阅读说明：本技术 一种镁基磁性微球的制备方法 (Preparation method of magnesium-based magnetic microspheres ) 是由 梁军浩 贺辛亥 刘明霞 李海燕 于 2020-10-21 设计创作，主要内容包括：本发明的一种镁基磁性微球的制备方法,首先将碳纳米管通过化学镀的方法进行磁改性,在碳纳米管表面均匀镀一层5nm～10nm的磁性颗粒,然后将改性后的碳纳米管与镁在一定条件下进行搅拌复合后,得到碳纳米管质量含量5％～10％的镁基复合材料,最后利用金属微滴喷射技术将复合材料在630℃～650℃下喷射成形50μm～100μm的磁性微球。该镁基磁性微球既具有良好的机械强度,又可以利用镁与人体相容性高的特点使制备的磁性微球具有通用性。(The invention relates to a preparation method of magnesium-based magnetic microspheres, which comprises the steps of carrying out magnetic modification on carbon nanotubes by a chemical plating method, uniformly plating a layer of 5-10 nm magnetic particles on the surfaces of the carbon nanotubes, stirring and compounding the modified carbon nanotubes and magnesium under certain conditions to obtain a magnesium-based composite material with the mass content of the carbon nanotubes of 5-10%, and finally spraying the composite material at 630-650 ℃ by using a metal droplet spraying technology to form the magnetic microspheres with the particle size of 50-100 microns. The magnesium-based magnetic microsphere has good mechanical strength, and the prepared magnetic microsphere has universality by utilizing the characteristic of high compatibility of magnesium and a human body.)

1. A preparation method of magnesium-based magnetic microspheres is characterized by comprising the following steps: firstly, the carbon nano tube is magnetically modified by a chemical plating method, namely, a layer of magnetic particles with the thickness of 10nm to 20nm is uniformly plated on the surface of the carbon nano tube to obtain the modified carbon nano tube, then the modified carbon nano tube and magnesium are stirred and compounded to obtain the magnesium-based composite material with the mass content of the carbon nano tube of 5 percent to 10 percent, and finally the magnesium-based composite material is sprayed and formed into the magnetic microspheres with the thickness of 50 mu m to 100 mu m by utilizing a metal micro-droplet spraying technology under the protection of a covering agent SJ-5 at the temperature of 630 ℃ to 650 ℃.

2. The method of claim 1, wherein the magnesium-based magnetic microsphere comprises: the magnetic particles are cobalt, nickel and one of cobalt, nickel alloy or oxide thereof.

3. The method of claim 1, wherein the magnesium-based magnetic microsphere comprises: the carbon nano tube is one of a multi-wall carbon nano tube and a single-wall carbon nano tube.

4. The method of claim 1, wherein the magnesium-based magnetic microsphere comprises: the magnesium is any one of pure magnesium and AZ31 magnesium alloy.

5. The method of claim 1, wherein the magnesium-based magnetic microsphere comprises: the stirring is solid stirring or semi-solid stirring;

stirring in semi-solid state under vacuum of 5 × 10⁴Pa～1×10⁵Mechanically stirring at 520-560 ℃ and a stirring speed of 1000-1500 rpm under Pa or RJ-5 covering agent, pouring into a steel mould preheated to 200 ℃ at 620 ℃, and putting the composite material into a crucible of a piezoelectric metal droplet jetting device;

while stirring in the solid state in Ar gas or CO₂+SF₆And (3) carrying out stirring friction processing under the protection of gas, wherein the rotating speed is 800-1200 rpm, and the advancing speed is 20-50 mm/min.

Technical Field

The invention belongs to the technical field of magnetic composite materials, and particularly relates to a preparation method of magnesium-based magnetic microspheres.

Background

The magnetic microsphere is a novel functional material, is widely applied to the rapid separation of biological target products in the fields of biomedicine, cytology, bioengineering and the like, and is widely applied to targeted drug delivery in the aspect of clinical medicine. The common magnetic microsphere is a high molecular material as a substrate, and the high molecular material and body protein are easy to generate non-specificity and hardly have universality. Therefore, it is necessary to develop a magnetic microsphere with a metallic material and excellent compatibility with the body.

Disclosure of Invention

The invention aims to provide a preparation method of magnesium-based magnetic microspheres, which solves the problem that the prior art has nonspecific characteristics between high-molecular magnetic microspheres and human proteins.

The invention adopts the technical scheme that a magnesium-based magnetic microsphere is prepared by carrying out magnetic modification on a carbon nano tube by a chemical plating method, namely uniformly plating a layer of magnetic particles with the thickness of 10-20 nm on the surface of the carbon nano tube to obtain a modified carbon nano tube, then stirring and compounding the modified carbon nano tube and magnesium to obtain a magnesium-based composite material with the mass content of the carbon nano tube of 5-10 percent, and finally spraying and forming the magnesium-based composite material into the magnetic microsphere with the thickness of 50-100 mu m under the protection of an SJ-5 covering agent at the temperature of 630-650 ℃ by utilizing a metal microdroplet spraying technology.

The invention is also characterized in that:

the magnetic particles are cobalt, nickel and one of cobalt, nickel alloy or oxide thereof.

The carbon nanotube is one of a multi-walled carbon nanotube and a single-walled carbon nanotube.

The magnesium is any one of pure magnesium and AZ31 magnesium alloy.

Stirring is solid stirring or semi-solid stirring:

stirring in semi-solid state under vacuum of 5 × 10⁴Pa～1×10⁵Pa or RJ-5 covering agent, at 520-560 deg.C and 1000-1500 rpm, mechanically stirring, and pouring at 620 deg.CPreheating a steel mould at 200 ℃, and putting the composite material into a crucible of a piezoelectric metal droplet jetting device;

while stirring in the solid state in Ar gas or CO₂+SF₆And (3) carrying out stirring friction processing under the protection of gas, wherein the rotating speed is 800-1200 rpm, and the advancing speed is 20-50 mm/min.

Wherein the metal droplet ejection technology is continuous and drop-on-demand.

The invention has the advantages that

The invention relates to a preparation method of magnesium-based magnetic microspheres, which comprises the steps of carrying out magnetic modification on carbon nanotubes by a chemical plating method, uniformly plating a layer of 5-10 nm magnetic particles on the surfaces of the carbon nanotubes, stirring and compounding the modified carbon nanotubes and magnesium under certain conditions to obtain a magnesium-based composite material with the mass content of the carbon nanotubes of 5-10%, and finally spraying the composite material at 630-650 ℃ by using a metal droplet spraying technology to form the magnetic microspheres with the particle size of 50-100 microns. The magnesium-based magnetic microsphere has good mechanical strength, and the prepared magnetic microsphere has universality by utilizing the characteristic of high compatibility of magnesium and a human body.

Detailed Description

The present invention will be described in detail with reference to the following embodiments.

The invention provides a method for magnetic adsorption local vacuum evaporation, which specifically comprises the following steps: firstly, the carbon nano tube is magnetically modified by a chemical plating method, a layer of magnetic particles with the diameter of 5nm to 10nm is uniformly plated on the surface of the carbon nano tube, then the modified carbon nano tube and magnesium are stirred and compounded under a certain condition to obtain a magnesium-based composite material with the mass content of the carbon nano tube of 5 percent to 10 percent, and finally the composite material is sprayed and formed into magnetic microspheres with the diameter of 50 mu m to 100 mu m at the temperature of 630 ℃ to 650 ℃ by utilizing a metal microdroplet spraying technology.

Stirring in semi-solid state under vacuum of 5 × 10⁴Pa～1×10⁵Pa or RJ-5 covering agent at 520-560 deg.c and 1000-1500 rpm, mechanically stirring, pouring in steel mold preheated to 200 deg.c at 620 deg.c, and setting the composite material in the moldIn a crucible of a piezoelectric metal droplet jetting apparatus;

while stirring in the solid state in Ar gas or CO₂+SF₆And (3) carrying out stirring friction processing under the protection of gas, wherein the rotating speed is 800-1200 rpm, and the advancing speed is 20-50 mm/min.

Example 1

First, carbon nanotubes are added to a mixture of CoSO₄、NaH₂PO₂、Pb(NO₃)₂、Na₃C₆H₅O₇In the formed plating solution, the pH value of the plating solution is 5, the plating temperature is 60 ℃, the plating time is 20 minutes, a uniform 5nm cobalt plating layer is plated on the surface of the carbon nano tube, the cobalt-plated carbon nano tube is embedded into pure magnesium, and the cobalt is embedded in the pure magnesium₂+SF₆Under the protection of gas, the rotation speed is 1000rpm, the running speed is 50mm/min, the composite material is compounded through a stirring and rubbing process, the composite material is put into a crucible of a piezoelectric type metal microdroplet spraying device, and under the protection of a covering agent SJ-5 and the deposition distance of 100mm, the magnetic microspheres with the particle size of 50-100 microns are sprayed and formed.

Example 2

First, carbon nanotubes are added to NiSO₄·6H₂O、NaH₂PO₂·2H₂O、NH₄Cl、 Na₃C₆H₅O₇·2H₂O and PdCI₂In the formed plating solution, the pH value of the plating solution is 7, the plating temperature is 90 ℃, the plating time is 30 minutes, a layer of uniform cobalt plating layer with the thickness of 7nm is plated on the surface of the carbon nano tube, the nickel-plated carbon nano tube is pre-embedded into AZ31 magnesium alloy at the temperature of 530 ℃, and the vacuum degree is 1 multiplied by 10⁵And Pa, stirring mechanically at the stirring speed of 1000rpm, pouring into a steel die preheated to 200 ℃ at the temperature of 620 ℃, putting the composite material into a crucible of a piezoelectric metal droplet spraying device, and spraying and forming the magnetic microspheres of 50-100 mu m at the temperature of 620 ℃ under the protection of Ar gas and the deposition distance of 120 mm.

Example 2

First, carbon nanotubes are added to NiSO₄·6H₂O、NaH₂PO₂·2H₂O、NH₄Cl、 Na₃C₆H₅O₇·2H₂O and PdCI₂In the formed plating solution, the pH value of the plating solution is 8, the plating temperature is 90 ℃, the plating time is 30 minutes, a uniform cobalt-nickel layer with the thickness of 10nm is plated on the surface of the carbon nano tube, the nickel-plated carbon nano tube is pre-embedded into AZ31 magnesium alloy at the temperature of 530 ℃ and the vacuum degree of 1 multiplied by 10⁵And Pa, stirring mechanically at the stirring speed of 1000rpm, pouring into a steel die preheated to 200 ℃ at the temperature of 620 ℃, putting the composite material into a crucible of a piezoelectric metal droplet spraying device, and spraying and forming the magnetic microspheres of 50-100 mu m at the temperature of 630 ℃, under the protection of Ar gas and the deposition distance of 120 mm.

Example 3

First, carbon nanotubes are added to NiSO₄·6H₂O、NaH₂PO₂·2H₂O、NH₄Cl、 Na₃C₆H₅O₇·2H₂O and PdCI₂In the formed plating solution, the pH value of the plating solution is 8, the plating temperature is 90 ℃, the plating time is 30 minutes, a layer of uniform 10nm nickel plating layer is plated on the surface of the carbon nano tube, the nickel-plated carbon nano tube is pre-embedded into AZ31 magnesium alloy, RJ-5 covering agent is added at the temperature of 530 ℃, and mechanical stirring is carried out at the stirring speed of 1300 rpm; and finally, pouring the composite material into a steel die preheated to 200 ℃ at the temperature of 620 ℃, putting the composite material into a crucible of a piezoelectric metal microdroplet spraying device, and spraying and forming the magnetic microspheres with the particle size of 50-100 mu m at the temperature of 630 ℃ under the protection of Ar gas and the deposition distance of 120 mm.

Example 4

First, multi-walled carbon nanotubes were added to a solution of CoSO₄、NaH₂PO₂、Pb(NO₃)₂、Na₃C₆H₅O₇In the formed plating solution, the pH value of the plating solution is 5, the plating temperature is 60 ℃, the plating time is 20 minutes, a uniform 5nm cobalt plating layer is plated on the surface of the carbon nano tube, the cobalt-plated carbon nano tube is embedded into pure magnesium, and the cobalt is embedded in the pure magnesium₂+SF₆Under the protection of gas, the rotation speed is 800rpm, the advancing speed is 20mm/min, the composite material is compounded through a stirring and rubbing process, the composite material is put into a crucible of a piezoelectric type metal droplet spraying device, and the covering agent is SJ-5 at 650 DEG CUnder the protection and deposition distance of 100mm, magnetic microspheres with the particle size of 50-100 μm are formed by spraying.

Example 5

Firstly, adding single-walled carbon nanotubes into a reactor consisting of CoSO₄、NaH₂PO₂、Pb(NO₃)₂、Na₃C₆H₅O₇In the formed plating solution, the pH value of the plating solution is 5, the plating temperature is 60 ℃, the plating time is 20 minutes, a uniform 5nm cobalt plating layer is plated on the surface of the carbon nano tube, the cobalt-plated carbon nano tube is embedded into pure magnesium, and the cobalt is embedded in the pure magnesium₂+SF₆Under the protection of gas, the rotation speed is 1200rpm, the running speed is 50mm/min, the composite material is compounded through a stirring and rubbing process, the composite material is put into a crucible of a piezoelectric type metal microdroplet spraying device, and under the protection of 650 ℃ and SJ-5 covering agent and the deposition distance of 100mm, the magnetic microspheres with the particle size of 50-100 microns are sprayed and formed.

Example 6

Firstly, adding single-walled carbon nanotubes into a reactor consisting of CoSO₄、NaH₂PO₂、Pb(NO₃)₂、Na₃C₆H₅O₇In the formed plating solution, the pH value of the plating solution is 5, the plating temperature is 60 ℃, the plating time is 20 minutes, a layer of uniform 5nm cobalt plating layer is plated on the surface of the carbon nano tube, the cobalt-plated carbon nano tube is pre-embedded into AZ31 magnesium alloy at the temperature of 560 ℃ and the vacuum degree of 5 multiplied by 10⁴Pa, stirring mechanically at 1500rpm, pouring into a steel mold preheated to 200 ℃ at 620 ℃, putting the composite material into a crucible of a piezoelectric metal droplet jetting device, putting the composite material into the crucible of the piezoelectric metal droplet jetting device, and jetting and forming 50-100 mu m magnetic microspheres under 650 ℃, protection of SJ-5 covering agent and deposition distance of 100 mm.

The magnetic microsphere prepared by the invention can be applied to various fields such as targeted drug delivery, biological detection, biological separation and the like.