Preparation method of three-dimensional porous white phosphorus calcium stone ceramic scaffold with piezoelectric biological activity

Abstract

The invention discloses a preparation method of a three-dimensional porous white phosphorus calcium stone ceramic bracket with piezoelectric biological activity, and belongs to the field of brackets. The preparation method of the scaffold comprises the following steps: uniformly dipping a polymer foam template with a certain pore size and porosity in slurry composed of beta-tricalcium phosphate and a binder, carrying out high-temperature sintering to remove organic matters, carrying out a hydrothermal reaction on the inorganic scaffold in an aqueous solution containing magnesium ions, converting beta-tricalcium phosphate into white calcomanite, and carrying out drying to obtain the scaffold. And then carrying out high-temperature annealing treatment to obtain the white calcomanite porous ceramic bracket with piezoelectric biological activity. The prepared ceramic scaffold is controllable in composition and degradation rate, excellent in mechanical property, electroactive, free of cytotoxicity and remarkable in osteogenesis induction effect, and the porosity and aperture of the scaffold are suitable for cells to enter and grow. The preparation method of the white phosphorite three-dimensional piezoelectric ceramic bracket is simple and easy to implement, controllable in process and easy to amplify.

Description

Technical Field

[0001] The present invention relates to a method for preparing a three-dimensional porous ceramic scaffold, and in particular to a preparation technology of a piezoelectric bioactive ceramic scaffold for bone tissue engineering, which can be used for regeneration and repair of bone defects. Background Art

[0002] Bone tissue is widely present in the human body and plays important physiological functions such as supporting the body, transporting nutrients and hematopoiesis. It is composed of inorganic minerals and organic matter, with the inorganic mineral content as high as 60-70%. Although vascularized bone has strong physiological remodeling and self-healing ability, when the defect size exceeds the critical value for self-healing, it needs to be intervened by bone transplantation or tissue engineering. In view of the various limitations and disadvantages of autologous and allogeneic bone transplantation, it is of great significance to prepare bone filling scaffolds through bone tissue engineering and realize bone regeneration and repair through the osteoconduction and osteoinduction effects of the scaffolds.

[0003] From the perspective of materials science, it is generally believed that bones are composed of collagen nanofibers and non-chemically dosed nanohydroxyapatite (HA: Ca 10 In recent years, researchers have gained further understanding of white phosphate, a magnesium-containing calcium phosphate (WH:Ca 18 Mg2(HPO4)2(PO4) 12 ). Although leucasite is a relatively rare mineral in nature, it is the second most abundant mineral in human bones, accounting for about 20% of the bone weight, especially in bones with high dynamic loads, because magnesium has been shown to be a bioactive element that can promote multiple biological functions such as cell recruitment, proliferation, angiogenesis, and osteogenesis. The results of a study comparing organic-inorganic composite scaffolds with the addition of leucasite, hydroxyapatite, or β-tricalcium phosphate showed that the in vitro osteogenic differentiation behavior of leucasite composite scaffolds was enhanced compared with hydroxyapatite composite scaffolds, and the leucasite composite scaffolds had the best bone regeneration effect in vivo compared with hydroxyapatite and β-tricalcium phosphate composite scaffolds, and the bioabsorbability was better than that of hydroxyapatite. Therefore, the preparation of ceramic scaffolds based on leucasite is undoubtedly an inorganic bone repair material with excellent bioactivity.

[0004] Existing studies have found that the non-centrosymmetry of collagen molecules is the main cause of bioelectricity (such as piezoelectricity, pyroelectricity, and ferroelectricity) in living bones, and the bioelectric effect of bones is a key factor in regulating metabolic activities (such as bone growth, structural remodeling, and fracture healing). During physical activities such as walking, stretching, and climbing, collagen fibers undergo various movements, such as rotation and sliding. Therefore, bones are compressed or tensile, and the resulting endogenous electric field helps control cell metabolism, such as proliferation and differentiation. Piezoelectric ceramics / polymers can generate surface charges when external stress is applied. It is reported that polarized piezoelectric materials can improve bone regeneration efficiency. This is because scaffolds with piezoelectric effects are implanted in bone defects, and the stress generated by physiological loads generates electrical stimulation, which biomimetic reconstructs the electric field microenvironment of natural bones. Therefore, compared with scaffolds without piezoelectric properties, biocompatible scaffolds with piezoelectric properties can promote early repair and later functional reconstruction of damaged bone tissue more quickly. Piezoelectric bioceramics mainly include barium titanate, potassium sodium niobate, zinc oxide, boron nitride, hydroxyapatite, etc., and piezoelectric polymers mainly include polyvinylidene fluoride (PVDF), poly L-lactic acid (PLLA), polyhydroxybutyrate (PHB), etc. Hydroxyapatite, which has a crystal structure similar to inorganic materials of bones and teeth, is often used as a bone filling material. However, clinical studies have reported that synthetic hydroxyapatite not only degrades and absorbs very slowly, mainly manifesting as space-occupying repair, lacks bone induction activity, but also has very weak piezoelectric properties (piezoelectric coefficient is 8pm / V), and usually needs to be polarized at high temperature and high voltage (at 300℃, 1kV / cm DC electric field). Therefore, the hydroxyapatite bone filling materials currently used in clinical applications do not have significant piezoelectric activity. Due to the doping of magnesium ions, white calcium apatite nanoparticles will undergo domain transformation after annealing and polarization due to their non-centrosymmetric structure, thus showing piezoelectric properties and being bioabsorbable. In vitro cell proliferation and osteogenic differentiation studies showed that the piezoelectric whirlpoolite nanoparticles exhibited enhanced cellular behavior compared with unannealed whirlpoolite nanoparticles.

[0005] Three-dimensional porous structures play a vital role in tissue engineering by providing a supportive environment that can accommodate repair cells and growth factors, both of which are crucial for tissue regeneration. Traditional techniques for developing porous scaffolds include gaseous or chemical foams, template methods, freeze drying (lyophilization), solvent evaporation / particle leaching, phase separation, and 3D printing.

[0006] However, the current research reports on piezoelectric whicrastone are very limited, and are prepared in the form of nanoparticles and composited with other bioceramics or biopolymers to prepare scaffolds for bone tissue engineering. Therefore, it is necessary to develop a suitable method to prepare porous ceramic scaffolds containing whicrastone with piezoelectric properties, which can be used as a new type of bone filling material to improve the regeneration and repair efficiency of vascularized bone. Summary of the invention

[0007] The purpose of the present invention is to provide a preparation technology of a porous white calcium phosphate ceramic scaffold with piezoelectric activity for bone tissue engineering, which is based on the fact that the non-centrosymmetric structure of white calcium phosphate can generate piezoelectricity. The principle is to utilize the crystal similarity between β-tricalcium phosphate and white calcium phosphate, and soak the porous β-tricalcium phosphate ceramic scaffold in a Mg-containing 2+ In a simulated body fluid, β-tricalcium phosphate is converted into whilapite under hydrothermal conditions to prepare a whilapite ceramic scaffold, and then the whilapite ceramic scaffold is converted into a whilapite ceramic scaffold with piezoelectric effect by annealing. In this preparation technology, a mixed slurry is prepared from the simple and easily available β-tricalcium phosphate, and an organic polymer foam is used as a scaffold template. The preparation of the target whilapite piezoelectric ceramic scaffold is completed through the steps of impregnation, high-temperature sintering, hydrothermal treatment, annealing, etc. The process is controllable, easy to scale up, and electrically active, so it can promote the early repair of damaged bone tissue and achieve structural and functional reconstruction.

[0008] A method for preparing a porous white calcium phosphate ceramic support having piezoelectric activity comprises the following steps:

[0009] (1) polymer foam template impregnation molding: using an ethanol solution of a hydrophilic polymer substance as a dispersion liquid, the concentration of the dispersion liquid is 0.4-0.8 g / mL, and mixing it with β-tricalcium phosphate powder at a solid-liquid ratio of 1 g: 3 mL-1 g: 5 mL, and then ball milling it with a planetary ball mill to obtain a slurry with dispersed particles and uniform mixing, and then immersing the organic polymer foam template in the slurry, and repeating the vacuum impregnation-centrifugation-drying operation for 3-5 times until the pore wall thickness reaches 50-200 μm, and drying it in a vacuum oven at 80°C for 48 hours to obtain a porous scaffold with a hydrophilic polymer as a binder and an organic polymer foam template as a molding;

[0010] (2) placing the porous scaffold prepared in step (1) in a muffle furnace, heating the temperature to 800-1100° C. at a heating rate of 3-5° C. / min, and maintaining the temperature for 3 h to obtain a β-tricalcium phosphate inorganic ceramic scaffold;

[0011] (3) placing the β-tricalcium phosphate inorganic ceramic scaffold prepared in step (2) in a Mg-containing 2+ in a simulated body fluid, hydroheating at 80-140° C. until all β-tricalcium phosphate is converted into whilapite, taking out, washing with deionized water, and drying in a vacuum oven at 60° C. for 48 hours to obtain a whilapite inorganic ceramic scaffold;

[0012] (4) placing the white calcium phosphate inorganic ceramic support prepared in step (3) in a muffle furnace, heating the temperature to 550-700°C at a heating rate of 3-5°C / min, and keeping the temperature at this temperature for 1-5h, and cooling the temperature to room temperature at a cooling rate of 3-5°C / min for annealing to obtain a white calcium phosphate porous ceramic support with piezoelectric activity.

[0013] The organic polymer foam template in the aforementioned step (1) is an open-cell connected-pore polyurethane foam with a pore size ranging from 200 to 600 μm and a porosity greater than 80%.

[0014] In the above step (1), the polymer binder is selected from polyvinyl butyral and polyvinyl pyrrolidone.

[0015] The simulated body fluid described in the aforementioned step (3) is configured according to the standard simulated body fluid specified in ISO23317-2014 "Surgical implants. In vitro evaluation of apatite-forming ability of implant materials", wherein the magnesium ion concentration is 1.5 mmol / L.

[0016] The piezoelectrically active whitlockite porous ceramic scaffold obtained by the invention is used as a bone defect regeneration and repair material.

[0017] Beneficial effects of the present invention:

[0018] (1) The piezoelectric whiojasite porous scaffold prepared by the method of the present invention is composed of whiojasite with piezoelectricity. According to the reported research results, the bioelectricity of bones, such as piezoelectricity, pyroelectricity and ferroelectricity, is a key factor in regulating metabolic activities, such as growth, structural remodeling and fracture healing. The ceramic scaffold prepared by the present invention is composed of piezoelectric whiojasite, has significant electrical activity and good biocompatibility, and can release magnesium ions with multiple biological functions. Theoretically, compared with other calcium phosphate ceramic materials, such as hydroxyapatite and β-tricalcium phosphate, it can promote the adhesion, spreading and growth of bone marrow mesenchymal stem cells (BMSC) to the greatest extent, and can more significantly promote the expression of osteogenic differentiation-related proteins and genes, and achieve optimal vascularized bone regeneration in situ in vivo.

[0019] (2) The present invention uses organic foam to impregnate ceramic slurry, and then heat treats to remove the organic foam template after drying. This is a simple method for obtaining porous ceramics. This method of the present invention is suitable for preparing porous ceramic scaffolds for bone tissue engineering with a highly through-hole structure, high porosity, and controllable pore size. This method used in the present invention can prepare cancellous bone-like particles for filling and repairing non-load-bearing parts.

[0020] (3) In combination with the preparation method of the present invention and the characteristics of white patrolite itself, the pore structure characteristics of the organic template, the hydrothermal reaction conditions and the annealing treatment parameters can be adjusted to further regulate the pore structure, electroactivity, mechanical strength, degradation and ion dissolution rate of the piezoelectric white patrolite porous scaffold to meet the needs of different bone defect regeneration and repair.

[0021] (4) The method of the present invention is obviously simple, easy to operate, controllable, and cost-effective. It is feasible for mass production and has a wide range of applications in the field of bone regeneration and repair. BRIEF DESCRIPTION OF THE DRAWINGS

[0022] Figure 1 This is a macroscopic image of the magnesium ion-containing calcium phosphate porous ceramic support with piezoelectric activity provided by the present invention.

[0023] Figure 2 Figures a and b are micro-CT scanning three-dimensional reconstruction images and cross-sectional images of the magnesium ion-containing porous ceramic scaffold with piezoelectric activity prepared in Example 1 of the present invention, and the interconnected gaps in the ceramic scaffold can be clearly seen.

[0024] Figure 3 3 and 4. These are XRD diagrams of the electrically active white jatropha ceramic scaffold (PWH) and the electrically inactive white jatropha ceramic scaffold (WH) prepared in Examples 1 and 2 of the present invention.

[0025] Figure 4 It is an AC impedance diagram of the electrically active white jatropha ceramic scaffold prepared in Example 1 and Example 2 of the present invention and the electrically inactive white jatropha ceramic scaffold.

[0026] Figure 5 Figures a and b are live-dead staining images of BMSCs cells of the electrically active whitzpah ceramic scaffolds and the inactive whitzpah ceramic scaffolds prepared in Examples 1 and 2 of the present invention.

[0027] Figure 6 These are the cell proliferation images of the CCK-8 test of the electrically active whitzpah ceramic scaffolds, the electrically inactive whitzpah ceramic scaffolds and the β-tricalcium phosphate ceramic scaffolds prepared in Examples 1, 2 and 3 of the present invention.

[0028] Figure 7 These are alkaline phosphatase detection (ALPassay) images of the electrically active white patrolite ceramic scaffold, the electrically inactive white patrolite ceramic scaffold, and the β-tricalcium phosphate ceramic scaffold prepared in Examples 1, 2, and 3 of the present invention. DETAILED DESCRIPTION

[0029] The process and significant features of the present invention are further illustrated below in conjunction with examples, but the embodiments of the present invention are not limited thereto.

[0030] A method for preparing a magnesium ion-containing whitlockite porous ceramic support with piezoelectric activity comprises the following steps:

[0031] Preparation example:

[0032] Preparation Example 1: Preparation of simulated body fluid

[0033] The simulated body fluid was prepared according to the standard simulated body fluid formula specified in ISO 23317 2014 "Surgical implants. In vitro evaluation of the apatite-forming ability of implant materials". The drugs and amounts used to prepare 1L of solution are shown in the following table.

[0034] serial number Chemical formula Mass / g 1 NaCl 8.035 2 <![CDATA[NaHCO3]]> 0.355 3 KCl 0.225 4 <![CDATA[K2HPO4·3H2O]]> 0.231 5 <![CDATA[MgCl2·6H2O]]> 0.311 6 <![CDATA[NaSO4]]> 0.072 7 Tris 10 8 <![CDATA[CaCl2]]> 0.292

[0035] The specific operation is as follows: add 800mL of deionized water to a plastic container with a smooth inner wall, heat it to 37°C in a water bath, add drugs No. 1-6 listed in the table in turn, use a pH meter to monitor the pH of the solution in real time, and use 1mol / L hydrochloric acid solution to adjust the system pH to 7.4. It should be noted in this process that the next drug can only be added after the previous drug is completely dissolved. After all drugs No. 1-6 are added, add Tris to the solution, and at the same time use 1mol / L hydrochloric acid solution to adjust the system pH to 7.4-7.6 until all 10g of Tris is added, and then at the system pH = 7.4, add the pre-dissolved calcium chloride aqueous solution, dilute the solution to 1000mL, adjust the pH to 7.4 and set aside.

[0036] Preparation Example 2: Preparation of polyurethane foam template

[0037] A polyurethane foam of model 60PPI was selected, and a cylinder with a height of 10 mm and a diameter of 20 mm was made from it using a puncher. The cylinder was then immersed in anhydrous ethanol, and ultrasonically cleaned for 10 min × 3 times. The cylinder was then placed in a vacuum oven at 40°C and fully dried for use.

[0038] Embodiment 1:

[0039] The polyvinyl butyral was mixed with ethanol, and stirred at room temperature for more than 3 hours to fully dissolve the polymer and then prepared into a 0.6 g / mL transparent solution. 6 g of β-tricalcium phosphate powder and 25 mL of the above polyvinyl butyral ethanol solution were mixed and placed in a ball mill. The mixture was first horizontally ground for 1 hour and then rotary ground for 1 hour using a planetary ball mill to obtain a uniform and stable suspension slurry. The suspension was taken out and transferred to a beaker. The polyurethane foam template prepared in Preparation Example 2 was completely immersed in the slurry. After vacuuming until the template was completely infiltrated, the excess slurry in the template pores was removed by low-speed centrifugation (300 rpm) for 1 minute, and then dried in a vacuum oven at 80°C for 10 minutes. The vacuum impregnation-centrifugation-drying process was repeated 3 times. Finally, the impregnated composite was placed in a vacuum oven at 80°C for 4 minutes. After 8 hours, it was transferred to a muffle furnace for high-temperature sintering treatment, and the temperature was increased to 1000°C at a heating rate of 5°C / min, and maintained at this temperature for 3 hours to ensure complete removal of the organic template and the adhesive polyvinyl butyral, to obtain a porous ceramic scaffold of β-tricalcium phosphate, and then the ceramic scaffold was immersed in the simulated body fluid configured in Preparation Example 1, the solid-liquid ratio was set to 4 mg / mL, and the hydrothermal reaction was carried out at 120°C for 48 hours. After the hydrothermal autoclave naturally cooled to room temperature, the scaffold was taken out, washed with ethanol, and dried in a vacuum oven at 60°C for 48 hours to obtain a porous white calcium phosphate ceramic scaffold, and then the scaffold was placed in a muffle furnace and heated to 650°C at a heating rate of 5°C / min, and kept at this temperature for 3 hours, and cooled to room temperature at a cooling rate of 4°C / min for annealing to obtain a piezoelectric white calcium phosphate ceramic scaffold (PWH).

[0040] Embodiment 2:

[0041] Polyvinyl butyral and ethanol were mixed, stirred at room temperature for more than 3 hours to fully dissolve the polymer and then prepared into a 0.6 g / mL transparent solution. 6 g of β-tricalcium phosphate powder and 25 mL of the above-mentioned polyvinyl butyral ethanol solution were mixed and placed in a ball mill. The mixture was first horizontally ground for 1 hour and then rotary ground for 1 hour using a planetary ball mill to obtain a uniform and stable suspension slurry. The suspension slurry was taken out and transferred to a beaker. The polyurethane foam template prepared in Preparation Example 2 was completely immersed in the slurry. After vacuuming until the template was completely infiltrated, the excess slurry in the template pores was removed by low-speed centrifugation (300 rpm) for 1 minute, and then dried in a vacuum oven at 80°C for 10 minutes, and then the above process was repeated. The vacuum impregnation-centrifugation-drying process was repeated three times, and finally the impregnated composite was placed in a vacuum oven at 80°C and dried for 48 hours, and then transferred to a muffle furnace for high-temperature sintering treatment, and the temperature was raised to 1000°C at a heating rate of 5°C / min, and maintained at this temperature for 3 hours to ensure that the organic template and the adhesive polyvinyl butyral were completely removed to obtain a porous ceramic scaffold of β-tricalcium phosphate, and then the ceramic scaffold was immersed in the simulated body fluid configured in Preparation Example 1, the solid-liquid ratio was set to 4 mg / mL, and the hydrothermal reaction was carried out at 120°C for 48 hours. After the hydrothermal autoclave naturally cooled to room temperature, the scaffold was taken out, washed with ethanol, and dried in a vacuum oven at 60°C for 48 hours to obtain a porous ceramic scaffold of white calcium phosphate.

[0042] Embodiment 3:

[0043] The polyvinyl butyral was mixed with ethanol, stirred at room temperature for more than 3 hours to fully dissolve the polymer and then prepared into a 0.6 g / mL transparent solution. 6 g of β-tricalcium phosphate powder and 25 mL of the above polyvinyl butyral ethanol solution were mixed and placed in a ball mill. The mixture was first horizontally ground for 1 hour and then rotary ground for 1 hour using a planetary ball mill to obtain a uniform and stable suspension slurry. The suspension was taken out and transferred to a beaker. The polyurethane foam template prepared in Preparation Example 2 was completely immersed in the slurry. After vacuuming until the template was completely infiltrated, the suspension was centrifuged at low speed. (300rpm) for 1min to remove excess slurry in the template pores, and then dry in a vacuum oven at 80°C for 10min, then repeat the above vacuum impregnation-centrifugation-drying process 3 times, and finally place the impregnated composite in a vacuum oven at 80°C to dry for 48h, then transfer it to a muffle furnace for high-temperature sintering treatment, heating it to 1000°C at a heating rate of 5°C / min and maintaining it at this temperature for 3h to ensure complete removal of the organic template and the adhesive polyvinyl butyral, to obtain a porous ceramic scaffold of β-tricalcium phosphate.

[0044] Characterization of Piezoelectrically Active Porous Scaffolds:

[0045] Figure 1This is a macroscopic front view of the porous ceramic scaffold prepared in Example 1 of the present invention. The picture shows that the prepared scaffold is cylindrical, and its rich pore structure can be seen from the surface of the scaffold.

[0046] Figure 2 The microscopic morphology of the porous ceramic scaffold prepared in Example 1 reconstructed under micro-CT scanning can be seen that the scaffold has a continuous through pore structure, and the pore wall is a rough ceramic pore wall structure.

[0047] Figure 3 X-ray diffraction analysis diagram of the electroactive white patite ceramic support (PWH) prepared by Example 1 and Example 2 of the present invention and the white patite ceramic support (WH) without electroactivity. According to the white patite standard XRD card (PDF#70-2064), the main peak position of the diffraction spectrum of crystalline white patite is 31.03°, 34.37° and 27.77° respectively according to the peak height sorting, and the corresponding crystal planes are (02 10), (2 2 0) and (2 1 4) respectively. From the comparison of the support prepared by Example 1 and 2 in the figure with the standard spectrum, it can be confirmed that the ceramic support prepared by Example 1 and 2 is composed of white patite, and annealing has no obvious effect on its main crystal structure.

[0048] Figure 4 The AC impedance diagrams of the electrically active white calcium phosphate ceramic scaffold (PWH) and the electrically inactive white calcium phosphate ceramic scaffold (WH) prepared in Examples 1 and 2 of the present invention are obtained by evaluating the standard three-electrode system, specifically, the sample is fixed on the working platinum sheet electrode, another platinum sheet without sample is used as the counter electrode, and Ag / AgCl is used as the reference electrode to provide a potential reference. Before the test, the working electrode loaded with the sample is pre-immersed in 1M H2SO4 electrolyte for 1h to ensure that the electrolyte completely infiltrates the material. The electrochemical impedance of the sample is tested at a frequency of 0.1-0.5Hz in an electrochemical window of 0-0.9V. It can be seen that at different test frequencies, the AC impedance of the scaffold prepared in Example 1 is significantly smaller than that of the scaffold prepared in Example 2, that is, the former has a reduced charge transfer resistance, indicating that after annealing at 650°C for 3h, white calcium phosphate can indeed be given significant electrical activity.

[0049] Figure 5 From the live-dead staining images of BMSCs cells of the electroactive white patite ceramic scaffold (PWH) and the inactive white patite ceramic scaffold (WH) prepared in Examples 1 and 2 of the present invention, it can be seen that the cells in both groups proliferated significantly, the green fluorescence was obvious and of high intensity, indicating that the cells were vigorous, and almost no red fluorescence indicating dead cells was observed; the cell proliferation trends between the groups were similar, and both materials had no obvious cytotoxicity.

[0050] Figure 6 The CCK-8 test cell proliferation images of the electroactive white patite ceramic scaffold (PWH), the non-electroactive white patite ceramic scaffold (WH) and the β-tricalcium phosphate ceramic scaffold prepared in Examples 1, 2 and 3 of the present invention show that the BMSCs cells in the three groups proliferate continuously from the 1st day to the 7th day, showing good growth vitality. In general, there is no significant difference between the groups, which indicates that the dissolution of all scaffold materials is not cytotoxic, indicating that the scaffold has good biocompatibility.

[0051] Figure 7 The alkaline phosphatase assay (ALP assay) images of the electroactive white patite ceramic scaffold (PWH), the inactive white patite ceramic scaffold (WH) and the β-tricalcium phosphate ceramic scaffold prepared in Examples 1, 2 and 3 of the present invention show that the WH or PWH scaffold has higher ALP expression than the β-TCP scaffold, and the PWH scaffold group can promote the expression of ALP more than the WH scaffold group. This shows that the PWH scaffold has more significant osteogenic activity than the β-TCP scaffold and the WH scaffold.

[0052] The embodiments of the present invention are only for the convenience of those skilled in the art to understand and use the invention, and are not intended to limit the present invention. Various modifications made to the embodiments as needed by those familiar with the art after reading the specification are protected by patent law if the improvements and modifications are made without departing from the scope of the present invention.

Claims

1. A method for preparing a porous ceramic support of white calcium phosphate with piezoelectric activity, characterized in that: The steps include: (1) Polymer foam template impregnation molding: using an ethanol solution of a hydrophilic polymer as a dispersion liquid, the dispersion liquid is mixed with β-tricalcium phosphate powder, and the mixture is ball-milled by a planetary ball mill to obtain a slurry with dispersed particles and uniform mixing. The organic polymer foam template is impregnated in the slurry, and vacuum impregnation-centrifugation-drying is repeated 3-5 times until the pore wall thickness reaches 50-200 μm, and then dried to obtain a porous scaffold with a hydrophilic polymer as a binder and an organic polymer foam template as a molding; (2) placing the porous scaffold prepared in step (1) in a muffle furnace, heating the temperature to 800-1100° C. at a heating rate of 3-5° C. / min, and maintaining the temperature for 3 h to obtain a β-tricalcium phosphate inorganic ceramic scaffold; (3) placing the β-tricalcium phosphate inorganic ceramic scaffold prepared in step (2) in a Mg-containing 2+ in a simulated body fluid, hydroheating at 80-140° C. until all the β-tricalcium phosphate is converted into whilapite, then taking out, washing with deionized water, and drying to obtain a whilapite inorganic ceramic scaffold; (4) placing the white calcium phosphate inorganic ceramic support prepared in step (3) in a muffle furnace, heating the temperature to 550-700°C at a heating rate of 3-5°C / min, and keeping the temperature at this temperature for 1-5h, and cooling the temperature to room temperature at a cooling rate of 3-5°C / min for annealing to obtain a white calcium phosphate porous ceramic support with piezoelectric activity.

2. The method according to claim 1, characterized in that The concentration of the dispersion in step (1) is 0.4-0.8 g / mL, and the dispersion is mixed with β-tricalcium phosphate powder at a solid-liquid ratio of 1 g:3 mL-1 g:5 mL.

3. The method according to claim 1, characterized in that The organic polymer foam template in the aforementioned step (1) is an open-cell connected-pore polyurethane foam with a pore size ranging from 200 to 600 μm and a porosity greater than 80%.

4. The method according to claim 1, characterized in that In the above step (1), the polymer binder is selected from polyvinyl butyral and polyvinyl pyrrolidone.

5. The method according to claim 1, characterized in that The drying step (1) is performed by placing the mixture in a vacuum oven at 80°C for 48 hours, and the drying step (2) is performed by placing the mixture in a vacuum oven at 60°C for 48 hours.

6. The method according to claim 1, characterized in that The simulated body fluid described in the aforementioned step (3) is configured according to the standard simulated body fluid specified in ISO23317-2014 "Surgical implants. In vitro evaluation of apatite-forming ability of implant materials", wherein the magnesium ion concentration is 1.5 mmol / L.

7. A porous ceramic support of white jasperite having piezoelectric activity obtained by the method according to any one of claims 1 to 6.

8. Use of the porous white calcium phosphate ceramic scaffold with piezoelectric activity obtained by the method according to any one of claims 1 to 6 as a bone defect regeneration and repair material.

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