阅读说明：本技术 一种sic增强羟基磷灰石复合纳米陶瓷材料及其制备方法 (SIC (SIC-reinforced hydroxyapatite) composite nano ceramic material and preparation method thereof ) 是由 王威 冯慧慧 兰清泉 于 2019-02-21 设计创作，主要内容包括：本申请涉及一种SIC增强羟基磷灰石复合纳米陶瓷材料及其制备方法。本发明首次利用溶液喷纺技术制备得到了在气孔率、比表面积、生物活性和机械强度等方面的综合性能得以改善的SIC增强羟基磷灰石复合纳米陶瓷材料,其抗弯强度高、断裂韧性强、抗压强度高,是一种有效的增韧补强材料。相较于现有技术,抗弯强度和断裂韧性大大提高,复合陶瓷材料的抗弯强度为470～600MPa,断裂韧性为4.5～6.0MPam<Sup>1/2</Sup>。其生物相容性和力学性能优良,可作为强承载力的骨替换材料,以满足骨科临床对骨材料生物学性能和力学性能的要求,用于骨组织工程或作为生物体骨替换材料或生物支架材料,功能多样,便于大批量生产,具有良好的应用前景。(The application relates to a SIC reinforced hydroxyapatite composite nano ceramic material and a preparation method thereof. The invention firstly utilizes the solution jet spinning technology to prepare the SIC reinforced hydroxyapatite composite nano ceramic material with improved comprehensive properties in the aspects of porosity, specific surface area, bioactivity, mechanical strength and the like, has high bending strength, strong fracture toughness and high compressive strength, and is an effective toughening and reinforcing material. Compared with the prior art, the bending strength and the fracture toughness are greatly improved, the bending strength of the composite ceramic material is 470-600 MPa, and the fracture toughness is 4.5-6.0 MPam 1/2 . It has excellent biocompatibility and mechanical property, can be used as bone replacement material with strong bearing capacity,the composite material meets the requirements of orthopedics clinic on the biological performance and the mechanical performance of bone materials, is used for bone tissue engineering or used as an organism bone replacement material or a biological scaffold material, has various functions, is convenient for mass production, and has good application prospect.)

1. A SIC enhanced hydroxyapatite composite nano ceramic material prepared by adopting a solution jet spinning technology under high-pressure airflow is characterized in that: the composite ceramic material is (NH)₄)₂HPO₄Solution, Ca (NO)₃)₂Mixing the solution, ammonia water solution and polyethylene glycol as raw materials, reacting, adding SIC nano powder and polyethylene glycol, magnetically stirring to obtain precursor solution, pumping the precursor solution through a gun mouth of a solution spinning device, and simultaneously spraying the precursor solution into a collector by using high-pressure airflow to form (NH)₄)₂HPO₄The concentration of the solution is 0.1-2.5 mol/L, Ca (NO)₃)₂The concentration of the solution is 0.05-2.0 mol/L, and the addition amount of SIC nano powder is (NH)₄)₂HPO₄And Ca (NO)₃)₂10 to 70 percent of the total molar weight, the bending strength of the composite ceramic material is 470 to 600MPa, and the fracture toughness is 4.5 to 6.0MPam^1/2。

2. The SIC reinforced hydroxyapatite composite nanoceramic material prepared by the high-pressure jet-flow solution-jet technology according to claim 1, wherein the (NH) is₄)₂HPO₄The concentration of the solution is 0.15-2.0 mol/L, Ca (NO)₃)₂The concentration of the solution is 0.1-2.0 mol/L.

3. The SIC reinforced hydroxyapatite composite nanoceramic material prepared by the solution jet spinning technology according to the claims 1-2, wherein the flexural strength of the composite nanoceramic material is 490-E590MPa and 4.7-5.5 MPam of fracture toughness^1/2。

4. The SIC reinforced hydroxyapatite composite nano ceramic material prepared by the high-pressure airflow lower solution spraying technology according to the claims 1 to 3, characterized in that the adding amount of SIC nano powder is (NH)₄)₂HPO₄And Ca (NO)₃)₂20 to 60 percent of the total molar amount.

5. A preparation method of a SIC reinforced hydroxyapatite composite nano ceramic material comprises the following steps:

(1) respectively preparing (NH) with a solubility of 0.1-2.5 mol/L₄)₂HPO₄The solution and Ca (NO) with the concentration of 0.05-2.0 mol/L₃)₂Mixing the solution and the solution, adding ammonia water to adjust the pH value of the reaction solution to 10-11, adding SIC nano powder and polyethylene glycol after the reaction is finished, and magnetically stirring to obtain uniform dispersion liquid, namely precursor solution, (NH)₄)₂HPO₄The solution is prepared by using a mixed solution of deionized water and absolute ethyl alcohol, and Ca (NO)₃)₂Preparing the solution by using absolute ethyl alcohol;

(2) metering the precursor solution prepared in the step (1) by a metering pump, pumping the precursor solution into a nozzle by a muzzle pump, spraying a trickle from a spinneret orifice along with the precursor solution, and simultaneously blowing and stretching the trickle by a high-pressure airflow spraying device at a high speed to obtain the SIC/hydroxyapatite composite material deposited on a collector, wherein the airflow pressure is 50-80 psi;

(3) sintering the SIC/hydroxyapatite composite material at high temperature, and then cooling to obtain the SIC reinforced hydroxyapatite composite nano ceramic material.

6. The method for preparing SIC enhanced hydroxyapatite composite nano ceramic material according to claim 5, wherein the (NH) is₄)₂HPO₄The concentration of the solution is 0.15-2.0 mol/L, Ca (NO)₃)₂The concentration of the solution is 0.1-2.0 mol/L.

7. The method for preparing SIC reinforced hydroxyapatite composite nanoceramic material according to claim 5, wherein the air flow pressure in step (2) is 70 psi.

8. The preparation method of the SIC-reinforced hydroxyapatite composite nano-ceramic material according to claim 5, wherein the bending strength of the composite ceramic material is 490-590 MPa, and the fracture toughness is 4.7-5.5 MPam^1/2。

9. The method for preparing SIC enhanced hydroxyapatite composite nano ceramic material according to claim 5, wherein the adding amount of SIC nano powder is (NH)₄)₂HPO₄And Ca (NO)₃)₂20 to 60 percent of the total molar amount.

10. An application of SIC reinforced hydroxyapatite composite nano ceramic material prepared by a solution jet spinning technology under high-pressure airflow as a biological bone tissue replacement material.

Technical Field

The application belongs to the field of preparation of bionic materials, relates to preparation of a biological ceramic material, and particularly relates to SIC (SIC-reinforced hydroxyapatite) composite ceramic prepared by adopting a solution jet spinning technology.

Background

The bioceramic material is required to have higher biological elasticity, biocompatibility and stable chemical characteristics, and can be made into various tissues and organs such as teeth, body bones and the like by utilizing the characteristics for repairing or replacing human bodies, and the bioceramic material has the advantages of good biocompatibility, corrosion resistance and the like as an inorganic biomedical material and is more and more valued by people.

The biological ceramics comprise inert biological ceramics, active biological ceramics and absorbable biological ceramics according to different activities in organisms, wherein hydroxyapatite is a representative of the active biological ceramic materials, the ceramic materials are concerned by scholars at home and abroad in preparation process, biocompatibility, drug carriers and other aspects, the hydroxyapatite is one of quaternary inorganic compound apatite and belongs to a hexagonal crystal system, and compared with other biological materials, the hydroxyapatite contains substances which are the same as inorganic substances of human hard tissues, so the hydroxyapatite has good biocompatibility and no biological toxicity with biological tissues, has bone inductivity, can provide a bracket and a channel for the growth of new bone tissues, and the aperture, the porosity and the communication inside the pores are decisive factors of the bone growth mode and quantity, but the mechanical property of the hydroxyapatite material in a wet physiological environment is poor, the material is brittle, and the research on the hydroxyapatite material aims to overcome the brittleness and fatigue damage of the hydroxyapatite biological ceramic material in a physiological environment and enable the hydroxyapatite biological ceramic material to be used as a bone replacement material with strong bearing capacity, so that the problem that how to improve the obdurability of the nano hydroxyapatite material and the biocompatibility so as to meet the requirements of orthopedics clinics on biological performance and mechanical performance is to be solved urgently is solved. SiC belongs to inert biological ceramics, is not easy to dissolve in human body, is combined with biological hard tissues into a mechanical lock, has high bending strength, strong fracture toughness and high compressive strength, and is an effective toughening and reinforcing material.

The solution jet spinning technology is a novel method for preparing micro-nano fibers, and compared with the traditional electrostatic spinning method, the method does not need an electric field environment, does not need high-voltage equipment or any conductive collector, is simpler in equipment, can be used for spinning at a higher injection speed, is easy to operate, is low in cost, and is higher in spinning efficiency. The selection range of raw materials is wider, the raw materials are not limited to polymers with higher dielectric constants, and the adopted solvent is easy to volatilize, free of toxicity and more environment-friendly. The solution jet spinning technique is to deposit the fibers on the surface of a substrate or carrier by dissolving the raw materials in a volatile solvent and treating the mixture solution with a pressurized gas flowing at a high speed to promote the volatilization of the solvent and the deposition refinement of the fibers. The prepared micro-nanofiber has wide commercial value, and can be applied to polymer reinforcement, medical treatment, PM2.5 filtration, electrical and optical devices and the like.

According to the invention, the SIC enhanced hydroxyapatite composite nano ceramic material with improved comprehensive properties in the aspects of porosity, specific surface area, bioactivity, mechanical strength and the like is prepared by using the solution jet spinning technology for the first time, compared with electrostatic spinning, the production efficiency of the nano ceramic fiber prepared by using the solution jet spinning technology is improved by 5-8 times, the constraint of a high-voltage electric field is omitted, the occurrence of the phenomenon of blockage of high-concentration inorganic salt spinning mother liquor near the tip of a syringe needle is obviously reduced, the safety performance is high, and the spinning efficiency is high.

Disclosure of Invention

In order to solve the above problems, the following technical solutions have been proposed through intensive research.

A SIC enhanced hydroxyapatite composite nano ceramic material prepared by adopting a solution jet spinning technology under high-pressure airflow is characterized in that: the composite ceramic material is (NH)₄)₂HPO₄Solution, Ca (NO)₃)₂Mixing the solution, ammonia water solution and polyethylene glycol as raw materials, reacting, adding SIC nano powder and polyethylene glycol, magnetically stirring to obtain precursor solution, pumping the precursor solution through a gun mouth of a solution spinning device, and simultaneously spraying the precursor solution into a collector by using high-pressure airflow to form (NH)₄)₂HPO₄The concentration of the solution is 0.1-2.5 mol/L, Ca (NO)₃)₂The concentration of the solution is 0.05-2.0 mol/L, and the addition amount of SIC nano powder is (NH)₄)₂HPO₄And Ca (NO)₃)₂10 to 70 percent of the total molar weight, the bending strength of the composite ceramic material is 470 to 600MPa, and the fracture toughness is 4.5 to 6.0MPam^1/2。

Preferably, said (NH)₄)₂HPO₄The concentration of the solution is 0.15-2.0 mol/L, Ca (NO)₃)₂The concentration of the solution is 0.1-2.0 mol/L.

Preferably, the bending strength of the composite ceramic material is 490-590 MPa, and the fracture toughness is 4.7-5.5 MPam^1/2。

Preferably, the adding amount of SIC nanopowder is (NH)₄)₂HPO₄And Ca (NO)₃)₂20 to 60 percent of the total molar amount.

A preparation method of a SIC reinforced hydroxyapatite composite nano ceramic material comprises the following steps:

(1) respectively preparing (NH) with a solubility of 0.1-2.5 mol/L₄)₂HPO₄The solution and Ca (NO) with the concentration of 0.05-2.0 mol/L₃)₂Mixing the solution and the solution, adding ammonia water to adjust the pH value of the reaction solution to 10-11, adding SIC nano powder and polyethylene glycol after the reaction is finished, and magnetically stirring to obtain uniform dispersion liquid, namely precursor solution, (NH)₄)₂HPO₄The solution is prepared by using a mixed solution of deionized water and absolute ethyl alcohol, and Ca (NO)₃)₂Preparing the solution by using absolute ethyl alcohol;

(2) metering the precursor solution prepared in the step (1) by a metering pump, pumping the precursor solution into a nozzle by a muzzle pump, spraying a trickle from a spinneret orifice along with the precursor solution, and simultaneously blowing and stretching the trickle by a high-pressure airflow spraying device at a high speed to obtain the SIC/hydroxyapatite composite material deposited on a collector, wherein the airflow pressure is 50-80 psi;

(3) sintering the SIC/hydroxyapatite composite material at high temperature, and then cooling to obtain the SIC reinforced hydroxyapatite composite nano ceramic material.

Preferably, the (NH)₄)₂HPO₄The concentration of the solution is 0.15-2.0 mol/L, Ca (NO)₃)₂The concentration of the solution is 0.1-2.0 mol/L.

Preferably, the gas stream pressure in step (2) is 70 psi.

Preferably, the bending strength of the composite ceramic material is 490-590 MPa, and the fracture toughness is 4.7-5.5 MPam^1/2。

Preferably, the adding amount of SIC nanopowder is (NH)₄)₂HPO₄And Ca (NO)₃)₂20 to 60 percent of the total molar amount.

An application of SIC reinforced hydroxyapatite composite nano ceramic material prepared by a solution jet spinning technology under high-pressure airflow as a biological bone tissue replacement material.

Advantageous effects

The technical scheme provided by the invention has the beneficial effects that: the invention firstly utilizes the solution jet spinning technology to prepare the SIC reinforced hydroxyapatite composite nano ceramic material with improved comprehensive properties in the aspects of porosity, specific surface area, bioactivity, mechanical strength and the like, has high bending strength, strong fracture toughness and high compressive strength, and is an effective toughening and reinforcing material. Compared with the prior art, the bending strength and the fracture toughness are greatly improved, the bending strength of the composite ceramic material is 470-600 MPa, and the fracture toughness is 4.5-6.0 MPam^1/2. The material has excellent biocompatibility and mechanical property, can be used as a bone replacement material with strong bearing capacity to meet the requirements of orthopedics clinic on the biological property and the mechanical property of the bone material, is used for bone tissue engineering or used as an organism bone replacement material or a biological support material, has various functions, is convenient for mass production, and has good application prospect. Compared with electrostatic spinning, the production efficiency of the nano ceramic fiber prepared by adopting the solution jet spinning technology is improved by 5-8 times, the constraint of a high-voltage electric field is eliminated, the phenomenon of blockage of the high-concentration inorganic salt spinning mother liquor near the tip of the syringe needle is obviously reduced, the safety performance is high, and the spinning efficiency is high.

Detailed Description