distributed in a vertically ordered prismatic shape, connected by a small amount of organic matrix, forming a composite structure of "rigid framework-flexible interface," which endows it with high compressive strength and excellent wear resistance.

[0003] Currently, some research teams are simulating prism structures by controlling the oriented growth of inorganic nanoparticles, or by using organic-inorganic interfaces to modify and replicate the composite mechanism of enamels. Although the biomimetic materials prepared have certain mechanical properties, there are still many bottlenecks in the preparation technology. For example, the directional arrangement of nanocrystals is difficult to control precisely; the interfacial bonding force between the organic matrix and the inorganic phase is insufficient; most preparation processes rely on high-temperature sintering or complex template assistance, which consumes a lot of energy and makes it difficult to achieve the forming of large-area, complex-shaped materials, thus limiting their practical applications.

[0004] Therefore, based on the above analysis, the preparation of high-strength and high-rigidity dental enamel structural materials is of great significance. How to provide a lightweight, high-strength composite material with a dental enamel structure and composition that combines ordered and controllable microstructure, good interfacial bonding, mild experimental conditions, simple and easy experimental operation, and short preparation cycle has become a key problem that urgently needs to be solved by those skilled in the art. Summary of the Invention

[0005] To address the aforementioned issues, this invention provides a zirconia-based composite material with a tooth enamel-like structure and composition, and its preparation method. The preparation method of this high-performance composite material is convenient to operate, has mild reaction conditions, is environmentally friendly, and is suitable for large-scale practical production. Furthermore, the composite material possesses excellent properties of both high stiffness and high hardness, and its microstructure can be precisely controlled, providing an innovative material technology solution that combines practicality and reliability for practical engineering applications.

[0006] To achieve the above objectives, the present invention adopts the following technical solution:

[0007] A method for preparing a zirconia-based composite material with a tooth enamel-like structure and composition includes the following steps:

[0008] (1) Add ammonium fluoride, glycerol and formamide to deionized water in sequence to prepare an electrolyte;

[0009] (2) The zirconium sheet is immersed in the electrolyte and subjected to three-step anodizing to obtain an amorphous zirconium oxide nanotube array; wherein, the three-step anodizing is specifically as follows: firstly, the zirconium sheet is subjected to a first constant voltage anodizing using a DC power supply, then subjected to a second constant voltage anodizing by ultrasonic cleaning with hydrochloric acid, then subjected to a third constant voltage anodizing by power-off and power-on, and then the zirconium sheet is removed and subjected to ultrasonic cleaning in ethanol to remove the protective layer, thereby obtaining an amorphous zirconium oxide nanotube array A-ZNT with neat tube tops;

[0010] (3) The amorphous zirconia nanotube array A-ZNT attached to the zirconium sheet is immersed in PMMA solution and dried. Then, PMMA solution is added dropwise and vacuum dried. The composite A-ZNT / PMMA is peeled off from the zirconium sheet to obtain a zirconia-based composite material with a tooth enamel structure and composition.

[0011] Preferably, in step (1), the mass percentage of ammonium fluoride in the electrolyte is 0.5-2%, the mass percentage of deionized water is 2-6%, and the volume ratio of glycerol to formamide is 7:3.

[0012] Preferably, the zirconium sheet in step (2) has a purity of 0.995-0.998 and a thickness of 0.1-0.3 mm.

[0013] Preferably, the time for the first constant voltage anodizing in step (2) is 0.5 h, the time for the second constant voltage anodizing is 1-3 h, and the time for the third constant voltage anodizing is 3 h.

[0014] Preferably, the ultrasonic cleaning with dilute hydrochloric acid in step (2) specifically involves ultrasonically cleaning the zirconium sheet with 0.5M dilute hydrochloric acid for 10-15 minutes, followed by cleaning with deionized water and ethanol, and then drying it. The power-off time is 8-12 minutes, and the ultrasonic cleaning time of the zirconium sheet in ethanol is 30-60 minutes.

[0015] Preferably, the voltage for the three-step anodizing process in step (2) is 30-60V.

[0016] Preferably, the outer diameter of the amorphous zirconia nanotube array in step (2) is 40-100 nm and the length is 10-50 μm.

[0017] Preferably, the concentration of the PMMA solution in step (3) is 1-5 wt%, the solvent is N,N-dimethylformamide, and the soaking time is 1-5 h.

[0018] Preferably, the PMMA solution in step (3) is added dropwise in batches, with each drop containing 10-30 μL of the PMMA solution; the thickness of the zirconia-based composite material of the dental enamel structure and composition is 15-60 μm; and the vacuum drying conditions are: drying in a drying oven at 50-60°C and a vacuum of -0.1 MPa for 8-12 minutes.

[0019] A zirconia-based composite material with a dental enamel structure and composition obtained by the preparation method described above.

[0020] Compared with the prior art, the present invention has the following beneficial effects:

[0021] (1) This invention mimics the structural characteristics of natural tooth enamel by using a three-step anodizing method to prepare an amorphous ceramic nanotube array. Organic polymer PMMA is injected between / inside the array tubes by vacuum perfusion method to mimic the protein matrix reinforcing components in the enamel column gaps of the tooth enamel structure.

[0022] (2) The present invention uses a three-step anodizing method, using the nanotubes grown in the second step of anodizing as a protective layer to effectively protect the final nanotube array required in the third step of anodizing, and can effectively maintain the orderly arrangement and complete columnar structure of the zirconium oxide nanotube array.

[0023] (3) This invention addresses the characteristics of tooth enamel components by adjusting the interlocking of inorganic and organic phases and enhancing the mechanical properties of the tooth enamel-like composite material through interfacial strengthening. Nanoindentation testing revealed a Young's modulus of approximately 68.9 GPa and a hardness close to 3.90 GPa. Tensile testing showed a fracture strength of approximately 14.87 MPa and a fracture energy of 144.7 J / m. 3 It possesses multiple properties and has significant application potential in fields such as aerospace and biomedicine;

[0024] (4) The preparation method of the present invention uses inexpensive materials, is easy to operate, has mild reaction conditions, and is highly efficient, making it easy to prepare on a large scale. Attached Figure Description

[0025] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. The drawings in this description are merely embodiments of the present invention.

[0026] Figure 1 SEM images of the tooth-like enamel structure and composition of the zirconia-based composite materials prepared in Examples 1-4;

[0027] Figure 2 The image shows the SEM image of the zirconia-based composite material with the dental enamel structure and composition prepared in Example 1 after being subjected to external shear force.

[0028] Figure 3 SEM image of the amorphous zirconia nanotube array prepared in Example 1 without ultrasonic cleaning with ethanol;

[0029] Figure 4 SEM image of the amorphous zirconia nanotube array prepared in Example 1;

[0030] Figure 5 XRD pattern of a single amorphous zirconia nanotube array prepared in Example 1;

[0031] Figure 6 The nanoindentation load-displacement curves and modulus-hardness comparison diagrams of the PMMA, amorphous zirconia nanotube array and zirconia-based composite material with tooth-like enamel structure and composition prepared in Example 1 are shown.

[0032] Figure 7 The nanoindentation load-displacement curves and modulus-hardness comparison diagrams of PMMA, amorphous zirconia nanotube arrays and zirconia-based composite materials with tooth-like enamel structure and composition prepared in Example 1 are obtained by the cyclic stiffness method.

[0033] Figure 8 The tensile stress-strain curve of the zirconia-based composite material with the dental enamel structure and composition prepared in Example 1 is shown. Detailed Implementation

[0034] Embodiments of the present invention are described below, examples of which are shown in the accompanying drawings. The embodiments described with reference to the drawings are exemplary and intended to explain the present invention, but are not to be construed as limiting the present invention.

[0035] Example 1

[0036] This invention provides a method for preparing a zirconia-based composite material with a tooth enamel-like structure and composition, specifically including the following steps:

[0037] (1) Weigh 1 wt% of ammonium fluoride and dissolve it in 4 wt% of deionized water. After the ammonium fluoride is dissolved, add 280 ml of glycerol and 120 ml of formamide in sequence, mix well and prepare the electrolyte.

[0038] (2) A 0.1 mm thick zirconium sheet (purity 0.995-0.998, size 2.5 cm × 1.0 cm) was ultrasonically cleaned with acetone, isopropanol, ethanol and deionized water to remove surface stains and grease. The sheet was then dried in a 50°C oven. The dried zirconium sheet was held vertically by electrodes and immersed in the electrolyte prepared in step (1). Anodizing was performed for 0.5 h using a DC power supply at a constant voltage (50 V). Afterwards, the sheet was ultrasonically treated with 0.5 M dilute hydrochloric acid for 15 min. The zirconium sheet, which was brightened after ultrasonication, was cleaned with deionized water and ethanol respectively. After drying, the second step of anodizing was carried out for 3 hours. After the second step, the power was turned off for 10 minutes, and then the power was turned on again for 3 hours of the third step of anodizing. After the third step, the zirconium sheet was ultrasonicated in ethanol for 45 minutes. Finally, after a total of three steps of anodizing, an amorphous zirconium oxide nanotube array was obtained. The average outer diameter of the nanotube array was 64.6 nm, the average inner diameter was 39.7 nm, and the length of the nanotube array was 27.7 μm.

[0039] (3) Weigh polymethyl methacrylate (PMMA) and dissolve it in N,N-dimethylformamide (DMF) to prepare a 5wt% PMMA solution. Immerse the amorphous zirconia nanotube array obtained in step (3) in the PMMA solution for 5 hours, and then take it out and let it dry naturally. Each time, take 20 μL of PMMA solution and drop it onto the dried amorphous zirconia nanotube array, and then put it into a vacuum drying oven at 60℃ and a vacuum degree of -0.1MPa for 8 minutes. After taking it out, drop PMMA solution again and repeat 3 times. A single-layer composite material with a thickness of 29.3 μm can be obtained by peeling it off from the zirconia sheet.

[0040] Example 2

[0041] This invention provides a method for preparing a zirconia-based composite material with a tooth enamel-like structure and composition. The difference between this embodiment and Example 1 lies in the different contents of ammonium fluoride and deionized water. Specifically, the method includes the following steps:

[0042] (1) Weigh 0.5 wt% of ammonium fluoride and dissolve it in 6 wt% deionized water. After the ammonium fluoride is dissolved, add 280 ml of glycerol and 120 ml of formamide in sequence, mix well and prepare the electrolyte.

[0043] (2) A 0.1 mm thick zirconium sheet (purity 0.995-0.998, size 2.5 cm × 1.0 cm) was ultrasonically cleaned with acetone, isopropanol, ethanol and deionized water to remove surface stains and grease. Then it was dried in an oven at 50 °C. The dried zirconium sheet was held vertically by an electrode clamp and immersed in the electrolyte prepared in step (1). The first step was anodizing with a constant voltage (50 V) for 0.5 h using a DC power supply. After that, it was ultrasonically treated with 0.5 M dilute hydrochloric acid for 15 min. The ultrasonically glossy zirconium sheet was cleaned with deionized water and ethanol respectively. After drying, the second step of anodizing was carried out for 3 hours. After the second step, the power was turned off for 10 minutes, and then the power was turned on again for 3 hours of the third step of anodizing. After the third step, the zirconium sheet was ultrasonicated in ethanol for 45 minutes. Finally, after a total of three steps of anodizing, an amorphous zirconium oxide nanotube array was obtained. The average outer diameter of the nanotube array was 47.91 nm, the average inner diameter was 24.93 nm, and the length of the nanotube array was 24.8 μm.

[0044] (3) Weigh polymethyl methacrylate (PMMA) and dissolve it in N,N-dimethylformamide (DMF) to prepare a 5wt% PMMA solution. Immerse the amorphous zirconia nanotube array obtained in step (3) in the PMMA solution for 5 hours, and then take it out and let it dry naturally. Each time, take 20 μL of PMMA solution and drop it onto the dried amorphous zirconia nanotube array, and then put it into a vacuum drying oven at 60℃ and a vacuum degree of -0.1MPa for 8 minutes. After taking it out, drop PMMA solution again and repeat 3 times. A single-layer composite material with a thickness of 27.2 μm can be obtained by peeling it off from the zirconia sheet.

[0045] Example 3

[0046] This invention provides a method for preparing a zirconia-based composite material with a tooth enamel-like structure and composition. The difference between this embodiment and Embodiment 1 lies in the anodizing time in the second step, and specifically includes the following steps:

[0047] (1) Weigh 1 wt% of ammonium fluoride and dissolve it in 4 wt% of deionized water. After the ammonium fluoride is dissolved, add 280 ml of glycerol and 120 ml of formamide in sequence, mix well and prepare the electrolyte.

[0048] (2) A 0.1 mm thick zirconium sheet (purity 0.995-0.998, size 2.5 cm × 1.0 cm) was ultrasonically cleaned with acetone, isopropanol, ethanol and deionized water to remove surface stains and grease. The sheet was then dried in a 50°C oven. The dried zirconium sheet was held vertically by electrodes and immersed in the electrolyte prepared in step (1). Anodizing was performed for 0.5 h using a DC power supply at a constant voltage (50 V). Afterwards, the sheet was ultrasonically treated with 0.5 M dilute hydrochloric acid for 15 min. The zirconium sheet, which was brightened after ultrasonication, was cleaned with deionized water and ethanol respectively. After drying, the second step of anodizing was carried out for 2 hours. After the second step, the power was turned off for 10 minutes, and then the power was turned on again for 3 hours of the third step of anodizing. After the third step, the zirconium sheet was ultrasonicated in ethanol for 45 minutes. Finally, after a total of three steps of anodizing, an amorphous zirconium oxide nanotube array was obtained. The average outer diameter of the nanotube array was 67.4 nm, the average inner diameter was 41.0 nm, and the length of the nanotube array was 20.6 μm.

[0049] (3) Weigh polymethyl methacrylate (PMMA) and dissolve it in N,N-dimethylformamide (DMF) to prepare a 5wt% PMMA solution. Immerse the amorphous zirconia nanotube array obtained in step (3) in the PMMA solution for 5 hours, and then take it out and let it dry naturally. Each time, take 20 μL of PMMA solution and drop it onto the dried amorphous zirconia nanotube array, and then put it into a vacuum drying oven at 60℃ and a vacuum degree of -0.1MPa for 8 minutes. After taking it out, drop PMMA solution again and repeat 3 times. A single-layer composite material with a thickness of 22.6 μm can be obtained by peeling it off from the zirconia sheet.

[0050] Example 4

[0051] This invention provides a method for preparing a zirconia-based composite material with a tooth enamel-like structure and composition. The difference between this embodiment and Example 1 lies in the number of times the PMMA solution is repeatedly added. Specifically, the method includes the following steps:

[0052] (1) Weigh 1 wt% of ammonium fluoride and dissolve it in 4 wt% of deionized water. After the ammonium fluoride is dissolved, add 280 ml of glycerol and 120 ml of formamide in sequence, mix well and prepare the electrolyte.

[0053] (2) A 0.1 mm thick zirconium sheet (purity 0.995-0.998, size 2.5 cm × 1.0 cm) was ultrasonically cleaned with acetone, isopropanol, ethanol and deionized water to remove surface stains and grease. The sheet was then dried in a 50°C oven. The dried zirconium sheet was held vertically by electrodes and immersed in the electrolyte prepared in step (1). Anodizing was performed for 0.5 h using a DC power supply at a constant voltage (50 V). Afterwards, the sheet was ultrasonically treated with 0.5 M dilute hydrochloric acid for 15 min. The zirconium sheet, which was brightened after ultrasonication, was cleaned with deionized water and ethanol respectively. After drying, the second step of anodizing was carried out for 3 hours. After the second step, the power was turned off for 10 minutes, and then the power was turned on again for 3 hours of the third step of anodizing. After the third step, the zirconium sheet was ultrasonicated in ethanol for 45 minutes. Finally, after a total of three steps of anodizing, an amorphous zirconium oxide nanotube array was obtained. The average outer diameter of the nanotube array was 66.9 nm, the average inner diameter was 37.4 nm, and the length of the nanotube array was 28.7 μm.

[0054] (3) Weigh polymethyl methacrylate (PMMA) and dissolve it in N,N-dimethylformamide (DMF) to prepare a 5wt% PMMA solution. Immerse the amorphous zirconia nanotube array obtained in step (3) in the PMMA solution for 5 hours, and then take it out and let it dry naturally. Each time, take 20 μL of PMMA solution and drop it onto the dried amorphous zirconia nanotube array, and then put it into a vacuum drying oven at 60℃ and a vacuum degree of -0.1MPa for 8 minutes. After taking it out, drop PMMA solution again and repeat 8 times. A single-layer composite material with a thickness of 52.1 μm can be obtained by peeling it off from the zirconia sheet.

[0055] The characterization of the zirconia-based composite materials with tooth-like enamel structure and composition prepared in Examples 1-4 is as follows:

[0056] Figure 1 The figures show cross-sectional views of the zirconia-based composite materials prepared in Examples 1-4, characterized by field emission scanning electron microscopy, where A corresponds to Example 1, B to Example 2, C to Example 3, and D to Example 4. As can be seen from the figures, the cross-sectional views of different examples can reflect the microscopic columnar structure characteristics of the composite enamel prepared in the composite materials.

[0057] Figure 2The images show cross-sectional views of the zirconia-based composite material prepared in Example 1, characterized by field emission scanning electron microscopy, after being subjected to external shear force. A clearly shows PMMA being infused into the A-ZNT nanotubes, and B clearly shows PMMA adhering to the wall of the A-ZNT nanotubes. This indicates that PMMA effectively fills the inside and interstitial spaces of the A-ZNT nanotubes. By combining the inorganic ceramic zirconia nanotubes with the organic polymer polymethyl methacrylate, the characteristics of the interleaved distribution of inorganic and organic phases in tooth enamel are successfully imitated.

[0058] Figure 3 The images show field emission scanning electron microscope (FESEM) images of individual zirconia nanotube arrays prepared by the three-step anodic oxidation method in Example 1 without ultrasonic cleaning with ethanol. A and B show the state of the top and cross-section of the nanotube array, respectively. It can be clearly seen from the images that the top exhibits nanotube collapse, while the cross-section shows discontinuity caused by power-off operation. This morphology of the nanotube array is not conducive to polymer filling.

[0059] Meanwhile, the present invention prepares a zirconium nanotube array through a three-step anodizing method. The first step is based on the template method to obtain a uniform template on the zirconium substrate. Then, the second step is anodizing. However, the nanotube array prepared by only these two steps of anodizing has a top collapse phenomenon, which is not conducive to polymer filling. Therefore, a three-step anodizing method is adopted. The nanotube array grown by the second step of anodizing is removed by ultrasonic cleaning with ethanol. Finally, PMMA vacuum infusion is performed on the array based on the third step of anodizing. This morphology is more conducive to filling and composite.

[0060] Figure 4 The images shown are field emission scanning electron microscope images of the individual zirconia nanotube arrays prepared by the three-step anodic oxidation method in Example 1. A and B show the orderly arrangement of the top and bottom of the nanotube arrays, respectively. C is a tubular cross-section, indicating that the synthesized zirconia nanotube arrays are unidirectionally open and have morphological characteristics similar to the columnar array structure of tooth enamel.

[0061] Figure 5 The X-ray diffraction pattern of the zirconia nanotubes prepared by the three-step anodic oxidation method in Example 1 shows a relatively obvious bulge in the range of diffraction angle 2θ = 30°, which indicates that the zirconia nanotubes are amorphous materials.

[0062] Figure 6The quasi-static nanoindentation test results are shown for polymethyl methacrylate (PMMA) with a thickness of 20-22 μm, amorphous zirconia nanotubes (A-ZNT) with a thickness of 25-28 μm, and the zirconia-based composite material (A-ZNT / PMMA) with the dental enamel-like structure and composition of Example 1. A function mode of loading for 5 s, holding for 2 s, and unloading for 5 s is used, targeting PMMA (… Figure 6 In A), the peak force is set at 1000 μN, while A-ZNT ( Figure 6 B) and A-ZNT / PMMA ( Figure 4 In C), a peak force of 10000 μN was set. Figure 6 The D in the figure shows the Young's modulus and hardness results of the material measured under this function mode. The Young's modulus and hardness of PMMA are approximately 3.42 GPa and 0.21 GPa, respectively. The Young's modulus and hardness of A-ZNT are approximately 51.5 GPa and 3.30 GPa, respectively. The Young's modulus and hardness of A-ZNT / PMMA are approximately 68.9 GPa and 3.90 GPa, respectively. Compared with PMMA and A-ZNT, they are significantly improved, indicating that they have high stiffness and high hardness and excellent resistance to deformation.

[0063] Figure 7 The image shows the quasi-static nanoindentation test results of polymethyl methacrylate (PMMA), amorphous zirconia nanotubes (A-ZNT), and a zirconia-based composite material with a dental enamel-like structure and composition (A-ZNT / PMMA) using the cyclic stiffness method. The function mode underwent 20 loading and unloading cycles, yielding Young's modulus and hardness at 20 different contact depths. Similarly, for PMMA... Figure 7 In A), the maximum peak force is set to 1000 μN, while A-ZNT ( Figure 7 B) and A-ZNT / PMMA ( Figure 7 In C), a maximum peak force of 10000 μN was set for all components. The average Young's modulus and hardness of PMMA are approximately 4.34 GPa and 0.27 GPa, respectively; the average Young's modulus and hardness of A-ZNT are approximately 59.8 GPa and 3.78 GPa, respectively; and the average Young's modulus and hardness of A-ZNT / PMMA are approximately 70.5 GPa and 3.33 GPa, respectively. Figure 7 As can be seen from E in the figure, the Young's modulus of A-ZNT decreases more significantly with increasing contact depth compared to the other two materials, while the Young's modulus and hardness of PMMA and A-ZNT / PMMA change more steadily with contact depth, indicating that the prepared zirconia-based dental enamel composite material has good mechanical stability.

[0064] Figure 8The figure shows the tensile test results of the zirconia-based composite material with the simulated tooth enamel structure and composition prepared in Example 1, which was tested using a universal testing machine. As can be seen from the stress-strain curve, the fracture strength of the material is 14.87 MPa and the fracture strain is 1.39%, indicating that the material has reliable strength and toughness.

[0065] The above embodiments are only used to illustrate the technical solutions of the present invention, and are not intended to limit it. Although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that modifications can still be made to the technical solutions described in the foregoing embodiments, or equivalent substitutions can be made to some of the technical features. Such modifications or substitutions do not cause the essence of the corresponding technical solutions to deviate from the spirit and scope of the technical solutions of the embodiments of the present invention.

Claims

1. A method for preparing a zirconia-based composite material with a structure and composition similar to tooth enamel, characterized in that, Includes the following steps: (1) Add ammonium fluoride, glycerol and formamide to deionized water in sequence to prepare an electrolyte; (2) The zirconium sheet is immersed in the electrolyte and subjected to three-step anodizing to obtain an amorphous zirconium oxide nanotube array; wherein, the three-step anodizing is specifically as follows: firstly, the zirconium sheet is subjected to a first constant voltage anodizing using a DC power supply, then subjected to a second constant voltage anodizing by ultrasonic cleaning with hydrochloric acid, then subjected to a third constant voltage anodizing by disconnecting and reconnecting the power, and then the zirconium sheet is removed and subjected to ultrasonic cleaning in ethanol to remove the protective layer, thereby obtaining an amorphous zirconium oxide nanotube array A-ZNT with neat tube tops; (3) The amorphous zirconia nanotube array A-ZNT attached to the zirconium sheet is immersed in PMMA solution and dried. Then, PMMA solution is added dropwise and vacuum dried. The composite A-ZNT / PMMA is peeled off from the zirconium sheet to obtain a zirconia-based composite material with a tooth enamel structure and composition.

2. The method for preparing a zirconia-based composite material with a tooth-enamel-like structure and composition according to claim 1, characterized in that, In step (1), the mass percentage of ammonium fluoride in the electrolyte is 0.5-2%, the mass percentage of deionized water is 2-6%, and the volume ratio of glycerol to formamide is 7:

3.

3. The method for preparing a zirconia-based composite material with a tooth-enamel-like structure and composition according to claim 1, characterized in that, The zirconium sheet mentioned in step (2) has a purity of 0.995-0.998 and a thickness of 0.1-0.3 mm.

4. The method for preparing a zirconia-based composite material with a tooth-enamel-like structure and composition according to claim 1, characterized in that, The time for the first constant voltage anodizing in step (2) is 0.5h, the time for the second constant voltage anodizing is 1-3h, and the time for the third constant voltage anodizing is 3h.

5. The method for preparing a zirconia-based composite material with a tooth-enamel-like structure and composition according to claim 1, characterized in that, The dilute hydrochloric acid ultrasonic cleaning in step (2) specifically involves ultrasonically cleaning the zirconium sheet with 0.5M dilute hydrochloric acid for 10-15 minutes, followed by cleaning with deionized water and ethanol, and then drying. The power-off time is 8-12 minutes, and the ultrasonic time of the zirconium sheet in ethanol is 30-60 minutes.

6. The method for preparing a zirconia-based composite material with a tooth-enamel-like structure and composition according to claim 1, characterized in that, The voltage for the three-step anodizing process in step (2) is 30-60V.

7. The method for preparing a zirconia-based composite material with a tooth-enamel-like structure and composition according to claim 1, characterized in that, The amorphous zirconia nanotube array described in step (2) has an outer diameter of 40-100 nm and a length of 10-50 μm.

8. The method for preparing a zirconia-based composite material with a tooth-enamel-like structure and composition according to claim 1, characterized in that, The concentration of the PMMA solution in step (3) is 1-5 wt%, the solvent is N,N-dimethylformamide, and the soaking time is 1-5 h.

9. The method for preparing a zirconia-based composite material with a tooth-enamel-like structure and composition according to claim 1, characterized in that, The PMMA solution in step (3) is added dropwise in batches, with each drop containing 10-30 μL of the PMMA solution; the thickness of the zirconia-based composite material of the dental enamel structure and composition is 15-60 μm; the vacuum drying conditions are: drying in a drying oven at 50-60℃ and a vacuum of -0.1 MPa for 8-12 min.

10. A zirconia-based composite material with a dental enamel structure and composition obtained by the preparation method according to any one of claims 1-9.

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