阅读说明：本技术 金属板材的表面镀膜方法 (Surface coating method for metal plate ) 是由 赖奇 廖先杰 李亮 刘翘楚 罗学萍 于 2020-05-29 设计创作，主要内容包括：本发明涉及一种金属板材的表面镀膜方法,属于金属表面处理技术领域。金属板材的表面镀膜方法包括：a.间歇式等离子刻蚀：在真空度1～10<Sup>-2</Sup>Pa,用流量50～4000sccm的Ar直接对金属板材进行间歇式等离子刻蚀,至金属板材的温度达到200～1200℃停止间歇式等离子刻蚀；b.镀膜：a步骤停止间歇式等离子刻蚀后,立即在金属板材上镀膜；所述间歇式等离子刻蚀的每次溅射刻蚀时间为1～60s,停机冷却时间10～3600秒。本发明可连续化生产,生产效率高。防止金属板材被烧蚀。低成本、无污染、速度快、膜层附着力高和效率高。(The invention relates to a surface coating method of a metal plate, belonging to the technical field of metal surface treatment. The surface coating method of the metal plate comprises the following steps: a. intermittent plasma etching: in a vacuum degree of 1 to 10 ‑2 Pa, directly carrying out intermittent plasma etching on the metal plate by using Ar with the flow rate of 50-4000 sccm, and stopping the intermittent plasma etching until the temperature of the metal plate reaches 200-1200 ℃; b. film coating: a, immediately plating a film on a metal plate after the intermittent plasma etching is stopped in the step a; the sputtering etching time of each time of the intermittent plasma etching is 1-60 s, and the shutdown cooling time is 10-3600 s. The invention can realize continuous production and has high production efficiency. Preventing the metal plate from being ablated. Low cost, no pollution, high speed, high film adhesion and high efficiency.)

1. The surface coating method of the metal plate is characterized by comprising the following steps:

a. intermittent plasma etching: in a vacuum degree of 1 to 10^-2Pa, directly carrying out intermittent plasma etching on the metal plate by using Ar with the flow rate of 50-4000 sccm, and stopping the intermittent plasma etching until the temperature of the metal plate reaches 200-1200 ℃; preferably, stopping the intermittent plasma etching when the temperature of the metal plate reaches 300-800 ℃;

b. film coating: a, immediately plating a film on a metal plate after the intermittent plasma etching is stopped in the step a;

the sputtering etching time of each time of the intermittent plasma etching is 1-60 s, and the shutdown cooling time is 10-3600 s;

the coating film is preferably an electron beam evaporation coating film.

2. The method of claim 1, wherein the metal plate in step a has a width of 100 to 1500mm and a thickness of 0.1 to 0.5 mm.

3. The method for coating the surface of a metal plate according to claim 1 or 2, wherein the metal plate is a stainless steel plate, preferably a ST12, Q235 or 410 steel plate.

4. The method for coating the surface of the metal plate according to any one of claims 1 to 3, wherein the magnetic field intensity conditions of the plasma etching in the step a are as follows: 10-60 mT; the duty ratio of the positive and negative pulses of the power supply for the intermittent plasma etching in the step a is preferably 40-80%.

5. The method for coating the surface of the metal plate according to any one of claims 1 to 4, wherein the target base distance of the intermittent plasma etching in the step a is 50 to 200 mm.

6. The method for coating the surface of the metal plate according to any one of claims 1 to 5, wherein the power supply conditions in the step a are as follows: the frequency is 10-100 KHz, the working voltage is 200-1200V, and the current is 5-80A.

7. The surface coating method of the metal plate as claimed in any one of claims 1 to 6, wherein the duty ratio of positive and negative pulses of the power source of the intermittent plasma etching in the step a is 40-80%.

8. The method for coating the surface of the metal strip plate according to any one of claims 1 to 7, wherein the average etching depth of the intermittent plasma etching in the step a is 3.9 to 8.6 μm.

9. The method for coating the surface of the metal strip plate according to any one of claims 1 to 8, wherein the etching rate of the intermittent plasma etching in the step a is 2.4 to 2.7 nm/s.

10. The method for coating the surface of the metal plate according to any one of claims 1 to 9, wherein before Ar is introduced in the step a, the vacuum degree is controlled to be 10^-3～10^-4Pa。

Technical Field

The invention relates to a surface coating method of a metal plate, belonging to the technical field of metal surface treatment.

Background

Metal surfaces typically require painting, printing patterns, or surface coatings. The purpose of these surface treatments is to artificially form a surface layer on the surface of the base material, which is different from the mechanical, physical and chemical properties of the base. More advanced surface treatments include chemical vapor deposition CVD, physical vapor deposition PVD, ion implantation, ion plating, laser surface treatment, and the like. The purpose of the surface treatment is to meet the requirements of corrosion resistance, wear resistance, decoration or other special functions of the product.

For metal surface processing, Chemical Vapor Deposition (CVD), Physical Vapor Deposition (PVD), ion implantation, ion plating and laser surface treatment, operations such as cleaning, deburring, degreasing, descaling and the like are often required on the surface of a workpiece. In engineering applications, mechanical grinding, chemical treatment, surface heat treatment, spraying and the like are generally adopted. The surface treatment of the metal steel comprises chemical treatment and physical treatment, wherein the chemical treatment and the physical treatment are mainly performed on the surface of the metal steel, the steel is subjected to chemical reaction on the surface of the steel for corrosion treatment, and then a steel wire brush roller made of 304# stainless steel wires (acid and alkali resistant solution) is used for cleaning, so that the effect can be achieved. The physical treatment is achieved by means of mechanical processing, such as shot blasting, sand blasting, high-pressure water and the like.

However, the pickling chemical treatment needs to immerse the metal parts in the pickling passivation solution, and although the technical requirements and the operation are simple, the pickling solution pollutes the environment and is currently under great environmental protection pressure. The electroplating treatment is to place the workpiece in an electrified solution, improve the microscopic geometry of the metal surface and reduce the roughness of the metal surface under the combined action of the current of the anode and the cathode and the electrolytic polishing solution. So as to improve the flatness of the surface of the metal workpiece. The electrolytic polishing solution also faces great environmental protection pressure.

Plasma etching is a commonly used surface treatment method in the semiconductor field. Patent 200610116855.6 discloses a plasma etching method and apparatus, the method comprising: providing a semiconductor substrate in a reaction chamber, wherein the substrate comprises a material layer to be etched; introducing etching gas, wherein the gas is ionized into plasma by a radio frequency power source; the radio frequency power source outputs radio frequency power in a pulse output mode. The invention can generate the plasma output in a pulse form for etching, and improves the control precision of the etching end point.

Etching on the surface treatment of dynamic metal steel strips is a major challenge. The invention with application number 201510762515.X discloses a metal etching device and method which can be applied in the manufacturing environment of large-scale integrated circuit industry. Especially, the magnetic tunnel junction of a Magnetic Random Access Memory (MRAM) can be etched and post-etched in a reactive ion plasma etching chamber and an ion beam etching chamber in a vacuum uninterrupted environment, and the surface of a coating film is protected in the coating film chamber, so that the side wall of the magnetic tunnel junction after etching has no metal contamination, the chemical and physical structures of the magnetic tunnel junction are consistent with those before etching, and the magnetic tunnel junction can be taken out of an etching device and not damaged by an air environment, thereby effectively improving the yield of the MRAM device. In addition, the invention is also applicable to etching of the resistive random access memory and other metals. However, the plasma etching of the invention adopts two vacuum transition chambers as vacuum treatment, can only carry out the plasma etching in a semi-continuous way, and has slow etching speed and low efficiency. In addition, the invention fails to apply plasma etching to the surface treatment of bulk metal steel strip.

The application numbers are: 201710328563.7 discloses a TiAlSiN coating preparation method based on a reactive sputtering hysteresis effect. The method comprises the steps of workpiece pretreatment, gas path cleaning, argon ion bombardment, deposition of a bonding layer Ti, deposition of a transition layer TiN, deposition of a functional layer TiAlSiN, cooling, furnace discharge and the like. The invention effectively controls the 'transition mode' of the reactive sputtering hysteresis effect, obtains the film with proper chemical proportion and excellent structural performance while ensuring the film deposition rate, solves the problems of difficult structure control, low deposition rate, lack of process stability and repeatability and the like in the prior art, realizes the rapid and stable preparation of the TiAlSiN coating with high hardness (38GPa), low friction coefficient (0.3), good adhesive force (more than 80N) and good high temperature resistance (more than 1000 ℃), and shows great advantages in the aspects of surface wear resistance, lubrication and high temperature resistance of high-speed dry cutting tools and high-temperature forming dies prepared by the coating, thereby having great economic and social benefits. However, after the workpiece is heated to 300-500 ℃, high-purity argon is introduced into a vacuum chamber of the coating equipment, a bias power supply is turned on, and the workpiece is bombarded and cleaned, so that the production efficiency is not high.

Disclosure of Invention

In order to improve the film coating efficiency, the invention provides a surface film coating method of a metal plate.

To solve the first technical problem of the present invention, the method includes:

a. intermittent plasma etching: in a vacuum degree of 1 to 10^-2Pa, directly carrying out intermittent plasma etching on the metal plate by using Ar with the flow rate of 50-4000 sccm, and stopping the intermittent plasma etching until the temperature of the metal plate reaches 200-1200 ℃; preferably, stopping the intermittent plasma etching when the temperature of the metal plate reaches 300-800 ℃;

b. film coating: a, immediately plating a film on a metal plate after the intermittent plasma etching is stopped in the step a;

the sputtering etching time of each time of the intermittent plasma etching is 1-60 s, and the shutdown cooling time is 10-3600 s;

the coating film is preferably an electron beam evaporation coating film.

In one embodiment of the invention, the metal plate in the step a has a width of 100 to 1500mm and a thickness of 0.1 to 0.5 mm.

In one embodiment of the present invention, the metal plate is a stainless steel plate, preferably ST12, Q235 or 410 steel plate.

In one embodiment of the present invention, the magnetic field strength conditions of the plasma etching in step a are as follows: 10-60 mT; the duty ratio of the positive and negative pulses of the power supply for the intermittent plasma etching in the step a is preferably 40-80%.

In one embodiment of the present invention, the target base distance of the intermittent plasma etching in the step a is 50 to 200 mm.

In one embodiment of the present invention, the power supply conditions in step a are: the frequency is 10-100 KHz, the working voltage is 200-1200V, and the current is 5-80A.

In one embodiment of the invention, the duty ratio of positive and negative pulses of the power supply for the intermittent plasma etching in the step a is 40-80%.

In one embodiment of the invention, the average etching depth of the intermittent plasma etching in the step a is 3.9-8.6 μm.

In one embodiment of the invention, the etching rate of the intermittent plasma etching in the step a is 2.4-2.7 nm/s.

In one embodiment of the present invention, before Ar is introduced in the step a, the vacuum degree is controlled to 10^-3～10^-4Pa。。

Has the advantages that:

(1) the invention omits the step of heating the workpiece, adopts the specific plasma etching process and then directly evaporates and coats the film, and greatly improves the production efficiency.

(2) The process of the invention can prevent the metal plate from being ablated when being etched.

(3) The method has the characteristics of low cost, no pollution, high speed, high film adhesion and high efficiency, and the prepared coated metal composite material has good quality and is worthy of popularization and application.

Detailed Description

To solve the technical problem of the present invention, an embodiment of the present invention is:

the coating material is placed in a metal strip plasma etching cavity, a steel plate is used as a substrate material, Ar gas is introduced, and the substrate material is etched in the plasma etching cavity, so that the purpose of cleaning the surface is achieved.

The plasma etching is intermittent, the time of each sputtering etching of the plasma etching is 1-60 s, and the shutdown cooling time is 10-3600 s.

Wherein the width of the steel plate is 100-1500 mm, and the thickness of the steel plate is 0.1-0.5 mm.

Wherein, the plasma etching cavity is provided with a front vacuum processing chamber and a rear vacuum processing chamber or is directly vacuumized without the vacuum processing chamber, and the vacuum degree of the working cavity of the plasma etching cavity is controlled to be 10^-3～10^-4Pa。

Wherein, onThe flow rate of the Ar gas is 50-4000 sccm (standard cubic centimeter per minute). The vacuum degree of the working cavity is kept between 1 and 10^-2Pa。

Wherein, the power supply conditions of the plasma etching are as follows: the frequency is 10-100 KHz, the working voltage is 200-1200V, and the current is 5-80A.

Wherein, the magnetic field intensity conditions of the plasma etching are as follows: 10 to 60 mT.

Wherein the plasma etching has a target base distance of 50-200 mm.

Wherein, the power positive and negative pulse duty ratio required by the plasma etching plasma is 40-80%.

The steel plate is a stainless steel plate, for example, steel plates such as ST12, Q235, and 410, and may be other metal plates.

Wherein the average etching depth of the plasma etching is 3.9-8.6 μm.

Wherein the etching rate of the plasma etching is 2.4-2.7 nm/s.

The following examples are provided to further illustrate the embodiments of the present invention and are not intended to limit the scope of the present invention.