阅读说明：本技术 一种负载钛锌的ZrO2增强羟基磷灰石抗菌复合纳米陶瓷材料及其制备方法 (ZrO loaded with titanium and zinc2Reinforced hydroxyapatite antibacterial composite nano ceramic material and preparation method thereof ) 是由 鄢军 兰清泉 于 2019-02-21 设计创作，主要内容包括：本申请涉及一种负载钛锌的ZrO<Sub>2</Sub>增强羟基磷灰石抗菌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抗菌性、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负载钛锌的ZrO<Sub>2</Sub>增强羟基磷灰石抗菌复合纳米陶瓷材料,其抗弯强度高、断裂韧性强、抗压强度高。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330～560MPa,断裂韧性为3.5～5.7MPam<Sup>1/2</Sup>。其抗菌性、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抗菌性、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 titanium-zinc-loaded ZrO 2 A reinforced hydroxyapatite antibacterial composite nano ceramic material and a preparation method thereof. The invention firstly utilizes the solution jet spinning technology to prepare the ZrO loaded with titanium and zinc and with improved comprehensive properties in the aspects of antibacterial property, porosity, specific surface area, bioactivity, mechanical strength and the like 2 The reinforced hydroxyapatite antibacterial composite nano ceramic material has high bending strength, strong fracture toughness and high compressive strength. Compared with the prior art, the bending strength and the fracture toughness are greatly improved, the bending strength of the composite ceramic material is 330-560 MPa, and the fracture toughness is 3.5-5.7 MPam 1/2 . Its antibacterial propertyThe composite material has excellent biocompatibility and mechanical property, can be used as a bone replacement material with strong bearing capacity to meet the requirements of bone material antibacterial property, biological property and mechanical property in orthopedics clinic, 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. Preparation of titanium-zinc-loaded ZrO by solution jet spinning technology under high-pressure airflow₂The reinforced hydroxyapatite antibacterial composite nano ceramic material is characterized in that: the composite ceramic material is H₃PO₄Solution, Ti (SO)₄)₂Solution, Ca (NO)₃)₂Solution, Zn (NO)₃)₂The solution, ammonia water solution and polyethylene glycol are used as raw materials, mixed and reacted, and added with ZrO₂The nanometer powder and polyethylene glycol are magnetically stirred uniformly to obtain precursor solution, the precursor solution is pumped through a muzzle of a solution spinning device and is sprayed into a collector by utilizing high-pressure airflow at the same time to form the nanometer powder, wherein H₃PO₄The concentration of the solution is 0.1-2.0 mol/L, Ca (NO)₃)₂The concentration of the solution is 0.05-1.0 mol/L, Ti (SO)₄)₂The concentration of the solution is 0.05-1.0 mol/L, Zn (NO)₃)₂The concentration of the solution was 0.01mol/L, ZrO₂The addition of the nano powder is H₃PO₄、Ti(SO₄)₂、Ca(NO₃)₂、Zn(NO₃)₂20 to 60 percent of the total molar weight, and the bending strength of the composite ceramic material is 300 to 560MPa, fracture toughness of 3.6 to 5.7MPam^1/2。

2. The method for preparing titanium-zinc-loaded ZrO by using high-pressure solution jet spinning under airflow according to claim 1₂The reinforced hydroxyapatite antibacterial composite nano ceramic material is characterized in that the H is₃PO₄The concentration of the solution is 0.15-2.0 mol/L, Ca (NO)₃)₂The concentration of the solution is 0.15-1.0 mol/L, Ti (SO)₄)₂0.15-1.0 mol/L of the solution.

3. The method for preparing titanium-zinc-loaded ZrO by using high-pressure solution jet spinning under airflow according to claims 1-2₂The reinforced hydroxyapatite antibacterial composite nano ceramic material is characterized in that the bending strength of the composite ceramic material is 370-500 MPa, and the fracture toughness is 3.8-5.0 MPam^1/2。

4. A method for preparing Ti-Zn loaded ZrO by high pressure under-stream solution jet spinning according to claims 1 to 3₂The reinforced hydroxyapatite antibacterial composite nano ceramic material is characterized in that ZrO₂The addition of the nano powder is H₃PO₄、Ti(SO₄)₂、Ca(NO₃)₂、Zn(NO₃)₂25 to 50 percent of the total molar amount.

5. ZrO loaded with titanium and zinc₂The preparation method of the reinforced hydroxyapatite antibacterial composite nano ceramic material comprises the following steps:

(1) respectively preparing H with the solubility of 0.1-2.0 mol/L₃PO₄Solution, Ti (SO) with concentration of 0.05-1.0 mol/L₄)₂Solution of Zn (NO) at a concentration of 0.01mol/L₃)₂The solution and Ca (NO) with the concentration of 0.05-1.0 mol/L₃)₂Mixing the solutions, adding ammonia water to adjust the pH value of the reaction solution to 10-11, and adding ZrO after the reaction is finished₂Magnetically stirring the nano powder and polyethylene glycol to obtain a uniform dispersion liquid, namely a precursor solutionSaid H is₃PO₄Solution, Ti (SO)₄)₂Solution, Zn (NO)₃)₂The 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 thin flow from a spinneret orifice along with the precursor solution, and simultaneously carrying out high-speed airflow blowing and stretching on the thin flow by a high-pressure airflow spraying device to obtain ZrO deposited on a collector₂A/hydroxyapatite composite material, wherein the airflow pressure is 50-80 psi;

(3) ZrO 2 is mixed with₂Sintering the/hydroxyapatite composite material at high temperature, and then cooling to obtain the ZrO loaded with titanium and zinc₂The reinforced hydroxyapatite antibacterial composite nano ceramic material.

6. Titanium-zinc-loaded ZrO according to claim 5₂The preparation method of the reinforced hydroxyapatite antibacterial composite nano ceramic material is characterized in that the H is₃PO₄The concentration of the solution is 0.15-2.0 mol/L, Ca (NO)₃)₂The concentration of the solution is 0.15-1.0 mol/L, Ti (SO)₄)₂0.15-1.0 mol/L of the solution.

7. Titanium-zinc-loaded ZrO according to claim 5₂The preparation method of the reinforced hydroxyapatite antibacterial composite nano ceramic material is characterized in that the air flow pressure in the step (2) is 70 psi.

8. Titanium-zinc-loaded ZrO according to claim 5₂The preparation method of the reinforced hydroxyapatite antibacterial composite nano ceramic material is characterized in that the bending strength of the composite ceramic material is 370-500 MPa, and the fracture toughness is 3.8-5.0 MPam^1/2。

9. Titanium-zinc-loaded ZrO according to claim 5₂Reinforced hydroxyapatite antibacterial composite nanoA process for producing a rice ceramic material, characterized in that ZrO₂The addition of the nano powder is H₃PO₄、Ti(SO₄)₂、Ca(NO₃)₂、Zn(NO₃)₂25 to 50 percent of the total molar amount.

10. Titanium-zinc-loaded ZrO prepared by adopting solution spinning technology under high-pressure airflow₂The reinforced hydroxyapatite antibacterial composite nano ceramic material is applied 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 titanium-zinc-loaded ZrO prepared by adopting a solution jet spinning technology₂The hydroxyapatite composite ceramic is enhanced.

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. ZrO (ZrO)₂Belongs to inert biological ceramics, is not easy to dissolve in human body, is combined with biological hard tissue 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.

The invention firstly utilizes the solution jet spinning technology to prepare the ZrO loaded with titanium and zinc and with improved comprehensive properties in the aspects of porosity, specific surface area, bioactivity, mechanical strength and the like₂Compared 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 blocking phenomenon 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.

Preparation of titanium-zinc-loaded ZrO by solution jet spinning technology under high-pressure airflow₂The reinforced hydroxyapatite antibacterial composite nano ceramic material is characterized in that: the composite ceramic material is H₃PO₄Solution, Ti (SO)₄)₂Solution, Ca (NO)₃)₂Solution, Zn (NO)₃)₂The solution, ammonia water solution and polyethylene glycol are used as raw materials, mixed and reacted, and added with ZrO₂The nanometer powder and polyethylene glycol are magnetically stirred uniformly to obtain precursor solution, the precursor solution is pumped through a muzzle of a solution spinning device and is sprayed into a collector by utilizing high-pressure airflow at the same time to form the nanometer powder, wherein H₃PO₄The concentration of the solution is 0.1-2.0 mol/L,Ca(NO₃)₂the concentration of the solution is 0.05-1.0 mol/L, Ti (SO)₄)₂The concentration of the solution is 0.05-1.0 mol/L, Zn (NO)₃)₂The concentration of the solution was 0.01mol/L, ZrO₂The addition of the nano powder is H₃PO₄、Ti(SO₄)₂、Ca(NO₃)₂、Zn(NO₃)₂20 to 60 percent of the total molar amount, the bending strength of the composite ceramic material is 300 to 560MPa, and the fracture toughness is 3.6 to 5.7MPam^1/2。

Preferably, said H₃PO₄The concentration of the solution is 0.15-2.0 mol/L, Ca (NO)₃)₂The concentration of the solution is 0.15-1.0 mol/L, Ti (SO)₄)₂0.15-1.0 mol/L of the solution.

Preferably, the bending strength of the composite ceramic material is 370-500 MPa, and the fracture toughness is 3.8-5.0 MPam^1/2。

Preferably, ZrO₂The addition of the nano powder is H₃PO₄、Ti(SO₄)₂、Ca(NO₃)₂、Zn(NO₃)₂25 to 50 percent of the total molar amount.

ZrO loaded with titanium and zinc₂The preparation method of the reinforced hydroxyapatite antibacterial composite nano ceramic material comprises the following steps:

(1) respectively preparing H with the solubility of 0.1-2.0 mol/L₃PO₄Solution, Ti (SO) with concentration of 0.05-1.0 mol/L₄)₂Solution of Zn (NO) at a concentration of 0.01mol/L₃)₂The solution and Ca (NO) with the concentration of 0.05-1.0 mol/L₃)₂Mixing the solutions, adding ammonia water to adjust the pH value of the reaction solution to 10-11, and adding ZrO after the reaction is finished₂Mixing nanometer powder and polyethylene glycol under magnetic stirring to obtain uniform dispersion, i.e. precursor solution, wherein H is₃PO₄Solution, Ti (SO)₄)₂Solution, Zn (NO)₃)₂The 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) will step withMetering the precursor solution obtained by the configuration in the step (1) by a metering pump, pumping the precursor solution into a nozzle by a muzzle pump, spraying a thin flow from a spinneret orifice along with the precursor solution, and simultaneously carrying out high-speed airflow blowing and stretching on the thin flow by a high-pressure airflow spraying device to obtain ZrO deposited on a collector₂A/hydroxyapatite composite material, wherein the airflow pressure is 50-80 psi;

(3) ZrO 2 is mixed with₂Sintering the/hydroxyapatite composite material at high temperature, and then cooling to obtain the ZrO loaded with titanium and zinc₂The reinforced hydroxyapatite antibacterial composite nano ceramic material.

Preferably, said H₃PO₄The concentration of the solution is 0.15-2.0 mol/L, Ca (NO)₃)₂The concentration of the solution is 0.15-1.0 mol/L, Ti (SO)₄)₂0.15-1.0 mol/L of the solution.

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

Preferably, the bending strength of the composite ceramic material is 370-500 MPa, and the fracture toughness is 3.8-5.0 MPam^1/2。

Preferably, ZrO₂The addition of the nano powder is H₃PO₄、Ti(SO₄)₂、Ca(NO₃)₂、Zn(NO₃)₂25 to 50 percent of the total molar amount.

Titanium-zinc-loaded ZrO prepared by adopting solution spinning technology under high-pressure airflow₂The reinforced hydroxyapatite antibacterial composite nano ceramic material is applied 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 ZrO loaded with titanium and zinc and with improved comprehensive properties in the aspects of antibacterial property, porosity, specific surface area, bioactivity, mechanical strength and the like₂The reinforced hydroxyapatite antibacterial composite nano ceramic material has high bending strength, strong fracture toughness and high compressive strength. Compared with the prior art, the antibacterial property, the bending strength and the fracture toughness are greatly improved, and the bending strength of the composite ceramic material is 330 ℃560MPa, and the fracture toughness is 3.5-5.7 MPam^1/2. In addition, the photocatalytic decomposition bacteria of titanium (IV) and the antibacterial synergistic effect of zinc ions enable TiZnHAp to have excellent antibacterial effect, and tests on the antibacterial performance of the composite material according to the national standard GB/T20944.3-2008 have the antibacterial effect of more than 99% on escherichia coli and staphylococcus aureus. The antibacterial bone substitute material has excellent antibacterial property, biocompatibility and mechanical property, can be used as a bone substitute material with strong bearing capacity so as to meet the requirements of bone material antibacterial property, biological property and mechanical property in orthopedics clinic, is used for bone tissue engineering or used as an organism bone substitute material or a biological scaffold 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