WO2018214447A1 - Procédé de préparation d'un nanorevêtement protecteur multifonctionnel au moyen d'une décharge cyclique continue de faible puissance - Google Patents

Procédé de préparation d'un nanorevêtement protecteur multifonctionnel au moyen d'une décharge cyclique continue de faible puissance Download PDF

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WO2018214447A1
WO2018214447A1 PCT/CN2017/113189 CN2017113189W WO2018214447A1 WO 2018214447 A1 WO2018214447 A1 WO 2018214447A1 CN 2017113189 W CN2017113189 W CN 2017113189W WO 2018214447 A1 WO2018214447 A1 WO 2018214447A1
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coating
substrate
reaction chamber
discharge
environment
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PCT/CN2017/113189
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English (en)
Chinese (zh)
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宗坚
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江苏菲沃泰纳米科技有限公司
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Publication of WO2018214447A1 publication Critical patent/WO2018214447A1/fr
Priority to US16/688,845 priority Critical patent/US11742186B2/en
Priority to US16/688,589 priority patent/US11270871B2/en
Priority to US17/653,401 priority patent/US11587772B2/en

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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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • 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

Definitions

  • the invention belongs to the technical field of plasma chemical vapor deposition, and in particular relates to a method for preparing a multifunctional nano protective coating.
  • Corrosive environments are the most common factor in the destruction of electronic devices. Corrosion of solid materials in electronic devices due to environmental corrosion, reduced conductor/semiconductor insulation, and short-circuit, open circuit, or poor contact.
  • the proportion of electronic components is increasing, and the requirements for moisture, mildew and corrosion resistance of electronic products are becoming more and more strict.
  • the communication frequency is constantly increasing, and the requirements for the heat dissipation of communication equipment and the stability and reliability of signal transmission are also increasing. Therefore, a reliable method is needed to effectively protect the circuit board and electronic components without affecting normal heat dissipation and signal transmission.
  • Polymer coatings are often used for material surface protection due to their economical, easy-to-coat and wide application range, which can give materials good physical and chemical durability.
  • the protective film formed on the surface of electronic appliances and circuit boards can effectively isolate the circuit board, and protect the circuit from corrosion and damage in a corrosive environment, thereby improving the reliability of the electronic device. Increased safety factor and guaranteed service life are used as anti-corrosion coatings.
  • Conformal coating is a process of applying a specific material to a PCB to form an insulating protective layer conforming to the shape of the object to be coated. It is a commonly used circuit board waterproofing method, which can effectively isolate the circuit board. And protect the circuit from the erosion and damage of harsh environments. At present, there are some problems and disadvantages in the preparation process of the conformal coating: the solvent in the liquid phase method is easy to damage the circuit board device; the high temperature of the heat curing coating is likely to cause damage to the device; the photocurable coating is difficult to be sealed inside the device. . Union Carbide Co. developed and applied a new conformal coating material. Parylene coating is a para-xylene polymer with low water, gas permeability and high barrier effect to achieve moisture, water and defense.
  • Rust, acid and alkali corrosion resistance It has been found that parylene is deposited under vacuum and can be applied to fields that cannot be covered by liquid coatings such as high frequency circuits and extremely weak current systems.
  • the thickness of the polymer film coating is the main reason for the protection failure of the para-xylene vapor-deposited conformal coating.
  • the polymer film coating of the printed circuit board component is prone to local rust failure at a thickness of 3 to 7 microns without affecting the high.
  • the coating thickness should be ⁇ 30 ⁇ m in the case of frequency dielectric loss.
  • Parylene coating requires high pretreatment of printed circuit boards that need protection, such as conductive components, signal transmission components, RF components, etc., in the vapor deposition of conformal coatings, it is necessary to pre-mask the circuit board components to avoid Affects component performance. This drawback has brought great limitations to the application of parylene coating. Pyrene coatings have high cost of raw materials, harsh coating preparation conditions (high temperature, high vacuum requirements), low film formation rate, and are difficult to be widely used. In addition, thick coatings tend to cause poor heat dissipation, signal blocking, Problems such as increased coating defects.
  • Plasma chemical vapor deposition is a technique in which a reactive gas is activated by a plasma to promote a chemical reaction on a surface of a substrate or a near surface to form a solid film.
  • Plasma chemical vapor deposition coatings have the following advantages:
  • the plasma polymerization film is stable in chemical and physical properties such as solvent resistance, chemical corrosion resistance, heat resistance, and abrasion resistance.
  • the plasma polymerization film has good adhesion to the substrate.
  • a uniform film can also be formed on the surface of the substrate having irregular irregularities.
  • the coating preparation temperature is low, and can be carried out under normal temperature conditions, thereby effectively avoiding damage to temperature sensitive devices.
  • the plasma process can not only prepare a coating having a thickness of a micron order but also can prepare an ultra-thin nano-scale coating.
  • P2i Company of the United Kingdom has developed a polymer nano-coating based on a specific small duty cycle pulse discharge method using chemical vapor deposition technology.
  • the preparation process based on a specific small duty cycle pulse discharge method cannot achieve chemical
  • the bond length and bond energy of different groups in the raw materials, the molecular weight of the material and the effective coordination and control of the energy supply, the scratch resistance and durability of the prepared coating are not satisfactory. It is precisely because of the performance limitation of the coating that the coating can only form a liquid-repellent nano-coating on electronic and electrical equipment, and the corrosion resistance to the environment cannot be effectively solved.
  • the dense protective coating prepared based on the specific small duty cycle pulse discharge method has a fatal disadvantage: from a microscopic point of view, the smaller power density during the coating process is not conducive to the formation of a dense structure, or even a stable film. Structure; macroscopically, a smaller power density is not conducive to a large rate of growth of the coating, and its effectiveness in actual production is low, which limits its application.
  • the substrate In the preparation process of the existing plasma chemical vapor deposition coating, the substrate is fixed, and the motion state of the substrate is not related to the discharge energy of the plasma; the stationary substrate is treated by the continuous discharge method.
  • the activated chain scission in the monomer is generally formed into a film by simple stacking under the action of continuous discharge, and the obtained plating layer generally has a loose structure and even a high degree of pulverization, which is disadvantageous to the formation of a microscopic dense structure of the coating layer. Waterproof, moisture-proof, corrosion-resistant, solvent-resistant and other protective properties are poor.
  • the stationary state of the substrate may result in slow deposition of coatings in some regions, low production efficiency, and a large difference in uniformity and compactness.
  • the present invention provides a method for preparing a multifunctional nano-protective coating by circulating small power continuous discharge in order to solve the above technical problems.
  • the process mainly includes a pretreatment and coating stage, the plasma discharge mode of the pretreatment stage is high power continuous discharge, the plasma discharge mode of the coating stage is low power continuous discharge, and the pretreatment and coating process are repeated at least twice. Forming a dense structure of multiple layers. And the combination of the motion characteristics of the substrate and the plasma discharge energy, while the plasma discharge energy is output, the substrate remains in motion. Additional monomeric components with a polyfunctional crosslinked structure are introduced by plasma energy to introduce additional crosslinking sites to form a crosslinked structure.
  • Plasma discharge generates plasma
  • the effective activation of the higher energy active groups in the monomer component by the low temperature plasma is achieved, and the active site is introduced, and the additional active sites are introduced.
  • they cross-link and polymerize to form a dense network structure.
  • a method for preparing a multifunctional nano-protective coating by circulating small power continuous discharge comprising: the following steps:
  • the deposition process includes a pretreatment stage and a coating stage.
  • the plasma discharge power of the pretreatment stage is 120-400 W, the continuous discharge time is 60-450 s, and then enters the coating stage, and the plasma discharge power is adjusted to 10 to 75 W, and the discharge time is continued. 600 ⁇ 3600s;
  • the purpose of the pretreatment stage is to activate the surface of the substrate to form numerous active sites on the surface of the substrate.
  • the bombardment pretreatment can clean impurities on the surface of the substrate, and at the same time, can activate the surface of the substrate, facilitate deposition of the coating, improve the adhesion of the coating to the substrate, and perform repeated coating and coating processes for each coating.
  • a plurality of active sites can be formed on the surface of the membrane layer, and the surface of the membrane layer is activated to facilitate further deposition of the coating layer, improve the bonding force between the membrane layers, and form a binding force and a density.
  • the high multi-layer coating structure compared with the general single-time long-time coating, the bonding force and the density are increased by at least 20%-40% and 15%-30%, respectively, and the cycle low-power coating method is effective and practical. Stronger.
  • the monomer vapor component is:
  • the plasma discharge form is a continuous discharge with a high power of 120-400 W
  • the plasma discharge form in the coating stage is a continuous discharge of a small power of 10 to 75 W.
  • the plasma generated by the continuous plasma discharge deposition process has a certain etching on the deposited film; the low power continuous discharge combined with the substrate motion characteristics in the coating stage is beneficial to accelerate the speed of chemical deposition, compared with the existing small duty cycle pulse.
  • the discharge technology in a certain period of time, the film thickness is thicker and denser, and the coating efficiency is higher, thereby solving the preparation method of the British P2i company based on the specific small duty cycle pulse discharge mentioned in the background art. A fatal flaw in dense protective coatings.
  • the chemical bonds in the active monomer are controlled to break, forming higher-activity free radicals, excited free radicals and surface activation groups of mobile phones and other products.
  • the group initiates polymerization to form a nanometer waterproof film by chemical bonding, and forms a multifunctional nano-coating on the surface of the substrate.
  • the substrate generates motion in the reaction chamber, and the substrate moves in the form of a linear reciprocating motion or a curved motion of the substrate relative to the reaction chamber, the curved motion including circular motion, elliptical motion, planetary motion, Curved motion of spherical motion or other irregular routes.
  • the substrate in the step (1) is a solid material
  • the solid material is an electronic product, an electrical component, an electronic assembly semi-finished product, a PCB board, a metal plate, a polytetrafluoroethylene plate or an electronic component, and the surface of the substrate
  • any interface can be exposed to water environment, mold environment, acid, alkaline solvent environment, acid, alkaline salt spray environment, acidic atmospheric environment, organic solvent soaking environment, cosmetic environment, sweat environment , use in hot and cold cycle impact environment or wet heat alternating environment.
  • the volume of the reaction chamber in the step (1) is 50 to 1000 L, the temperature of the reaction chamber is controlled at 30 to 60 ° C, and the flow rate of the inert gas is 5 to 300 sccm.
  • the reaction chamber is a rotating body chamber or a cubic chamber.
  • the monomer steam is introduced into the reaction chamber by atomizing, volatilizing and introducing the monomer into the reaction chamber by a low pressure of 10 to 200 mTorr, and the flow rate of the monomer is 10 to 1000 ⁇ L/min;
  • the monofunctional unsaturated fluorocarbon resin includes:
  • the polyfunctional unsaturated hydrocarbon derivative includes:
  • the plasma discharge modes in the steps (3) and (4) are radio frequency discharge, microwave discharge, intermediate frequency discharge, high frequency discharge, and electric spark discharge, and the waveforms of the high frequency discharge and the intermediate frequency discharge are sinusoidal or bipolar pulses.
  • the radio frequency plasma is a plasma generated by discharge of a high frequency electromagnetic field.
  • the microwave method utilizes the energy of the microwave to excite the plasma, and has the advantages of high energy utilization efficiency. At the same time, since the electrodeless discharge and the plasma are pure, it is an excellent method for high-quality, high-rate, large-area preparation.
  • the motion characteristics of the substrate and the plasma discharge energy are combined.
  • the substrate generates motion, improves the deposition efficiency of the coating, and improves the uniformity and compactness of the coating thickness.
  • the prepared coating has waterproof, moisture proof, mold proof, acid resistance, alkaline solvent, acid resistance, alkaline salt spray, acid resistance atmosphere, organic solvent immersion resistance, cosmetics resistance, sweat resistance, cold and heat cycle impact resistance (-40 ° C ⁇ +75 ° C), resistance to heat and humidity (humidity 75% to 95%) and other characteristics.
  • the coating thickness is between 1 and 1000 nm, and the influence on the RF communication signal in the range of 10M to 8G is less than 5%.
  • the cyclic coating introduces a high-power pretreatment activation stage in the process stage.
  • the cycle introduction is beneficial to introduce more active sites on the surface of the substrate at this stage, increase the effective coating, and the film structure is more compact. Corrosive environment The protection effect is better.
  • the nano-coating of the multi-layer composite structure is obtained by the cyclic coating process, which provides multi-layer protection for the product itself, and the microscopically presents a denser coating structure, which is excellent in macroscopic performance. Hydrophobicity, adhesion, acid and alkali resistance, mechanical properties and moisture and heat resistance.
  • the substrate moves in the reaction chamber, so that the coating thickness of the substrate at different positions tends to be uniform, which solves the uneven thickness of the coating on the surface of the substrate due to the different monomer density in different regions of the reaction chamber. problem.
  • the introduction of the cross-linking structure of the polyfunctional group in the monomer material promotes the formation of the dense network structure of the coating on the microstructure, and improves the acid/alkali corrosion resistance of the coating to the environment while ensuring the hydrophobicity.
  • plasma polymerization uses a monofunctional monomer to obtain a coating having a certain crosslinked structure.
  • the crosslinked structure is formed by a plurality of active sites formed by chain scission of a monomer during plasma discharge by cross-linking.
  • this crosslinked structure is relatively loose, contains more linear components, and is resistant to solution penetration and solubility.
  • the present invention introduces additional crosslinking points by introducing other monomer components with a polyfunctional crosslinked structure to form a crosslinked structure.
  • the active group with higher energy in the monomer component is broken to form an active point by effective control and output of energy, and the additional active point introduced is in the plasma environment. They cross-link and polymerize to form a dense network structure.
  • the mesh structure Compared with the coating structure with loose linear components, the mesh structure has better compactness and can effectively improve the corrosion-resistant environment of the film.
  • the surface of the coated substrate is activated to obtain a plurality of active sites.
  • the active sites are combined with the active radicals of the plasma-excited monomeric material with strong chemical bonds, and various forms of primitives are generated.
  • the reaction makes the nano film of the base material have excellent bonding force and mechanical strength.
  • portable device keyboard has small and light features, commonly used in computers, mobile phones and other equipment. It makes it easy for users to work on the journey. However, when it encounters the contamination of common liquids, such as the accidental overturn of the water cup, the soaking of rain and sweat, the inside of the keyboard is easily short-circuited and damaged. After coating with this type of nano-coating, it can ensure that the surface of the keyboard is easy to clean and function properly after being exposed to water, so that the keyboard can adapt to a more severe environment.
  • LED display has product promotion, store decoration, lighting, warning and other purposes. Some of its uses need to face the harsh environment of rain or dust, such as the rainy days, the mall's open-air LED advertising screen, road warning lights, LED display control panel in the production workshop, these harsh environments lead to LED screen failure, and easy to accumulate dust, It is difficult to clean, and after using the nano-coating, the above problems can be effectively solved.
  • fingerprint lock is a smart lock, which integrates computer information technology, electronic technology, mechanical technology and modern hardware technology, is widely used in public security criminal investigation and judicial field. However, after it meets water, its internal circuit is short-circuited, difficult to repair, and requires violent de-locking. This coating can be used to avoid this problem.
  • Some sensors need to work in a liquid environment, such as water pressure, oil pressure sensors, and sensors used in underwater operation equipment, as well as sensors that often encounter water in the working environment. These sensors use this coating. After the layer, it can guarantee that the sensor will not malfunction due to the liquid invading the internal structure of the mechanical device.
  • the multifunctional nano-coating prepared by the method can also be applied to the following different environments and related products involved:
  • Acid and alkaline solvents, acid and alkali salt spray, acid resistant atmosphere are acids and alkaline solvents, acid and alkali salt spray, acid resistant atmosphere:
  • 1 such as paraffin, olefin, alcohol, aldehyde, amine, ester, ether, ketone, aromatic hydrocarbon, hydrogenated hydrocarbon, terpene olefin, halogenated hydrocarbon, heterocyclic compound, nitrogen-containing compound and sulfur compound solvent; 2 cosmetic packaging container ; 3 fingerprint lock, headphones.
  • Resistance to cold and heat cycle (-40 ° C ⁇ +75 ° C), resistance to heat and humidity (humidity 75% ⁇ 95%): electrical, electronic, automotive electrical, such as aviation, automotive, home appliances, scientific research and other fields of equipment.
  • a method for preparing a multifunctional nano-protective coating by circulating small power continuous discharge comprises the following steps:
  • the substrate in the step (1) is a solid material, and the solid material is a block-shaped polytetrafluoroethylene plate and an electrical component, and any interface of the surface of the substrate after the coating is prepared may be exposed to GJB150.10A-2009. Used in the mold test environment, any interface of the surface of the electrical component after the coating is prepared can be exposed to the environment described in the international industrial waterproof rating standard IPX7.
  • the volume of the reaction chamber in the step (1) was 50 L, the temperature of the reaction chamber was controlled at 30 ° C, and the flow rate of the inert gas was 5 sccm.
  • the substrate moves in the reaction chamber, and the substrate moves in the form of a circular motion of the substrate relative to the reaction chamber at a rotation speed of 1 rpm.
  • the deposition process includes a pretreatment stage and a coating stage, and the plasma discharge power in the pretreatment stage is 400 W. Continue discharge time 60s, then enter the coating stage, adjust the plasma discharge power to 75W, continuous discharge time 600s;
  • step (2)
  • the monomer vapor composition is:
  • the monofunctional unsaturated fluorocarbon resin is: 2-perfluorooctyl acrylate ethyl ester, 2-(perfluorohexyl) ethyl methacrylate;
  • the polyfunctional unsaturated hydrocarbon derivative is: ethylene glycol diacrylate, 1,6-hexanediol diacrylate;
  • the plasma discharge mode in steps (3) and (4) is continuous radio frequency discharge.
  • IPX 7 waterproof rating test underwater 1m immersion test for 30 minutes
  • the obtained IPX 7 waterproof rating test (underwater 1m immersion test for 30 minutes) of the electrical component deposited with the waterproof and electrical breakdown coating is as follows:
  • a method for preparing a multifunctional nano-protective coating by circulating small power continuous discharge comprises the following steps:
  • the substrate in the step (1) is a solid material, and the solid material is a block-shaped polytetrafluoroethylene plate and an electrical component, and any interface of the surface of the substrate after the coating is prepared may be exposed to GJB150.10A-2009. Used in the mold test environment, any interface of the surface of the electrical component after the coating is prepared can be exposed to the environment described in the international industrial waterproof rating standard IPX7.
  • the volume of the reaction chamber in the step (1) was 250 L, the temperature of the reaction chamber was controlled at 40 ° C, and the flow rate of the inert gas was 15 sccm.
  • the substrate is subjected to planetary motion, the revolution speed is 2 rpm, and the rotation speed is 2.5 rpm.
  • the deposition process includes a pretreatment stage and a coating stage.
  • the plasma discharge power of the pretreatment stage is 120 W, the discharge time is 450 s, and then enters the coating stage, and the plasma discharge power is adjusted to 10 W, and the continuous discharge time is 3600 s;
  • step (2)
  • the monomer steam is introduced into the reaction chamber by atomizing and volatilizing the monomer through a feed pump, and the flow rate of the monomer vapor is 500 ⁇ L/min;
  • the monomer vapor composition is:
  • the monofunctional unsaturated fluorocarbon resin is: 2-(perfluorodecyl)ethyl methacrylate, 2-(perfluorododecyl)ethyl acrylate, (perfluorocyclohexyl)methyl Acrylate;
  • the polyfunctional unsaturated hydrocarbon derivative is: tripropylene glycol diacrylate and polyethylene glycol diacrylate;
  • the plasma discharge mode is an intermediate frequency continuous discharge, and the waveform of the intermediate frequency discharge is a bipolar pulse.
  • IPX 7 waterproof rating test underwater 1m immersion test for 30 minutes
  • the obtained IPX 7 waterproof rating test (underwater 1m immersion test for 30 minutes) of the electrical component deposited with the waterproof and electrical breakdown coating is as follows:
  • a method for preparing a multifunctional nano-protective coating by circulating small power continuous discharge comprises the following steps:
  • the substrate is a solid material
  • the solid material is a bulk alloy steel plate material
  • any interface of the substrate surface is prepared to be exposed to an organic solvent test environment after being prepared by an organic solvent-immersed and cosmetic-resistant coating. in.
  • the volume of the reaction chamber in the step (1) was 480 L, the temperature of the reaction chamber was controlled at 50 ° C, and the flow rate of the inert gas was 50 sccm.
  • the substrate was subjected to a circular motion at a rotation speed of 4 rpm.
  • the deposition process includes a pretreatment stage and a coating stage.
  • the plasma discharge power of the pretreatment stage is 200 W, the discharge time is 150 s, and then enters the coating stage, and the plasma discharge power is adjusted to 20 W, and the continuous discharge time is 1000 s;
  • step (2)
  • the monomer steam is introduced into the reaction chamber by atomizing and volatilizing the monomer through a feed pump, and the flow rate of the monomer vapor is 550 ⁇ L/min;
  • the monomer vapor composition is:
  • the monofunctional unsaturated fluorocarbon resin is: (perfluorocyclohexyl) methacrylate and 2-(perfluorohexyl)ethyl methacrylate;
  • the polyfunctional unsaturated hydrocarbon derivative is: ethoxylated trimethylolpropane triacrylate and diethylene glycol divinyl ether;
  • the plasma discharge mode in the steps (3) and (4) is a high-frequency continuous discharge, and the waveform of the high-frequency discharge is sinusoidal.
  • a method for preparing a multifunctional nano-protective coating by circulating small power continuous discharge comprises the following steps:
  • the substrate in the step (1) is a solid material, the solid material is a bulk aluminum alloy material, and any interface of the surface of the substrate can be exposed to an acid or alkali test environment after preparing an acid-proof and alkaline environment coating. .
  • the volume of the reaction chamber in the step (1) was 680 L, the temperature of the reaction chamber was controlled at 50 ° C, and the flow rate of the inert gas was 160 sccm.
  • the substrate is linearly reciprocated at a moving speed of 20 mm/min.
  • the deposition process includes a pretreatment stage and a coating stage.
  • the plasma discharge power of the pretreatment stage is 300 W
  • the continuous discharge time is 250 s
  • the plasma discharge power is adjusted to 35 W
  • the continuous discharge time is 2000 s;
  • step (2)
  • the monomer steam is introduced into the reaction chamber by atomizing and volatilizing the monomer, and is introduced into the reaction chamber by a low pressure of 160 mTorr, and the flow rate of the monomer vapor is 220 ⁇ L/min;
  • the monomer vapor composition is:
  • the monofunctional unsaturated fluorocarbon resin is: 3,3,3-trifluoro-1-propyne, 3-(perfluoro-5-methylhexyl)-2-hydroxypropyl methacrylate, 1H , 1H, 2H, 2H-perfluorooctyl acrylate;
  • the polyfunctional unsaturated hydrocarbon derivatives are: ethoxylated trimethylolpropane triacrylate, ethylene glycol diacrylate and 1,6-hexanediol diacrylate;
  • the plasma discharge mode in steps (3) and (4) is microwave continuous discharge.
  • a method for preparing a multifunctional nano-protective coating by circulating small power continuous discharge comprises the following steps:
  • the substrate in the step (1) is a solid material, the solid material is an electronic component, and any interface of the surface of the substrate after the preparation of the moisture-resistant heat alternating coating can be exposed to the damp heat test environment.
  • the volume of the reaction chamber in the step (1) was 1000 L, the temperature of the reaction chamber was controlled at 60 ° C, and the flow rate of the inert gas was 300 sccm.
  • the substrate is subjected to planetary motion, the planetary revolution speed is 1 rpm, and the planetary rotation speed is 1.5 rpm.
  • the deposition process includes the pretreatment stage and the coating stage.
  • the plasma discharge power of the pretreatment stage is 150W
  • the continuous discharge time is 400s
  • the plasma discharge power is adjusted to 55W
  • the continuous discharge time is 3000s;
  • step (2)
  • the monomer steam is introduced into the reaction chamber by atomizing and volatilizing the monomer through a feed pump, and the flow rate of the monomer vapor is 10 ⁇ L/min;
  • the monomer vapor composition is:
  • the monofunctional unsaturated fluorocarbon resin is: 1H, 1H, 2H, 2H-perfluorooctyl acrylate, 3,3,3-trifluoro-1-propyne and 2-(perfluorohexyl)ethyl Methacrylate
  • the polyfunctional unsaturated hydrocarbon derivative is: tripropylene glycol diacrylate and ethylene glycol diacrylate;
  • the plasma discharge mode in steps (3) and (4) is a spark discharge.
  • Step (1) pumping the vacuum in the reaction chamber to 120 mTorr, and introducing an inert gas Ar;
  • Step (1) The substrate is a solid material, the solid material is a bulk aluminum material and a printed wiring board, and the surface of the substrate is prepared to be exposed to cold and heat after being subjected to a cold and heat resistant cyclic impact coating. In a loop test environment.
  • the volume of the reaction chamber is 400 L
  • the temperature of the reaction chamber is controlled at 40 ° C
  • the flow of the inert gas is introduced.
  • the amount is 150 sccm.
  • the deposition process includes a pretreatment stage and a coating stage.
  • the plasma discharge power of the pretreatment stage is 180 W, the continuous discharge time is 200 s, and then enters the coating stage, the plasma discharge power is adjusted to 60 W, and the continuous discharge time is 1500 s;
  • the monomer steam is introduced into the monomer through the feed pump for atomization, volatilization, introduced into the reaction chamber by a low pressure of 160 mTorr, the flow rate of the monomer vapor is 200 ⁇ L / min;
  • the monomer vapor composition is:
  • the monofunctional unsaturated fluorocarbon resin is: 2-(perfluorodecyl)ethyl methacrylate, 1H, 1H, 2H, 2H-perfluorooctyl acrylate, 3,3,3-trifluoro 1-propyne and 2-(perfluorohexyl)ethyl methacrylate;
  • the polyfunctional unsaturated hydrocarbon derivative is: tripropylene glycol diacrylate and diethylene glycol divinyl ether;
  • Step (5) Keep the reaction chamber vacuum at 160 mTorr for 5 min and then pass to the atmosphere to an atmospheric pressure.

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Abstract

L'invention concerne un procédé de préparation d'un nanorevêtement protecteur multifonctionnel au moyen d'une décharge cyclique continue de faible puissance. Le procédé comprend les étapes consistant à : (1) placer un substrat dans une cavité de réaction d'un dispositif de préparation de nanorevêtement, mettre la cavité de réaction sous vide en continu d'une manière telle que le degré de vide dans la cavité de réaction atteint 10 à 200 millitorrs, introduire le gaz inerte He ou Ar dans la cavité de réaction et lancer un mécanisme de déplacement de telle sorte que le substrat se déplace dans la cavité de réaction ; (2) introduire une vapeur de monomère dans la cavité de réaction jusqu'à atteindre un degré de vide de 30 à 300 millitorrs et initier une décharge de plasma permettant un dépôt chimique en phase vapeur ; (3) le processus de dépôt comprenant une phase de prétraitement et une phase de placage de film, la puissance de la décharge de plasma étant comprise entre 120 et 400 W et la durée de la décharge étant comprise entre 60 à 450 s au cours de la phase de prétraitement, puis la phase de placage de film est lancée, la puissance de la décharge de plasma étant alors régulée entre 10 et 75 W et la durée de la décharge étant régulée entre 600 et 3600 s ; (4) répéter de manière cyclique la phase de prétraitement et la phase de placage de film au cours de l'étape (3) au moins une fois de façon à préparer un nanorevêtement multifonctionnel sur une surface du substrat au moyen d'un dépôt chimique en phase vapeur ; le composant de la vapeur de monomère étant un mélange d'au moins une résine fluorocarbonée insaturée monofonctionnelle et d'au moins un dérivé d'hydrocarbure insaturé polyfonctionnel, la fraction massique du dérivé d'hydrocarbure insaturé polyfonctionnel dans la vapeur de monomère étant comprise entre 15 et 65 % ; et (5) interrompre l'introduction de la vapeur de monomère tout en interrompant la décharge de plasma, poursuivre la mise sous vide, maintenir la cavité de réaction à un degré de vide compris entre 10 et 200 millitorrs pendant 1 à 5 min, introduire l'atmosphère jusqu'à atteindre une pression atmosphérique, interrompre le déplacement du substrat et retirer le substrat.
PCT/CN2017/113189 2017-05-21 2017-11-27 Procédé de préparation d'un nanorevêtement protecteur multifonctionnel au moyen d'une décharge cyclique continue de faible puissance WO2018214447A1 (fr)

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US16/688,845 US11742186B2 (en) 2017-05-21 2019-11-19 Multi-functional protective coating
US16/688,589 US11270871B2 (en) 2017-05-21 2019-11-19 Multi-layer protective coating
US17/653,401 US11587772B2 (en) 2017-05-21 2022-03-03 Multi-layer protective coating

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CN201710360355.5A CN107142465B (zh) 2017-05-21 2017-05-21 一种循环小功率连续放电制备多功能性纳米防护涂层的方法
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PCT/CN2017/113190 Continuation-In-Part WO2018214448A1 (fr) 2017-05-21 2017-11-27 Procédé de préparation d'un nano-revêtement protecteur multifonctionnel au moyen d'une décharge d'impulsion à rapport cyclique élevé
PCT/CN2017/113190 Continuation WO2018214448A1 (fr) 2017-05-21 2017-11-27 Procédé de préparation d'un nano-revêtement protecteur multifonctionnel au moyen d'une décharge d'impulsion à rapport cyclique élevé
PCT/CN2017/113192 Continuation-In-Part WO2018214450A1 (fr) 2017-05-21 2017-11-27 Procédé de préparation d'un nano-revêtement protecteur multifonctionnel au moyen d'une décharge alternée périodique
PCT/CN2017/113188 Continuation-In-Part WO2018214446A1 (fr) 2017-05-21 2017-11-27 Procédé de préparation d'un nanorevêtement protecteur multifonctionnel au moyen d'une décharge continue de faible puissance

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US16/688,589 Continuation-In-Part US11270871B2 (en) 2017-05-21 2019-11-19 Multi-layer protective coating

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