WO2023216521A1 - Surface modification method for degradable pure magnesium or magnesium alloy, and pure magnesium or magnesium alloy material - Google Patents

Abstract

The embodiments of the present invention disclose a surface modification method for degradable pure magnesium or a degradable magnesium alloy, and a pure magnesium or magnesium alloy material, so as to solve the technical problems whereby an existing medical pure magnesium or magnesium alloy material is not resistant to corrosion and prone to bacterial infection after being implanted into a human body. The method in the embodiments of the present invention comprises the following steps: S1, pretreating pure magnesium or a magnesium alloy; S2, subjecting the pure magnesium or magnesium alloy to ion implantation by means of a metal ion implanter provided with a zinc cathode arc source; S3, subjecting the pure magnesium or magnesium alloy obtained after step S2 is completed to ion implantation by means of a metal ion implanter provided with a copper cathode arc source; S4, subjecting the pure magnesium or magnesium alloy obtained after step S3 is completed to oxygen injection by means of a gas injection machine; and S5, forming a coating, which contains copper and zinc, on the surface of the pure magnesium or magnesium alloy.

Description

A kind of degradable pure magnesium or magnesium alloy surface modification method and pure magnesium or magnesium alloy material

This application is required to be submitted to the China Patent Office on May 7, 2022, with the application number 202210493489.5 and the invention title being "A degradable pure magnesium or magnesium alloy surface modification method and pure magnesium or magnesium alloy material". priority, the entire contents of which are incorporated into this application by reference.

Technical field

The invention relates to the technical field of metal surface modification, and in particular to a degradable pure magnesium or magnesium alloy surface modification method and pure magnesium or magnesium alloy materials.

Background technique

Due to the excellent biocompatibility of pure magnesium and magnesium alloys, and their comprehensive mechanical properties such as elastic modulus are close to those of human bones, pure magnesium and magnesium alloys have attracted more and more attention in the fields of biomedicine and other fields. Pure magnesium and magnesium alloys are degradable. The use of magnesium's tendency to corrode in the human environment is used to achieve the medical and clinical purpose of gradually biodegrading pure magnesium and magnesium alloy implants in the body until they eventually disappear, unlike traditional metal implants. In comparison, secondary removal surgery can be avoided and the patient's mental and financial burden can be reduced.

However, pure magnesium and magnesium alloys degrade too quickly. However, rapid corrosion and degradation in physiological environments often cause the tissue to fail before it heals, losing the fixation and support of the injured part, affecting the repair and maintenance of the tissue. heal. In addition, pure magnesium and magnesium alloys themselves have no biological functions and are prone to infection after implantation. Bacterial infection caused by implants is one of the key factors leading to surgical failure. Foreign matter disrupts the normal operating system of the body and can easily destroy the body’s defense barrier, increasing The chance of retrograde infection. Infection caused by implants is very difficult and the incidence rate remains high. It brings huge physical pain and heavy economic burden to patients, and at the same time limits the widespread application of implanted devices.

Therefore, finding a degradable pure magnesium or magnesium alloy surface modification method and pure magnesium or magnesium alloy materials that can solve the above technical problems has become an important research topic for those skilled in the art.

Contents of the invention

The embodiment of the present invention discloses a degradable pure magnesium or magnesium alloy surface modification method and pure magnesium or magnesium alloy materials, which are used to solve the problem that the existing medical pure magnesium or magnesium alloy materials are not corrosion-resistant and easy to be implanted into the human body. Technical problem of bacterial infection.

The embodiment of the present invention provides a method for surface modification of degradable pure magnesium or magnesium alloy, including the following steps:

S1. Preprocess pure magnesium or magnesium alloy;

S2. Use a metal ion implanter equipped with a zinc cathode arc source to perform ion implantation on pure magnesium or magnesium alloy;

S3. Use a metal ion implanter equipped with a copper cathode arc source to ion implant the pure magnesium or magnesium alloy that has completed step S2;

S4. Use a gas injector to inject oxygen into the pure magnesium or magnesium alloy that has completed step S3;

S5. A coating containing copper and zinc elements is formed on the surface of pure magnesium or magnesium alloy.

Optionally, the preprocessing in step S1 includes:

Pure magnesium or magnesium alloy is polished, ultrasonic cleaned and dried in sequence.

Optionally, the step S2 specifically includes:

Use a metal ion implanter equipped with a zinc cathode arc source to perform ion implantation on pure magnesium or magnesium alloy. The pulse voltage is -5~-35kV, the injection pressure is 1~3×10 ^-3 Pa, and the injection time is 1~3h.

Optionally, the step S3 specifically includes:

Use a metal ion implanter equipped with a copper cathode arc source to ion implant the pure magnesium or magnesium alloy that has completed step S2. The pulse voltage is -5~-35kV, the injection pressure is 1~3× ^10-3 Pa, and the injection time is 1 ~3h.

Optionally, the step S4 specifically includes:

Use a gas injector to inject oxygen into the pure magnesium or magnesium alloy that has completed step S3: oxygen flow 30sccm, radio frequency 1000W, pulse voltage -20kV, pulse width 150μs, pulse frequency 50Hz, processing time 1 to 2 hours.

Optionally, the magnesium alloy is one of a magnesium-zinc-calcium magnesium alloy, a magnesium-zinc magnesium alloy, and a rare earth magnesium alloy.

Optionally, step S6 is also included;

S6. Clean the pure magnesium or magnesium alloy that forms the coating containing copper elements and zinc elements, and then blow dry and store it.

An embodiment of the present invention provides a pure magnesium or magnesium alloy material, which is characterized in that it is obtained by using the above-mentioned degradable pure magnesium or magnesium alloy surface modification method.

It can be seen from the above technical solutions that the embodiments of the present invention have the following advantages:

In this embodiment, copper elements and zinc elements are injected into the surface of pure magnesium or magnesium alloy through ion implantation, so that a coating containing copper elements and zinc elements is formed on the surface of pure magnesium or magnesium alloy. In an oxygen environment, copper Elements, zinc and oxygen form a thin film of zinc oxide and copper oxide on the surface of pure magnesium or magnesium alloy, which can greatly improve the stability of pure magnesium or magnesium alloy and at the same time improve the corrosion resistance of pure magnesium or magnesium alloy. , effectively slowing down the degradation rate of pure magnesium or magnesium alloy, and as the degradation process of pure magnesium or magnesium alloy proceeds, the zinc ions and copper ions released by the above coating can play a bactericidal effect and avoid bacterial infection.

Description of the drawings

In order to explain the embodiments of the present invention or the technical solutions in the prior art more clearly, the drawings needed to be used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings in the following description are only These are some embodiments of the present invention. For those of ordinary skill in the art, other drawings can be obtained based on these drawings without exerting any creative effort.

Figure 1 is a flow chart of a surface modification method for degradable pure magnesium or magnesium alloys.

Detailed ways

The embodiment of the present invention discloses a degradable pure magnesium or magnesium alloy surface modification method and pure magnesium or magnesium alloy materials, which are used to solve the problem that the existing medical pure magnesium or magnesium alloy materials are not corrosion-resistant and easy to be implanted into the human body. Technical problem of bacterial infection.

In order to enable those skilled in the art to better understand the solution of the present invention, the present invention will be further described in detail below in conjunction with the accompanying drawings and specific embodiments. Obviously, the described embodiments are only some of the embodiments of the present invention, but not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative efforts fall within the scope of protection of the present invention.

Embodiment 1

Please refer to Figure 1. A method for surface modification of degradable pure magnesium or magnesium alloy provided in an embodiment of the present invention includes the following steps:

S1. Preprocess pure magnesium or magnesium alloy;

S2. Use a metal ion implanter equipped with a zinc cathode arc source to perform ion implantation on pure magnesium or magnesium alloy;

S3. Use a metal ion implanter equipped with a copper cathode arc source to ion implant the pure magnesium or magnesium alloy that has completed step S2;

S4. Use a gas injector to inject oxygen into the pure magnesium or magnesium alloy that has completed step S3;

S5. A coating containing copper and zinc elements is formed on the surface of pure magnesium or magnesium alloy.

In this embodiment, copper elements and zinc elements are injected into the surface of pure magnesium or magnesium alloy through ion implantation, so that a coating containing copper elements and zinc elements is formed on the surface of pure magnesium or magnesium alloy. After being injected by a gas injector, After oxygen, the copper element, zinc element and oxygen element form a layer of zinc oxide and copper oxide film on the surface of pure magnesium or magnesium alloy, which can greatly improve the stability of pure magnesium or magnesium alloy and at the same time improve the stability of pure magnesium or magnesium alloy. The corrosion resistance of pure magnesium or magnesium alloy effectively slows down the degradation rate of pure magnesium or magnesium alloy. As the degradation process of pure magnesium or magnesium alloy proceeds, the zinc ions and copper ions released by the above coating can play a bactericidal effect and avoid bacterial infection.

Further, the preprocessing in step S1 includes:

Pure magnesium or magnesium alloy is polished, ultrasonic cleaned and dried in sequence.

It should be noted that during the above pretreatment process, contaminants adhering to the surface of pure magnesium or magnesium alloy can be cleaned, so that the subsequent ion implantation process can proceed smoothly.

Further, the step S2 specifically includes:

Use a metal ion implanter equipped with a zinc cathode arc source to perform ion implantation on pure magnesium or magnesium alloy. The pulse voltage is -5~-35kV, the injection pressure is 1~3×10 ^-3 Pa, and the injection time is 1~3h.

Further, the step S3 specifically includes:

Use a metal ion implanter equipped with a copper cathode arc source to ion implant the pure magnesium or magnesium alloy that has completed step S2. The pulse voltage is -5~-35kV, the injection pressure is 1~3× ^10-3 Pa, and the injection time is 1 ~3h.

Further, the step S4 specifically includes:

Use a gas injector to inject oxygen into the pure magnesium or magnesium alloy that has completed step S3: oxygen flow 30sccm, radio frequency 1000W, pulse voltage -20kV, pulse width 150μs, pulse frequency 50Hz, processing time 1 to 2 hours.

Further, the magnesium alloy is one of a magnesium-zinc-calcium magnesium alloy, a magnesium-zinc magnesium alloy, and a rare earth magnesium alloy.

It should be noted that this embodiment does not limit the specific type of magnesium alloy, and designers can select a suitable magnesium alloy for surface modification according to actual conditions.

Further, it also includes step S6;

S6. Clean the pure magnesium or magnesium alloy that forms the coating containing copper elements and zinc elements, and then blow dry and store it.

Embodiment 2

The degradable pure magnesium or magnesium alloy material provided in the embodiment of the present invention is specifically obtained by using the degradable pure magnesium or magnesium alloy surface modification method described in Embodiment 1.

It should be noted that the pure magnesium or magnesium alloy material modified by the surface modification method in this embodiment has good biological safety, excellent mechanical properties, corrosion resistance and antibacterial properties, and can meet the requirements of implant materials. Use requirements, and can be degraded and disappeared after achieving the use effect in the matrix, avoiding secondary surgical removal.

Experimental example one

In this experimental example, pure magnesium is cut into discs with a diameter of 10mm and a thickness of 3mm, and the surface is polished, polished, ultrasonic cleaned and dried in sequence. Pure magnesium discs were ion implanted using a metal ion implanter equipped with a zinc cathode arc source. The pulse voltage was -15kV, the injection pressure was 1××10 ^-3 Pa, and the injection time was 1 hour. Then, a metal ion implanter equipped with a copper cathode arc source was used to implant ions into the pure magnesium wafer. The pulse voltage was -15kV, the injection pressure was 1××10 ^-3 Pa, and the injection time was 1 hour. Then use a gas injector to inject oxygen into the pure magnesium wafer that has been injected with copper and zinc elements: oxygen flow 30sccm, radio frequency 1000W, pulse voltage -20kV, pulse width 150μs, pulse frequency 50Hz, processing time 1h.

The corrosion resistance of pure magnesium discs in this experimental example is shown in Table 1, and the antibacterial rate and cytotoxicity are shown in Table 2.

Experimental example two

In this experimental example, the Mg-2Zn-0.8Ca magnesium alloy was cut into discs with a diameter of 10mm and a thickness of 3mm, and the surface was polished, polished, ultrasonic cleaned and dried in sequence. A metal ion implanter equipped with a zinc cathode arc source was used to implant ions into the above-mentioned magnesium alloy discs. The pulse voltage was -15kV, the injection pressure was 1××10 ^-3 Pa, and the injection time was 2h. Then, a metal ion implanter equipped with a copper cathode arc source was used to implant ions into the magnesium alloy wafer. The pulse voltage was -15kV, the injection pressure was 1××10 ^-3 Pa, and the injection time was 2h. Then use a gas injector to inject oxygen into the magnesium alloy wafer that has been injected with copper and zinc elements: oxygen flow 30sccm, radio frequency 1000W, pulse voltage -20kV, pulse width 150μs, pulse frequency 50Hz, processing time 1h.

The corrosion resistance of the magnesium alloy discs in this experimental example is shown in Table 1, and the antibacterial rate and cytotoxicity are shown in Table 2.

Experimental example three

In this experimental example, the Mg-1Zn-0.2Nd-1Zr magnesium alloy was cut into discs with a diameter of 10mm and a thickness of 3mm, and the surface was polished, polished, ultrasonic cleaned and dried in sequence. A metal ion implanter equipped with a zinc cathode arc source was used to implant ions into magnesium alloy discs. The pulse voltage was -15kV, the injection pressure was 1××10 ^-3 Pa, and the injection time was 1.5h. Then, a metal ion implanter equipped with a copper cathode arc source was used to implant ions into the pure magnesium wafer. The pulse voltage was -15kV, the injection pressure was 1××10 ^-3 Pa, and the injection time was 1.5h. Then use a gas injector to inject oxygen into the magnesium alloy wafer that has been injected with copper and zinc elements: oxygen flow 30sccm, radio frequency 1000W, pulse voltage -20kV, pulse width 150μs, pulse frequency 50Hz, processing time 1h.

The corrosion resistance of the magnesium alloy discs in this experimental example is shown in Table 1, and the antibacterial rate and cytotoxicity are shown in Table 2.

Table 1: Annual corrosion rate of pure magnesium discs and magnesium alloy discs soaked in Hanks solution for 30 days in each experimental example

​	Annual corrosion rate (mm/y)
Control group (pure magnesium without surface modification)	4±0.5
Experimental example 1	2.3±0.3
Experimental example 2	1.8±0.2
Experimental example 3	2.2±0.2

Table 2: Antibacterial rate and cytotoxicity of pure magnesium discs and magnesium alloy discs in each experimental example

​	Antibacterial rate (%)	Cytotoxicity
Control group (pure magnesium without surface modification)	10	Level 1
Experimental example 1	90	Level 1
Experimental example 2	98	Level 1

Experimental example 3

95

Level 1

It can be seen from Table 1 and Table 2 that the pure magnesium or magnesium alloy material modified by the surface modification method of the present invention has good corrosion resistance and excellent antibacterial properties. It can meet the requirements for the use of implant materials, and can degrade and disappear after achieving the use effect in the matrix, avoiding secondary surgical removal.

The above is a detailed introduction to a degradable pure magnesium or magnesium alloy surface modification method and pure magnesium or magnesium alloy materials provided by the present invention. For those of ordinary skill in the art, based on the ideas of the embodiments of the present invention, in the specific implementation There may be changes in the manner and scope of application. In summary, the content of this specification should not be construed as limiting the present invention.

Claims (8)

1. A method for surface modification of degradable pure magnesium or magnesium alloy, which is characterized by including the following steps:

   S1. Preprocess pure magnesium or magnesium alloy;

   S2. Use a metal ion implanter equipped with a zinc cathode arc source to perform ion implantation on pure magnesium or magnesium alloy;

   S3. Use a metal ion implanter equipped with a copper cathode arc source to ion implant the pure magnesium or magnesium alloy that has completed step S2;

   S4. Use a gas injector to inject oxygen into the pure magnesium or magnesium alloy that has completed step S3;

   S5. A coating containing copper and zinc elements is formed on the surface of pure magnesium or magnesium alloy.
2. The method for surface modification of degradable pure magnesium or magnesium alloy according to claim 1, characterized in that the pretreatment in step S1 includes:

   Pure magnesium or magnesium alloy is polished, ultrasonic cleaned and dried in sequence.
3. The method for surface modification of degradable pure magnesium or magnesium alloy according to claim 1, characterized in that the step S2 specifically includes:

   Use a metal ion implanter equipped with a zinc cathode arc source to perform ion implantation on pure magnesium or magnesium alloy. The pulse voltage is -5~-35kV, the injection pressure is 1~3×10 ^-3 Pa, and the injection time is 1~3h.
4. The method for surface modification of degradable pure magnesium or magnesium alloy according to claim 3, characterized in that the step S3 specifically includes:

   Use a metal ion implanter equipped with a copper cathode arc source to ion implant the pure magnesium or magnesium alloy that has completed step S2. The pulse voltage is -5~-35kV, the injection pressure is 1~3× ^10-3 Pa, and the injection time is 1 ~3h.
5. The method for surface modification of degradable pure magnesium or magnesium alloy according to claim 1, characterized in that the step S4 specifically includes:

   Use a gas injector to inject oxygen into the pure magnesium or magnesium alloy that has completed step S3: oxygen flow rate 30sccm, radio frequency 1000W, pulse voltage -20kV, pulse width 150μs, pulse frequency 50Hz, processing time 1 to 2 hours.
6. The method for surface modification of degradable pure magnesium or magnesium alloy according to claim 1, characterized in that the magnesium alloy is one of magnesium zinc calcium series magnesium alloy, magnesium zinc series magnesium alloy and rare earth series magnesium alloy. .
7. The method for surface modification of degradable pure magnesium or magnesium alloy according to claim 1, characterized in that it also includes step S6;

   S6. Clean the pure magnesium or magnesium alloy that forms the coating containing copper elements and zinc elements, and then blow dry and store it.
8. A pure magnesium or magnesium alloy material, characterized in that it is obtained by using the degradable pure magnesium or magnesium alloy surface modification method as described in any one of claims 1 to 7.

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