CN113652674A - Preparation device and method of super-amphiphobic film layer based on magnetic confinement plasma - Google Patents
Preparation device and method of super-amphiphobic film layer based on magnetic confinement plasma Download PDFInfo
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Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/50—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating using electric discharges
- C23C16/513—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating using electric discharges using plasma jets
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/02—Pretreatment of the material to be coated
- C23C16/0227—Pretreatment of the material to be coated by cleaning or etching
- C23C16/0245—Pretreatment of the material to be coated by cleaning or etching by etching with a plasma
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
- C23C16/45561—Gas plumbing upstream of the reaction chamber
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Plasma & Fusion (AREA)
- Chemical Vapour Deposition (AREA)
Abstract
The invention relates to a preparation device and a preparation method of a super-amphiphobic film layer based on magnetic confinement plasma, which comprises the following steps: a reaction unit having a chamber formed therein for reaction; a microwave generating source connected in communication with the chamber of the reaction unit; an air extraction unit connected in a manner of communicating with the chamber of the reaction unit so as to extract the gas in the reaction unit; the first gas distribution unit is communicated with the chamber of the reaction unit through a supply pipeline so as to add activated gas; the second gas distribution unit is communicated with the chamber of the reaction unit through a supply pipeline so as to add vaporized or gaseous coating materials serving as a gas source of the graft copolymerization film layer; and a permanent magnet group unit arranged around the outside of the reaction unit for generating magnetic field restriction. Therefore, the super-amphiphobic interface can be completed in a low-cost, large-scale and one-time mode.
Description
Technical Field
The invention relates to the technical field of plasma physical engineering, in particular to a preparation device and a preparation method of a super-amphiphobic film layer based on magnetic confinement plasma.
Background
The plasma is in a fourth state except solid, liquid and gas, and is in an electrically neutral macroscopic state. At present, the plasma chemical vapor deposition technology is a commonly used coating technology, and on substrates such as PCB circuit boards, electronic devices, mobile phones, keyboards, computers and the like, plasma is driven by an electric field to cause a chemical reaction of gaseous substances containing coating constituent atoms, so as to deposit a coating on the surface of the substrate, thereby endowing good physical and chemical durability and enhancing the strength of the surface of the substrate. Other various functional films can be deposited according to the needs, and the performances of hydrophobicity, scratch resistance, water resistance, abrasion resistance, corrosion resistance, heat dissipation and the like of the surface of the base material are improved.
In recent years, superhydrophobic surfaces have attracted increasing attention. By superhydrophobic surface is meant a solid surface having a contact angle with water of more than 150 °. The surface has extremely important application prospect in many fields such as national defense, industrial and agricultural production, daily life and the like. The research shows that the wettability of the solid surface is determined by the roughness and the surface free energy of the solid surface. On a smooth solid surface, the hydrophobic property of the material can be improved by reducing the free energy of the solid surface, but the hydrophobic angle can only reach about 120 degrees at most. When the solid surface has larger roughness, the hydrophobicity of the solid surface is greatly improved, and the hydrophobic angle can reach about 150-170 degrees, so that the key for preparing the super-amphiphobic surface is the surface micro-nano structure with larger roughness.
At present, the methods for constructing the super-amphiphobic solid surface rough structure include the following methods: chemical etching technology, deposition method, sol-gel method, electrostatic spinning method, self-assembly method, dip coating, grafting, hydrothermal synthesis, template method, nano-imprinting technology and the like. However, these preparation methods have strict requirements on materials and complex processes. Moreover, chemical solvents and acid and alkali substances are commonly used in the production process, which is not favorable for environmental protection and is not suitable for large-scale production. In view of this, as described in patent document 1, a polished sample of copper after polishing pretreatment is processed using an ultrafast laser having a laser wavelength of 1030nm, a pulse width of 240fs, and a laser beam waist spot diameter of 35 μm; and adjusting the laser repetition frequency, the laser energy, the scanning speed and the repetition times to obtain the micron cone, the secondary grid and the nano particle solid surface structure prepared by the laser.
As described in patent document 2, the surface of the magnesium alloy is polished with a metallographic abrasive paper and a polishing paste, and then washed to obtain a polished magnesium alloy; and (3) performing laser processing on the polished magnesium alloy by adopting a cross-shaped path, etching a square grid structure, and cleaning to obtain the laser-processed magnesium alloy so as to obtain a solid surface with a rough surface. After obtaining a regular or rough surface, covering a low surface energy substance to obtain the super-amphiphobic surface.
However, as in the above two patent documents, since the processing cost is high due to the use of laser and a secondary energized surface is also required after laser processing, its large-scale application is limited in both aspects of cost effectiveness.
Prior art documents:
patent documents:
patent document 1: chinese patent publication CN 112427811A;
patent document 2: chinese patent publication CN 112358812A.
Disclosure of Invention
The problems to be solved by the invention are as follows:
aiming at the problems, the invention aims to provide a device and a method for preparing a super-amphiphobic membrane layer based on magnetic confinement plasma, which are low in cost, large in scale and capable of completing a super-amphiphobic interface at one time.
The technical means for solving the problems are as follows:
the invention provides a preparation device of a super-amphiphobic film layer based on magnetic confinement plasma, which comprises the following components:
a reaction unit having a chamber formed therein for reaction;
a microwave generating source connected in communication with the chamber of the reaction unit;
an air pumping unit connected in communication with the chamber of the reaction unit to pump the gas in the reaction unit;
the first gas distribution unit is communicated with the chamber of the reaction unit through a supply pipeline so as to add activated gas;
the second gas distribution unit is communicated with the chamber of the reaction unit through a supply pipeline so as to add vaporized or gaseous coating materials as a gas source of the graft copolymerization film layer; and
and the permanent magnet group unit is arranged around the outside of the reaction unit and used for generating magnetic field constraint.
According to the invention, the reaction unit is vacuumized by the air pumping unit, and the high-frequency electromagnetic wave generated by the microwave generating source is fed into the vacuum reaction unit connected with the rectangular waveguide and the horn antenna after being coupled. The plasma is generated in the reaction unit, and the plasma is not electrified as a whole, but the composition particles are positively or negatively charged, such as positively charged atomic nuclei and negatively charged electrons. The method comprises the steps that activated gas is introduced into a cavity of a reaction unit to serve as etching process gas, under the action of a strong electric field and the constraint of a magnetic field of a permanent magnet group unit, high-energy electrons are subjected to the dual action of Lorentz force generated by the magnetic field and electric field force generated by the electric field, a running path is changed into a spiral motion path from a linear motion path under single electric field force, the magnetic induction intensity is higher, the radial circular radius of the Lorentz force is larger, the length of a spiral motion path of the electrons is longer, the probability that the electrons randomly collide with neutral particles such as gas molecules or atoms is higher, the energy transfer is higher, the ionization degree is higher, and the generated free radicals and active groups are more. At the moment, the charged positive ion groups are accelerated to move towards the surface of the substrate to be plated by the sheath voltage and chemically react with atoms on the surface to form volatile substances and an immediate etching effect, so that deep etching at least exceeding the nanometer degree is generated, the secondary smooth surface of the substrate to be plated has a texturing effect of a surface micro-nano structure due to the influence of ion etching, and the roughness is greatly enhanced. Therefore, the uniformly covered nanoscale low-surface-energy super-amphiphobic film layer is formed on the substrate to be plated by utilizing the coating material through plasma graft copolymerization vapor deposition, the water contact angle is between 150 and 170 degrees, and the oil contact angle is between 120 and 140 degrees.
By means of the structure, the surface roughness of the base material can be greatly increased through a plasma etching mechanism formed by a high-frequency power supply and magnetic confinement, and then the super-amphiphobic film is formed on the surface of the base material to be plated by utilizing a plasma graft copolymerization vapor deposition technology. In other words, the method can complete the construction of the micro-nano structure on the surface of the substrate and the deposition of the low-surface-energy material at one time, does not need to additionally use laser, polishing and other process treatments, does not need to clean after etching, does not need chemical solvents and acid-base substances, does not need to cover the low-surface-energy substance for the second time (enable), and realizes simple process, environmental friendliness, low cost, high energy efficiency and suitability for large-scale production.
In the present invention, the microwave generating source may be communicated with the chamber of the reaction unit through a three-pin tuner, a rectangular waveguide, and a horn antenna.
In the present invention, the permanent magnet group unit may be provided independently or integrally outside the reaction unit, and may generate the permanent magnet magnetic field distributed in the axial direction substantially coaxially with the central axis of the reaction unit.
In the invention, the permanent magnet group unit is composed of a plurality of annularly stacked permanent magnet blocks, and the permanent magnet blocks are made of alloy permanent magnet materials.
In the invention, the alloy permanent magnet material may be any one of rubidium-iron-boron Nd2Fe14B, samarium-cobalt SmCo, and rubidium-nickel-cobalt NdNiCo.
In the present invention, the first gas distribution unit may include an activated gas line for supplying an activated gas into the reaction unit, and one end of the activated gas line may be connected to an activated gas source and the other end may be connected to the reaction unit; the second gas distribution unit is provided with a coating material pipeline which is independent of the activated gas pipeline and is used for supplying a coating material to the interior of the reaction unit, one end of the coating material pipeline is connected with a coating material source, and the other end of the coating material pipeline is connected with the reaction unit.
In the present invention, the reaction unit may be provided with two coating material supply ports respectively communicating with the coating material pipes, and symmetrically disposed at both sides of the reaction unit, and the reaction unit may be provided with two activated gas supply ports respectively communicating with the activated gas pipes, and symmetrically disposed at both sides of the reaction unit. Therefore, the supply ports are arranged on two sides, so that the uniform diffusion of the gasified coating material is facilitated, a uniform film layer is formed, and the product yield is improved.
In the present invention, the activating gas in the first gas distribution unit may be an inert gas, an oxidizing gas, a hydrocarbon gas, or a mixture of these gases.
In the present invention, the inert gas may be argon, helium, or SF 6; the oxidizing gas is oxygen or nitrogen oxide.
In the present invention, the coating material in the second gas distribution unit may be a silane monomer or an acrylate unsaturated monomer.
In the present invention, the silane monomer may be hexamethyldisiloxane and/or triethoxysilane.
In addition, the coating method based on the preparation apparatus for a magnetically confined plasma-based super-amphiphobic film layer in the present invention includes:
the reaction unit is vacuumized to a preset working pressure through the air pumping unit, activated gas is conveyed into the cavity of the reaction unit 5 through the first air distribution unit, and the vacuum pressure in the cavity is controlled through the air pumping unit;
starting a microwave generating source, feeding the microwave generating source into a cavity of the reaction unit through the three-pin tuner, the rectangular waveguide and the horn antenna, and generating plasma;
the permanent magnet group unit generates a magnetic field in a cavity of the reaction unit, ion groups impact the surface of a substrate to be plated to form deep etching at least reaching the micron level, and meanwhile, the surface of the substrate is activated and cleaned;
stopping supplying the activated gas, conveying the coating material into the cavity of the reaction unit through the second gas distribution unit, and controlling the vacuum pressure in the cavity through the gas extraction unit;
the coating material in the cavity of the reaction unit is subjected to molecular chemical bond breakage and reunion in the plasma atmosphere to generate a nanoscale hydrophobic film layer with low surface energy, and the nanoscale hydrophobic film layer is deposited on the surface of the substrate to be coated with at least micron-scale etching to form a continuous film layer.
The invention has the following effects:
the preparation device and method of the super-amphiphobic film based on the magnetic confinement plasma can form a micro-nano surface based on deep etching of magnetic confinement and form a super-amphiphobic polymer film based on plasma chemical vapor deposition, and achieves low cost, high quality and high yield of the plasma film.
Drawings
FIG. 1 is a schematic structural view of a coating apparatus according to an embodiment of the present invention;
FIG. 2 is a sectional view of the permanent magnet unit of the coating device shown in FIG. 1;
description of the symbols:
d-a film coating device; 1-a microwave generating source; 2-three-pin adapter; 3-a rectangular waveguide; 4-horn antenna; 5-a reaction unit; 6-a jig supporting frame; 7-a substrate carrier; 8-activated gas switching valve; 9-a first mass flow meter; 10-an activating gas source; 11-a pneumatic diaphragm valve; 12-a second mass flow meter; 13-a source of coating material; 14-permanent magnet group unit; 15-a substrate to be plated; 16-a coating material pipeline; 17-activating gas line.
Detailed Description
The present invention is further described below in conjunction with the following embodiments, which are to be understood as merely illustrative, and not restrictive, of the invention. The following detailed description of the embodiments of the present invention, presented in the figures, is not intended to limit the scope of the invention, as claimed, but is merely representative of selected embodiments of the invention. The same or corresponding reference numerals denote the same components in the respective drawings, and redundant description is omitted.
In the description of the present invention, it should be noted that the terms "center", "upper", "lower", "left", "right", "vertical", "horizontal", "inner", "outer", "front", "rear", and the like indicate orientations or positional relationships based on those shown in the drawings, and are only for convenience of description and simplicity of description, but do not indicate or imply that the referred device or element must have a specific orientation, be constructed in a specific orientation, and be operated, and thus, should not be construed as limiting the present invention. Furthermore, the terms "first," "second," and "third" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance.
Fig. 1 is a perspective view of a coating apparatus D according to an embodiment of the present invention, and discloses a coating apparatus D for a plasma graft copolymerization film layer (hereinafter, simply referred to as a coating apparatus D) including a microwave generation source 1, a reaction unit 5, an air-extracting unit, a first air-distributing unit, a second air-distributing unit, and a permanent magnet unit 14. The reaction unit 5 is internally provided with a hollow cavity for reaction, the microwave generating source 1 is installed outside the reaction unit 5 and communicated with the cavity of the reaction unit for generating high-frequency electromagnetic waves, the air extraction unit is installed outside the reaction unit 5 and communicated with the reaction unit 5 for extracting gas in the cavity, the first air distribution unit and the second air distribution unit are installed outside the reaction unit 5 and communicated with the reaction unit 5 through a supply pipeline for adding gas or steam required by coating, and the permanent magnet unit 14 is installed outside the reaction unit 5 for generating magnetic field constraint. In some embodiments, the coating material is a chemical monomer vapor. In some embodiments, the coating material is a monomer containing a specific low surface energy functional group. Preferably, the chemical monomer vapor is not hydrophilic, so that more excellent super-amphiphobic coating can be obtained. In some embodiments, the chemical monomer vapor is a vapor formed by vaporizing a chemical monomer for forming the graft copolymer film layer. Therefore, the method adopts the magnetic confinement plasma chemical vapor deposition to etch the micro-nano structure on the surface of the base material and deposit the polymeric film layer with low surface energy property, so that the base material has the surface super-amphiphobic characteristic. In some embodiments, the substrate also has excellent corrosion resistance, because the corrosive liquid is lifted by the super-amphiphobic interface and is not directly contacted with the substrate, and the corrosive liquid drops easily slide off, so that the substrate has certain corrosion resistance. The following detailed description is made with reference to the accompanying drawings.
As shown in fig. 1, a microwave generating source 1 is connected with a three-pin tuner 2, a rectangular waveguide 3 and a horn antenna 4 in sequence, wherein the three-pin tuner 2 is a commonly-used impedance tuner, can be carried by a microwave source, and the pin depth, the pin distance and the pin radius can be set according to requirements, which is a commonly-used device for realizing impedance matching in a high-power microwave system. The rectangular guided wave 3 is an important guided wave device for transmitting electromagnetic waves by adopting a metal pipe, the pipe wall of the rectangular guided wave is usually made of copper, aluminum or other metal materials, and the rectangular guided wave has the characteristics of simple structure and high mechanical strength. The rectangular waveguide 3 has no inner conductor, so that the loss is low, the power capacity is large, the electromagnetic energy is guided and transmitted in the inner space of the waveguide tube, and the leakage of external electromagnetic waves can be prevented. Although the rectangular waveguide is exemplified in the present embodiment, a circular waveguide may be used. The horn antenna 4 is a planar antenna, and is formed by gradually expanding the opening surface of a rectangular waveguide, so that the matching between the waveguide and a free space is improved, the reflection coefficient in the waveguide is small, namely most of energy transmitted in the waveguide is radiated by a horn, and the reflected energy is small. Based on the above, in the present invention, the microwave power source frequency of the microwave generating source 1 is 0.915 or 2.45GHz, or may be a frequency in a frequency band of 2.45-30 GHz, the power is 500W-5KW, and the diameter of the horn antenna 4 may be 100mm-400mm, but the size is not limited thereto, as long as it corresponds to the size of the reaction unit 5. Therefore, the microwave generating source 1 generates electromagnetic waves, the three-pin tuner 2 adjusts impedance to enable reflected power to be reduced to the minimum and incident power to be the maximum, the rectangular waveguide 3 and the horn antenna 4 jointly form a transmission path of the microwave electromagnetic waves, the electromagnetic waves are coupled and then fed into a hollow cavity of the reaction unit 5 connected with the rectangular waveguide, and plasma is generated in the vacuum cavity of the reaction unit 5 after the microwave reaches breakdown power.
The reaction unit 5 and the inner chamber thereof are preferably formed in a cylindrical shape in the present embodiment, the height ranges from 300mm to 400mm, the diameter of the inner chamber ranges from 100mm to 400mm, and they may be formed in a cubic, rectangular parallelepiped, hexagonal or other irregular structure. In the present embodiment, the horn antenna 4 is attached to the top of the reaction unit 5 by a cable, a fastener, or the like, not shown, the air-extracting unit is attached to the bottom of the reaction unit 5, the permanent magnet group unit 14 is attached to the outer peripheral surface of the reaction unit 5, and the two air distribution units are attached to the outer peripheral surface of the reaction unit 5 so as not to collide with the permanent magnet group unit 14. However, the installation position of the pumping unit and the horn antenna 4 (corresponding to the microwave generating source 1) can be flexibly adjusted according to the shape. The reaction unit 5 may be made of non-magnetic or weakly magnetic stainless steel, such as any one of 304 stainless steel, 321 stainless steel, 316 stainless steel, and 310 stainless steel.
Fig. 2 is a sectional view of the permanent magnet unit 14 of the plating device shown in fig. 1. As shown in fig. 2, the permanent magnet group unit 14 is provided outside the reaction unit 5, and specifically, in the present invention, the permanent magnet group unit 14 is provided outside the reaction unit 5 independently or integrally, and preferably, but not limited to, a permanent magnet magnetic field distributed in the axial direction is generated substantially coaxially with the central axis of the reaction unit 5, and is configured to generate a magnetic field strength enough to affect the plasmon inside the reaction unit 5. In the present invention, the permanent magnet assembly unit 14 may be detachably provided independently of the outer wall surface of the reaction unit 5, or may be integrally provided with the outer wall surface of the reaction unit 5. The permanent magnet group unit is made of alloy permanent magnet material, and can be formed by a whole annular permanent magnet block alone or formed by a plurality of annular stacked permanent magnet blocks. The permanent magnets can also be in a strip shape, a fan shape, a cylinder shape or other special shapes and are symmetrically distributed along the cylindrical reaction unit 5 from side to side. In addition, the permanent magnet unit 14 is formed to be detachable or assembled, so that the magnetic field constraint in the device can be adjusted according to the number of the substrates 15 to be plated in the cavity and the like, and the overall adaptability of the device is improved. The permanent magnet and the permanent magnet group formed by the permanent magnet can be provided with an S-level upper end and an N-pole lower end, or the magnetic field can be exchanged, namely the upper end of the permanent magnet is the N-pole and the lower end of the permanent magnet is the S-pole, or the magnetic field distribution of a cusp field is formed according to the situation, so as to meet different application requirements. The alloy permanent magnet material may be any one of rubidium-iron-boron Nd2Fe14B, samarium-cobalt SmCo, and rubidium-nickel-cobalt NdNiCo, but is not limited thereto. Therefore, electromagnetic waves generated by the microwave generating source 1 enter the cavity of the reaction unit 5 after being coupled by the three-pin tuner 2, the rectangular waveguide 3 and the horn antenna 4, plasma is generated after the microwaves reach breakdown power, meanwhile, the permanent magnet group units 14 positioned on two sides of the cavity can obviously enhance the ion concentration, excellent etching effect and cleaning effect are achieved, and guarantee is provided for subsequent plasma coating.
More specifically, the reaction unit 5 has, in its chamber: a flat substrate carrier 7 for placing a substrate 15 to be plated; and a jig support frame 6 for supporting the substrate carrier 7 and installed on the inner sidewall surface of the chamber. The jig support frames 6 are multiple and can be installed on the inner wall of the cavity in a mechanical or chemical mode such as pins, buckles, bonding and the like. The substrate carrier 7 is height adjustable according to specific requirements, and the carrier plane is preferably matched with the magnetic field constraint of the permanent magnet unit 14 in a manner of maximum contact area, and is preferably horizontal in the present embodiment. In the present invention, only one group is shown in fig. 1, but the number is not limited as long as the permanent magnet group unit 14 can cover the magnetic flux. In addition, the reaction unit 5 is provided with a grounding wire, and is also provided with an opening for taking and placing the substrate 15 to be plated, wherein the substrate to be plated can be metal, plastic, glass, an electrical PCBA assembly and the like.
The evacuation unit is a conventional arrangement including a vacuum pump, and thus, a detailed illustration thereof is omitted in fig. 1, and the evacuation unit is connected to the chamber of the reaction unit 5 through an evacuation line, and for example, an evacuation switch valve, a pressure regulating valve, a vacuum gauge, and the like may be provided in the evacuation line to control the degree of vacuum of the chamber so that the chamber is in an appropriate process condition, and when the sensor detects that the degree of vacuum of the chamber of the reaction unit 5 satisfies a predetermined requirement, the pressure regulating valve is dynamically controlled in real time based on a feedback value of the vacuum gauge. Specifically, the pumping unit of the present invention can pump the reaction unit 5 to a predetermined working pressure of 0.01mbar to 0.5mbar, and maintain the vacuum pressure of 0.01 to 0.35mbar when supplying gas into the chamber at a later stage.
The first gas distribution unit includes an activated gas switching valve 8, a first mass flow meter 9, an activated gas source 10, and an activated gas line 17. One end of the activated gas pipeline 17 is connected with the activated gas source 10, and the other end is branched into two ports as shown in fig. 1 and is respectively communicated with the chambers of the reaction unit 5, the activated gas enters the chambers of the reaction unit 5 from the activated gas source 10 through the activated gas pipeline 17 to generate an etching reaction in a strong magnetic field, and then the activated gas is pumped out through the pumping unit. The port at which the activation gas line 17 is connected to the reaction unit 5 is an activation gas supply port for supplying activation gas, and two activation gas supply ports are symmetrically formed on both sides of the reaction unit 5. The pipeline and the port are connected with the reaction unit 5 through a flange and a rubber ring, so that the vacuum sealing performance is ensured.
Further, the activated gas source 10 is connected to a first mass flow meter 9 and an activated gas switch valve 8 in turn, and the first mass flow meter 9 is used for controlling whether the activated gas source 10 outputs and the flow rate of the activated gas to the activated gas pipeline 17 through the activated gas pipeline 17. The activated gas pipe 17 is formed with a branch point, and the activated gas outputted from the activated gas source 10 is divided into two parts at the branch point and then respectively enters the chamber from both sides, which is beneficial to uniform diffusion of the activated gas and improves the yield of the product, but not limited thereto, the activated gas pipe 17 may be communicated with the reaction unit 5 through only one port without branching.
In this embodiment, the activating gas in the first gas distribution unit may be an inert gas, an oxidizing gas, a hydrocarbon gas, or a mixture of these gases, the inert gas may be argon, helium, or SF6, and the oxidizing gas may be oxygen or nitrogen oxide. The number of the activated gas sources 10 is not limited to one, and may be a plurality of activated gas sources, as long as each activated gas source is provided with an activated gas mass flow meter and an activated gas flow switching valve, and is connected in sequence, and then is connected to the activated gas pipeline 17. Since each of the activated gas sources 10 can be independently operated, the delivery time and flow rate of the activated gas can be adjusted at any time and independently according to the process sequence, and even other process gases than the activated gas can be supplied.
The second gas distribution unit is provided with a pneumatic diaphragm valve 11, a second mass flow meter 12, a coating material source 13 and a coating material pipeline 16, one end of the coating material pipeline 16 is connected with the coating material source 13, the other end is branched into two ports as shown in fig. 1 and is respectively communicated with the chamber of the reaction unit 5, the coating material enters the chamber of the reaction unit 5 from the coating material source 13 through the coating material pipeline 16 to participate in reaction, and unreacted substances and auxiliary reaction products are pumped out and discharged through an air pumping unit at the lower part of the chamber. The ports of the coating material piping 16 connected to the reaction unit 5 are coating material supply ports for supplying a coating material, and two coating material supply ports are symmetrically formed at both sides of the reaction unit 5 for more uniformly supplying the coating material. The pipeline and the port are connected with the reaction unit 5 through a flange and a rubber ring, so that the vacuum sealing performance is ensured.
Further, a pneumatic diaphragm valve 11 and a second mass flow meter 12 are arranged on a coating material pipeline 16 connected with the coating material source 13, the pneumatic diaphragm valve 11 is used for controlling the opening and closing of the pipeline according to different processes, and the second mass flow meter 12 is used for controlling the flow rate output from the coating material source 13 to the coating material pipeline 16. The coating material pipe 16 is formed with a bifurcation, and the coating material outputted from the coating material source 13 is divided into two parts at the bifurcation, and then the two parts enter the chamber through the coating material pipe 16, which is beneficial to the uniform diffusion of the gasified coating material, and forms a uniform film, and improves the yield of the product, but not limited thereto, the coating material pipe 16 is not bifurcated, and is communicated with the reaction unit 5 through only one port.
In this embodiment, the coating material is a coating material capable of forming a functional coating film. For example, the coating material may be one or more of coating materials that improve the hydrophobicity, hydrophilicity, scratch resistance, abrasion resistance, corrosion resistance, heat dissipation, etc. of the surface of the substrate according to the requirement of the coating layer. As mentioned above, in some embodiments, the coating material is chemical monomer vapor. In some embodiments, the coating material is a monomer containing a specific low surface energy functional group. Preferably, the chemical monomer vapor is not hydrophilic, so that more excellent super-amphiphobic coating can be obtained. In some embodiments, the chemical monomer vapor is a vapor formed by vaporizing a chemical monomer for forming the graft copolymer film layer. The coating material source 44 may be, for example, a chemical monomer evaporation device. The chemical monomers include, but are not limited to, silane-based monomers, acrylate-based unsaturated monomers, and the like. The silane monomer can be hexamethyldisiloxane and/or triethoxysilane. In the invention, the coating material in the second gas distribution unit can be silane monomer or acrylate unsaturated monomer, and the silane monomer is hexamethyldisiloxane and/or triethoxysilane, etc. Based on the above, the present invention can adjust the supply amount of the gas or monomer supplied to both sides of the reaction unit 5, so as to adjust the flow rate of the activating gas and the coating material supplied from the supply port in real time according to the specific reaction conditions, thereby greatly improving the uniformity of the plasma graft copolymer film layer prepared on the surface of the substrate. The activating gas functions to etch and/or clean. The etching is to etch the substrate by generating active free radicals by the active gas under the action of the plasma and generating a rough structure on the surface of the substrate. The cleaning is to strip and oxidize trace organic matters attached to the surface of the base material by the activated gas under the action of plasma. Generally, polymers containing fluorine or organosilicon, for example, are low surface energy materials with surface energy lower than that of water, chemical monomer vapor and fluorocarbon gas are used as coating materials, and are not hydrophilic materials in the super-amphiphobic preparation, while fluorocarbon gas can provide CF bonds in the reaction to reduce the surface energy, namely, a hydrophobic and low surface energy coating is obtained.
The specific steps of preparing the plasma super-amphiphobic membrane layer by adopting the preparation device D based on the magnetic confinement plasma super-amphiphobic membrane layer are described as follows:
the substrate 15 to be plated is placed on the substrate carrier 7 in the chamber of the reaction unit 5, the reaction unit 5 is evacuated to a predetermined working pressure by the evacuation unit, the activated gas on-off valve 8 is opened, the flow rate is controlled by the first mass flow meter 9, and the activated gas is supplied into the chamber of the reaction unit 5 through the activated gas line 17, while the vacuum pressure in the chamber is controlled by the evacuation unit.
And (3) starting the microwave generating source 1, transmitting the high-frequency electromagnetic waves through the three-pin tuner 2, the rectangular waveguide 3 and the horn antenna 4, and then feeding the high-frequency electromagnetic waves into a cavity of the reaction unit 5 to generate plasma after the breakdown power is reached.
The permanent magnet unit 14 generates a magnetic field in the chamber of the reaction unit 5, free electrons constrained by the magnetic field make spiral motion along magnetic lines of force to increase collision probability, and a large number of generated ion groups impact the surface of the substrate under the action of sheath voltage to form deep etching at least reaching micron level, and meanwhile, the surface of the substrate is subjected to activation and cleaning treatment.
The supply of the activation gas is stopped by closing the activation gas switching valve 8, the pneumatic diaphragm valve 11 is opened, the flow rate is controlled by the second mass flow meter 12 and the plating material is supplied into the chamber of the reaction unit 5 via the plating material line 16, and at the same time, the vacuum pressure in the chamber is controlled by the evacuation unit.
The cavity of the reaction unit 5 is in plasma atmosphere, the molecular chemical bonds of the coating material are broken, the branched chains between the molecules are polymerized again to generate a nanoscale hydrophobic film layer with low surface energy, and the coating material is continuously introduced to maintain the polymerization reaction, so that the film layer is continuously deposited on the surface of the substrate 15 to be coated with at least micron-scale etching, and a continuous film layer is further formed.
According to the invention, the surface roughness can be greatly increased through a plasma etching mechanism formed by integrating a high-frequency power supply and magnetic confinement, a necessary foundation is provided for realizing the super-amphiphobic film, then the construction of the micro-nano structure on the surface of the substrate and the deposition of the low-surface-energy material can be completed at one time by using the coating device through plasma chemical vapor deposition, cleaning is not needed in the midway, other equipment is not needed to be superposed, and the low cost and the high productivity are realized.
The present invention will be described in detail by way of examples. It is also to be understood that the following examples are illustrative of the present invention and are not to be construed as limiting the scope of the invention, and that certain insubstantial modifications and adaptations of the invention by those skilled in the art may be made in light of the above teachings. The specific process parameters and the like of the following examples are also only one example of suitable ranges, i.e., those skilled in the art can select the appropriate ranges through the description herein, and are not limited to the specific values exemplified below.
[ example 1]
In the coating device D, a microwave generating source 1 can generate high-frequency electromagnetic waves, and a three-pin tuner 2, a rectangular waveguide 3 and a horn antenna 4 are fed into a reaction unit 5 connected with the microwave generating source and an internal reaction chamber of the reaction unit, wherein the frequency of the microwave generating source 1 is 2.45GHz, the power of the microwave generating source is 1KWW, the model of the three-pin tuner 2 is RS232, the model of the rectangular waveguide 3 is WR340, the radius of the horn antenna 4 is 220mm, the reaction unit 5 and the internal chamber of the reaction unit are cylindrical, the inner diameter of the reaction unit 5 is 440mm, the inner diameter of the reaction unit is equivalent to that of the horn antenna 4, and the height of the reaction unit is 300 mm. Two gas supply ports are respectively arranged on two sides of the reaction unit 5 and are respectively connected with an activation gas source 10 and a coating material source 13, the ports are connected with a pipeline with KF25 as a standard flange, and vacuum sealing is ensured through rubber rings. A pair of permanent magnet sets are arranged on two sides of the outer side of the reaction unit 5 and serve as permanent magnet set units 14 to provide magnetic field restraint, and the upper end and the lower end of each permanent magnet set are respectively an S pole and an N pole, so that the magnetization direction is coaxial with the axis of the cylindrical cavity. The bottom of the reaction unit 5 is connected and communicated with the air extraction unit through a vacuum pipeline, and a substrate carrier 7 is arranged in the chamber, and a substrate 15 to be plated is placed on the substrate carrier. A pressure control unit is further provided for controlling the vacuum degree in the chamber to achieve suitable reaction process conditions.
The substrate 15 to be plated is placed on the substrate carrier 7 in the chamber of the reaction unit 5 of the plating device D, the reaction unit 5 is evacuated to a predetermined working pressure of 0.15mbar by the evacuation unit, the activated gas switch valve 8 is opened, oxygen is supplied into the chamber of the reaction unit 5 as an activated gas through the activated gas pipeline 17, and at the same time, the vacuum pressure in the chamber is maintained at 0.35mbar by the evacuation unit, and the gas flow rate is maintained at 2000sccm by the first mass flow meter 9.
The microwave generating source 1 is started to generate 2.45GHz high-frequency electromagnetic waves, the high-frequency electromagnetic waves are transmitted through the three-pin tuner 2, the rectangular waveguide 3 and the horn antenna 4 and then fed into a cavity of the reaction unit 5, and plasma is generated after breakdown power is achieved.
The permanent magnet unit 14 generates a magnetic field in the chamber of the reaction unit 5, free electrons constrained by the magnetic field make spiral motion along magnetic lines of force to increase collision probability, and a large number of generated ion groups impact the surface of the substrate under the action of sheath voltage to form deep etching at least reaching micron level, and meanwhile, the surface of the substrate is subjected to activation and cleaning treatment.
The supply of the activating gas was stopped by closing the activating gas switching valve 8, the pneumatic diaphragm valve 11 was opened, and C3F6 (hexafluoropropylene) was supplied as a chemical monomer vapor (i.e., a coating material) into the chamber of the reaction unit 5 through the coating material pipe 16, while the vacuum pressure in the chamber was maintained at 0.35mbar by the evacuation unit, and the gas flow rate was maintained at 100sccm by controlling the flow rate by the second mass flow meter 12.
The cavity of the reaction unit 5 is in plasma atmosphere, the molecular chemical bonds of the coating material are broken, the branched chains between the molecules are polymerized again to generate a nanoscale hydrophobic film layer with low surface energy, and the coating material is continuously introduced to maintain the polymerization reaction, so that the film layer is continuously deposited on the surface of the substrate 15 to be coated with at least micron-scale etching, and a continuous film layer is further formed.
After the above-mentioned experiments are performed for a plurality of times, the experimental detection is performed on the polymeric film layer formed on the surface of the product. The following table shows the water and oil contact angle test results:
based on the experimental data, multiple rounds of static contact angle tests show that the product has a strong amphiphobic property, the surface water contact angle of 150-170 degrees and the oil contact angle of 120-150 degrees.
[ example 2]
The substrate 15 to be plated is placed on the substrate carrier 7 in the chamber of the reaction unit 5 of the coating apparatus D of example 1, the reaction unit 5 is evacuated to a predetermined working pressure of 0.05mbar by the evacuation unit, the activated gas switch valve 8 is opened, oxygen is supplied into the chamber of the reaction unit 5 as an activated gas through the activated gas pipe 17, and at the same time, the vacuum pressure in the chamber is maintained at 0.25mbar by the evacuation unit, and the gas flow rate is maintained at 3500sccm by the first mass flow meter 9.
The microwave generating source 1 is started to generate 2.45GHz high-frequency electromagnetic waves, the high-frequency electromagnetic waves are transmitted through the three-pin tuner 2, the rectangular waveguide 3 and the horn antenna 4 and then fed into a cavity of the reaction unit 5, and plasma is generated after breakdown power is achieved.
The permanent magnet unit 14 generates a magnetic field in the chamber of the reaction unit 5, free electrons constrained by the magnetic field make spiral motion along magnetic lines of force to increase collision probability, and a large number of generated ion groups impact the surface of the substrate under the action of sheath voltage to form deep etching at least reaching micron level, and meanwhile, the surface of the substrate is subjected to activation and cleaning treatment.
The activating gas switch valve 8 is closed to stop the supply of the activating gas, the pneumatic diaphragm valve 11 is opened, triethoxysilane (CAS number: 998-30-1) is supplied as chemical monomer vapor (i.e., coating material) into the chamber of the reaction unit 5 through the coating material pipe 16, while the vacuum pressure in the chamber is maintained at 0.25mbar by the pumping unit, and the gas flow rate is maintained at 200sccm by controlling the flow rate by the second mass flow meter 12.
The cavity of the reaction unit 5 is in plasma atmosphere, the molecular chemical bonds of the coating material are broken, the branched chains between the molecules are polymerized again to generate a nanoscale hydrophobic film layer with low surface energy, and the coating material is continuously introduced to maintain the polymerization reaction, so that the film layer is continuously deposited on the surface of the substrate 15 to be coated with at least micron-scale etching, and a continuous film layer is further formed.
After the above-mentioned experiments are performed for a plurality of times, the experimental detection is performed on the polymeric film layer formed on the surface of the product. The following table shows the water and oil contact angle test results:
based on the experimental data, multiple rounds of static contact angle tests show that the product has a strong amphiphobic property, and the product surface has a water contact angle of 160-180 degrees and an oil contact angle of 120-150 degrees.
Based on the above, the preparation device and method of the super-amphiphobic film layer based on the magnetic confinement plasma provided by the invention can improve the traditional etching method, form a micro-nano surface based on the deep etching of the magnetic confinement and form the super-amphiphobic polymer film layer based on the plasma chemical vapor deposition, and realize the low cost, the high quality and the high yield of the plasma film.
The above embodiments are intended to illustrate and not to limit the scope of the invention, which is defined by the claims, but rather by the claims, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein. Any modification, equivalent replacement, improvement and the like made within the spirit and principle of the present invention shall be included in the protection scope of the present invention.
Claims (11)
1. The utility model provides a preparation facilities based on magnetic confinement plasma super-amphiphobic membrane layer which characterized in that possesses:
a reaction unit having a chamber formed therein for reaction;
a microwave generating source connected in communication with the chamber of the reaction unit;
an air pumping unit connected in communication with the chamber of the reaction unit to pump the gas in the reaction unit;
the first gas distribution unit is communicated with the chamber of the reaction unit through a supply pipeline so as to add activated gas;
the second gas distribution unit is communicated with the chamber of the reaction unit through a supply pipeline so as to add vaporized or gaseous coating materials as a gas source of the graft copolymerization film layer; and
and the permanent magnet group unit is arranged around the outside of the reaction unit and used for generating magnetic field constraint.
2. The preparation device based on the magnetically confined plasma super-amphiphobic membrane layer as claimed in claim 1,
the microwave generating source is communicated with the cavity of the reaction unit through a three-pin tuner, a rectangular waveguide and a horn antenna.
3. The preparation device based on the magnetically confined plasma super-amphiphobic membrane layer as claimed in claim 1,
the permanent magnet group unit is independently or integrally arranged outside the reaction unit, and generates permanent magnet magnetic fields distributed along the axial direction in a mode of being approximately coaxial with the central shaft of the reaction unit.
4. The preparation device based on the magnetically confined plasma super-amphiphobic membrane layer as claimed in claim 1,
the permanent magnet group unit is composed of a plurality of permanent magnet blocks which are annularly stacked, and the permanent magnet blocks are made of alloy permanent magnet materials.
5. The preparation device based on the magnetically confined plasma super-amphiphobic membrane layer as claimed in claim 3 or 4,
the alloy permanent magnet material is any one of rubidium-iron-boron Nd2Fe14B, samarium-cobalt SmCo and rubidium-nickel-cobalt NdNiCo.
6. The preparation device based on the magnetically confined plasma super-amphiphobic membrane layer as claimed in claim 1,
the first gas distribution unit is provided with an activated gas pipeline for supplying activated gas to the interior of the reaction unit, one end of the activated gas pipeline is connected with an activated gas source, and the other end of the activated gas pipeline is connected with the reaction unit;
the second gas distribution unit is provided with a coating material pipeline which is independent of the activated gas pipeline and is used for supplying a coating material to the interior of the reaction unit, one end of the coating material pipeline is connected with a coating material source, and the other end of the coating material pipeline is connected with the reaction unit.
7. The device for preparing the super-amphiphobic membrane layer based on the magnetic confinement plasma according to claim 6,
the activated gas in the first gas distribution unit is inert gas, or oxidizing gas, or hydrocarbon gas, or a mixed gas of the inert gas, the oxidizing gas and the hydrocarbon gas.
8. The device for preparing the super-amphiphobic membrane layer based on the magnetic confinement plasma according to claim 7,
the inert gas is argon, helium or SF 6; the oxidizing gas is oxygen or nitrogen oxide.
9. The device for preparing the super-amphiphobic membrane layer based on the magnetic confinement plasma according to claim 6,
and the coating material in the second gas distribution unit is a silane monomer or an acrylate unsaturated monomer.
10. The device for preparing the super-amphiphobic membrane layer based on the magnetic confinement plasma according to claim 9,
the silane monomer is hexamethyldisiloxane and/or triethoxysilane.
11. A method for producing a plasma super-amphiphobic membrane layer using the production apparatus according to any one of claims 1 to 10, comprising:
the reaction unit is vacuumized to a preset working pressure through the air pumping unit, activated gas is conveyed into the cavity of the reaction unit 5 through the first air distribution unit, and the vacuum pressure in the cavity is controlled through the air pumping unit;
starting a microwave generating source, feeding the microwave generating source into a cavity of the reaction unit through the three-pin tuner, the rectangular waveguide and the horn antenna, and generating plasma;
the permanent magnet group unit generates a magnetic field in a cavity of the reaction unit, ion groups impact the surface of a substrate to be plated to form deep etching at least reaching the micron level, and meanwhile, the surface of the substrate is activated and cleaned;
stopping supplying the activated gas, conveying the coating material into the cavity of the reaction unit through the second gas distribution unit, and controlling the vacuum pressure in the cavity through the gas extraction unit;
the coating material in the cavity of the reaction unit is subjected to molecular chemical bond breakage and reunion in the plasma atmosphere to generate a nanoscale hydrophobic film layer with low surface energy, and the nanoscale hydrophobic film layer is deposited on the surface of the substrate to be coated with at least micron-scale etching to form a continuous film layer.
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