WO2015157880A1 - Procédé de revêtement pour nano-revêtement de surface d'un métal de forme irrégulière - Google Patents

Procédé de revêtement pour nano-revêtement de surface d'un métal de forme irrégulière Download PDF

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WO2015157880A1
WO2015157880A1 PCT/CN2014/000863 CN2014000863W WO2015157880A1 WO 2015157880 A1 WO2015157880 A1 WO 2015157880A1 CN 2014000863 W CN2014000863 W CN 2014000863W WO 2015157880 A1 WO2015157880 A1 WO 2015157880A1
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oxide
fluorocarbon
layer
coating method
oxysilane
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傅榆
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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
    • C23C16/45523—Pulsed gas flow or change of composition over time
    • C23C16/45525—Atomic layer deposition [ALD]
    • 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
    • C23C16/22—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 deposition of inorganic material, other than metallic material
    • C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
    • C23C16/40—Oxides
    • C23C16/403—Oxides of aluminium, magnesium or beryllium
    • 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
    • C23C16/22—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 deposition of inorganic material, other than metallic material
    • C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
    • C23C16/40—Oxides
    • C23C16/405—Oxides of refractory metals or yttrium
    • 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
    • C23C16/22—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 deposition of inorganic material, other than metallic material
    • C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
    • C23C16/40—Oxides
    • C23C16/407—Oxides of zinc, germanium, cadmium, indium, tin, thallium or bismuth

Definitions

  • the present invention relates to a surface treatment method for a metal, and more particularly to a coating method for a nano surface coating on a profiled metal and a nano surface coating thereof, the surface treatment method such that the metal surface does not affect the appearance texture It can achieve surface characteristics of hydrophobic, oleophobic, anti-fouling, anti-fingerprint and low surface energy.
  • the anti-fouling coating on the metal is mostly a resin coating, and the resin coating has a high thickness (>1 micrometer to several hundred micrometers), which destroys the appearance of the product (if the mirror surface is used, the brightness of the original surface cannot be retained) Low hardness (1H ⁇ 5H), insufficient anti-staining ability and durability.
  • a non-resin coating such as methoxysilane fluorocarbon nano anti-fingerprint coating, the problem of such coating is very poor surface adhesion, as long as the cloth Wipe it a little and it will disappear.
  • a vacuum coating technique such as physical weather deposition (such as evaporation or magnetron sputtering) or chemical weather deposition CVD to deposit an oxide film having a hydroxyl group (-OH) on the metal surface (such as SiO 2 ), followed by coating of the subsequent methoxysilane fluorocarbon nano anti-fingerprint coating.
  • a vacuum coating technique such as physical weather deposition (such as evaporation or magnetron sputtering) or chemical weather deposition CVD to deposit an oxide film having a hydroxyl group (-OH) on the metal surface (such as SiO 2 ), followed by coating of the subsequent methoxysilane fluorocarbon nano anti-fingerprint coating.
  • the present invention provides a nano surface for use on a shaped metal.
  • Coating method of coating which can be uniformly plated on all surfaces of the shaped product, the thickness of the coating is only 10 nanometers, which does not affect the appearance of the product, has high hardness, strong anti-fouling ability, acid and alkali resistance, abrasion resistance Durable and durable.
  • One of the objects of the present invention is to provide a coating method for a nano surface coating on a profiled metal, the method comprising forming at least one oxide film layer on a metal surface by atomic vapor deposition, and then performing the oxidation At least one layer of fluorocarbon film is plated on the film layer.
  • an oxide film has a thickness of from 1 nm to 1 ⁇ m. It should be noted that the oxide thin film layer is formed by laminating a plurality of oxide films, or may be a single oxide film, which is determined according to specific production requirements.
  • the coating method for the nano surface coating on the shaped metal of the present invention specifically includes the following steps: step 1) placing the shaped metal into the vacuum chamber; and trimethyl aluminum, titanium tetrachloride or diethyl zinc, etc.
  • the organometallic compound vapor is introduced into a vacuum chamber of 100 ° C to 300 ° C to cause physical or chemical adsorption with the surface; nitrogen is used to remove excess unreacted organometallic compound; and then water vapor or ozone is introduced into the vacuum chamber.
  • step 2 repeats 50 cycles to make one Thin layer oxide
  • the atomic layer of the film is stacked to form a 5 nm dense oxide film layer; and step 3) applying an oxysilane-based fluorocarbon to the surface of the oxide film layer by vacuum evaporation or liquid immersion coating.
  • the oxysilane group of the oxysilane-based fluorocarbon reacts with the surface functional group hydroxyl group (-OH) of the oxide thin film layer, and finally is baked at 60 to 150 ° C to make the reaction more complete, thereby obtaining a metal surface.
  • Anti-fingerprint fluorinated film layer The above is the coating step of the anti-fingerprint fluorinated film layer on the metal surface.
  • the oxide thin film coating technology is an atomic layer vapor deposition technique
  • the atomic layer or the oxide thin film layer of the oxide thin film is silicon oxide (SiO 2 ), zirconium oxide (ZrO 2 ), or aluminum oxide ( Al 2 O 3 ), zinc oxide (ZnO), titanium oxide (TiO 2 ), tantalum oxide (Ta 2 O 5 ), indium oxide (In 2 O 3 ) or hafnium oxide (HfO 2 ).
  • the chemical structure of the oxysilane-based fluorocarbon is as follows: (I), consisting of a fluorinated anti-staining hydrophobic group and a reactive group;
  • a is 0 to 20
  • Y is H, F, C n F 2n+1 or C n H 2n+1
  • n is a positive integer, preferably n is 1 to 20, and X is H or F, K is 0 to 20, r is 0 to 20, and h is 0 to 20;
  • the chemical structure of the reaction-substituting group includes the following two chemical structural formulas (1) and (2):
  • n can be 1 to 20;
  • the oxysilane-based fluorocarbon is trimethoxysilane fluorocarbon, triethoxy silane fluorocarbon, trichlorosilane fluorocarbon;
  • the trimethoxy silane fluorocarbon is perfluoroanthracene a trimethoxysilane or a perfluorodecyltrimethoxysilane;
  • the triethoxysilane fluorocarbon is perfluorodecyltriethoxysilane;
  • the vacuum chamber of the vacuum chamber in step 1) has a vacuum pressure of 0.1 Torr.
  • the vacuum evaporation method in the step 2) comprises: placing the shaped metal coated with the oxide layer vapor-deposited with the atomic layer and the oxysilane-based fluorocarbon in a vacuum chamber, and the oxysilane The fluorocarbon is heated to vaporize it, and heated to 150 ° C in a vacuum chamber to close the pumping pipe, so that the vacuum tank is in a sealed state, and the vaporized oxysilane fluorocarbon is plated on the atomic layer. Vapor-depositing the oxide surface to form a structure of aluminum oxysiloxane, titanyl silicon oxide or zinc oxysilicon.
  • the pumping pipe is opened and nitrogen gas is introduced to remove excess oxysilane-based fluorocarbon vapor to make the surface A single layer of fluorocarbon molecules is left to form an anti-fingerprint fluorinated film layer.
  • the vacuum chamber has a vacuum pressure of less than 1 Torr.
  • the liquid soaking coating method in the step 2) comprises: dissolving the oxysilane-based fluorocarbon in a fluoroether solvent to form a solution; using conventional spraying, conventional smearing or conventional immersion
  • the surface of the shaped metal applied to the vapor-deposited oxide coated with the atomic layer is wetted to form a structure of aluminum oxysiloxane, titanyl silicon or zinc oxysilicon.
  • the ultrasonic vibration is used to remove the residue.
  • the remaining oxysilane-based fluorocarbon is washed to leave a single layer of oxysilicon fluorocarbon molecules on the surface to form an anti-fingerprint fluorinated film layer.
  • the solution has a weight concentration of 0.3 to 0.8 wt.%
  • the fluoroether solvent is 1,1,2,2-tetrafluoroethyl-2,2,3,3-tetrafluoropropyl ether.
  • the main working principle of the coating method of the present invention is to uniformly coat a metal surface with a nano-scale oxide film by utilizing the characteristics of three-dimensional all-round uniform plating of atomic layer vapor deposition (ALD).
  • the surface functional group of the oxide film is bonded to the oxysilane-based fluorocarbon, and the anti-fingerprint fluorinated film is strongly bonded to the metal surface to achieve a highly durable anti-wear effect.
  • ALD atomic layer vapor deposition
  • the oxide film may be one or more layers of alumina Al 2 O 3 plated on a metal surface.
  • the raw material is trimethylaluminum Al(CH 3 ) 3 and water.
  • the trimethyl aluminum and water are introduced into the vacuum chamber, and the temperature of the cavity is 100 ° C, which reacts with each other to form an aluminum oxide film.
  • the alumina film is uniformly applied to the surface of any product that is exposed to the gas.
  • the oxide can also be titanium oxide (TiO 2 ), silicon oxide (SiO 2 ), zinc oxide (ZnO), zirconium oxide (ZrO 2 ), tantalum oxide (Ta 2 O 5 ), indium oxide (In 2 O 3 )
  • An ALD-grown metal oxide such as hafnium oxide (HfO2).
  • the alumina produced per cycle has a thickness of about 0.1 nm.
  • the trimethyl aluminum cycle was alternately introduced into the cavity, and after completion of 50 cycles, an approximately 5 nm aluminum oxide film was plated on the surface of the product.
  • a trimethoxysilane fluorocarbon is plated on the surface of the Al 2 O 3 film by vacuum evaporation or liquid immersion coating, and baked at 60 to 150 ° C to form a primary antibody. Fingerprint fluorinated film layer.
  • the atomic layer vapor deposition technique oxide film can be physically or chemically bonded to the metal surface and uniformly plated over the entire product surface with the same film thickness.
  • the atomic layer vapor deposition technique has a chemical functional group on the surface in contact with air after the oxide film is grown to be a hydroxyl group (-OH), which is mainly used as a bonding functional group of the subsequent trimethoxysilane fluorocarbon.
  • a hydroxyl group (-OH)
  • trimethoxysilane fluorocarbon is coated on the oxide film, the chemical reaction is accelerated by baking, and finally an anti-fingerprint fluorinated film layer is obtained.
  • the anti-fingerprint fluorinated film has a thickness of about 10 nm.
  • Another object of the present invention is to provide a nano surface coating layer coated on a profiled metal by the coating method, the nano surface plating layer comprising an oxide film layer and an anti-fingerprint fluorinated film layer;
  • the thickness of the nano surface plating layer is from 1 nm to 1 ⁇ m.
  • the oxide thin film layer has a thickness of 1 to 5 nm
  • the anti-fingerprint fluorescent thin film layer has a thickness of 5 to 10 nm.
  • the oxide thin film layers are all silicon oxide (SiO 2 ), zirconium oxide (ZrO 2 ), aluminum oxide (Al 2 O 3 ), zinc oxide (ZnO), titanium oxide (TiO 2 ), and tantalum oxide (Ta). 2 O 5 ), indium oxide (In 2 O 3 ) or yttrium oxide (HfO 2 ).
  • the invention has the beneficial effects that the anti-fingerprint fluorinated film layer is finally obtained to have a thickness of about 10 nm, and the composition is an inner layer ALD-plated oxide film, and the outer layer is an anti-fingerprint fluorinated film layer. Due to the planar physical or chemical bonding between the metal and the oxide film, the methyl silane fluorocarbon is chemically bonded to the oxide film, so that the entire anti-fingerprint fluorinated film is a strong bond as a link, so the entire film Its mechanical strength and adhesion will be very good.
  • the metal product can change the surface properties of the surface without affecting the appearance.
  • the 10 nm nano-fluorinated film can achieve hydrophobic, oleophobic, anti-fouling, anti-fingerprint, low surface energy surface characteristics, and the treated metal can be treated.
  • the product has the advantages of being non-staining, easy to clean and smooth to the touch.
  • the film has high hardness, strong anti-staining ability and strong acid and alkali resistance.
  • Nano-scale anti-fingerprint anti-fouling surface fluorination technology is mainly formed by chemical reaction of oxysilane-based fluorocarbon molecules with hydroxyl groups (-OH) on the surface of the product, due to oxysilane-based fluorocarbons and surface functionalities.
  • -OH hydroxyl groups
  • nano-scale anti-fingerprint anti-fouling surface fluorination technology can only be used in glass products, the main reason is that the glass surface is filled with oxysilane-based fluorocarbons.
  • a functional group (silicon hydroxy (-OH)), which facilitates chemical adsorption of silane-based fluorocarbons to produce chemical bonds, which provides high-strength surface adsorption capacity of the nano-anti-fingerprint anti-fouling surface fluorinated coating.
  • the coating has anti-wear, acid and alkali resistance and durability.
  • the metal surface lacks a group (such as a silyl group) which can chemically react with the oxysilane-based fluorocarbon, the oxysilane-based fluorocarbon cannot form an effective and durable anti-fingerprint surface fluorination coating on the metal surface. .
  • the invention utilizes atomic layer vapor deposition (ALD) to coat a metal surface with a nano-scale oxide film which completely covers the surface and has a uniform thickness.
  • ALD atomic layer vapor deposition
  • the oxide film will be physically or chemically bonded to the surface of the metal surface, and
  • the surface provides an effective functional group (hydroxyl (-OH)) to form a bond with the oxysilane-based fluorocarbon, so that the anti-fingerprint fluorinated film is strongly bonded to the metal surface to achieve a highly durable anti-wear effect.
  • Atomic Layer Vapor Deposition is a surface-reaction deposition technique.
  • the principle of deposition is to use two or more gas precursors to circulate into the vacuum chamber to be reacted, so that the precursors react with each other to generate A solid film that will be uniformly plated onto all exposed surfaces of the object to be plated, the thickness of which is determined by the number of times the precursor circulates into the cavity.
  • the film that can be produced by this technology includes metal, polymer and metal oxide films.
  • a specific embodiment of the atomic layer vapor deposition technique (ALD) of the present invention is characterized in that the processed metal product is stainless steel and the film is an alumina Al 2 O 3 film, and trimethylaluminum (CH 3 ) 3 Al and water H 2 are used. O is used as a raw material for its reaction.
  • ALD atomic layer vapor deposition technique
  • the specific embodiment of the atomic layer vapor deposition technique (ALD) of the present invention is characterized in that the processed metal product is stainless steel, the film is a zirconia ZrO 2 film, and zirconium tetrachloride ZrCl 4 and water H 2 O are used as reaction raw materials. .
  • the stainless steel product is placed in a vacuum chamber heated at 300 ° C, and the vacuum chamber is evacuated to a vacuum state (pressure is about 0.1 Torr); 2) zirconium tetrachloride vapor is introduced into the vacuum chamber, tetrachloro
  • the zirconium vapor will chemically react with the OH group on the surface of the stainless steel product, releasing hydrochloric acid (HCl) and forming (-O-ZrCl 3 ) on the surface; 3) passing nitrogen into the vacuum chamber, and reacting excess with the surface
  • the zirconium tetrachloride is removed, leaving only a single molecular layer of zirconium tetrachloride on the surface of the stainless steel; 4) the water vapor is introduced into the vacuum chamber, and the zirconium tetrachloride that hits the surface of the water vapor will rapidly Reacts with its chloro-functional group and produces three parts of hydrochloric acid (HCl), so that the surface structure becomes (-
  • steps 1), 2), 3), 4) and 5) are referred to as a cycle, and one cycle will provide a one-molecular layer of ZrO 2 on the surface of the stainless steel, which grows to a thickness of about 0.06 nm. 6)
  • the control of the thickness of the surface zirconia ZrO 2 was achieved, so that the thickness of the zirconia film reached 3 nm, and the film growth was completed in the above 50 cycles.
  • the specific embodiment of the atomic layer vapor deposition technique (ALD) of the present invention is characterized in that the processed metal product is a chrome-plated metal member, and the thin film is a zinc oxide ZnO thin film, and diethyl zinc Zn(C 2 H 5 ) 2 and water H are used. 2 O is used as a raw material for its reaction.
  • the chrome-plated metal product is placed in a vacuum chamber heated at 100 ° C, and the vacuum chamber is evacuated to a vacuum state (pressure is about 0.1 Torr); 2) the diethyl zinc vapor is introduced into the vacuum chamber, The ethyl zinc vapor will chemically react with the OH group on the surface of the chrome-plated metal product, releasing hydrochloric acid (HCl) and forming (-O-Zn(C 2 H 5 )) on the surface; 3) passing nitrogen into the vacuum chamber To remove excess diethyl zinc that has not reacted with the surface, leaving only a single molecular layer of diethylzinc on the surface of the stainless steel; 4) then introducing water vapor into the vacuum chamber, and the water vapor hits the surface of the second Ethyl zinc will rapidly react with its ethyl group to form ethane (C 2 H 6 ), making the surface structure (-O-Zn(OH)); 5) then the same nitrogen gas will be redundant Unreacted water vapor is
  • steps 1), 2), 3), 4) and 5) are referred to as a cycle, and one cycle will provide a layer of ZnO on the chrome-plated metal surface, which grows to a thickness of about 0.2 nm. 6) After 50 cycles of the operation control, the thickness of the surface zinc oxide ZnO was controlled so that the thickness of the zinc oxide film reached 10 nm, and the film growth was completed in the above 50 cycles.
  • the specific embodiment of the atomic layer vapor deposition technique (ALD) of the present invention is characterized in that the processed metal product is stainless steel and the thin film is a titanium oxide TiO 2 film, and titanium tetrachloride TiCl 4 and water H 2 O are used as reaction raw materials. .
  • the stainless steel product is placed in a vacuum chamber heated at 300 ° C, and the vacuum chamber is evacuated to a vacuum state (pressure is about 0.1 Torr); 2) titanium tetrachloride vapor is introduced into the vacuum chamber, tetrachloro The zirconium vapor will chemically react with the OH group on the surface of the stainless steel product, releasing hydrochloric acid (HCl) and forming (-O-TiCl 3 ) on the surface; 3) passing nitrogen into the vacuum chamber, and reacting excess with the surface The titanium tetrachloride is pumped away, leaving only a single molecular layer of titanium tetrachloride on the surface of the stainless steel; 4) the water vapor is introduced into the vacuum chamber, and the titanium tetrachloride that hits the surface of the water vapor will rapidly Reacts with its chloro-functional group and produces three parts of hydrochloric acid (HCl), so that the surface structure becomes (-O-Ti(OH) 3 );
  • steps 1), 2), 3), 4) and 5) are referred to as a cycle, and one cycle will provide a layer of TiO 2 on the surface of the stainless steel which grows to a thickness of about 0.06 nm. 6)
  • the control of the thickness of the surface titanium oxide TiO 2 was achieved, so that the thickness of the zirconia film reached 3 nm, and the film growth was completed in the above 50 cycles.
  • the specific embodiment of the atomic layer vapor deposition technique (ALD) of the present invention is characterized in that the processed metal product is stainless steel and the film is a hafnium oxide HfO 2 film, and hafnium tetrachloride HfCl 4 and water H 2 O are used as reaction raw materials. .
  • steps 1), 2), 3), 4) and 5) are referred to as a cycle, and one cycle will provide a layer of HfO 2 on the surface of the stainless steel which grows to a thickness of about 0.06 nm. 6) After 50 cycles of the operation control, the thickness of the surface yttrium oxide HfO 2 was controlled so that the thickness of the zirconia film reached 3 nm, and the film growth was completed in the above 50 cycles.
  • the specific embodiment of the atomic layer vapor deposition technique (ALD) of the present invention is characterized in that the processed metal product is stainless steel and the film is a tantalum oxide (Ta 2 O 5 ) film, and the crucible pentachloride TaCl 5 and water H 2 O are used. As a raw material for its reaction.
  • ALD atomic layer vapor deposition technique
  • the antimony pentachloride is pumped away, leaving only a single molecular layer of antimony pentachloride on the surface of the stainless steel; 4) then passing water vapor into the vacuum chamber, the water vapor will hit the surface of the antimony pentachloride will be rapid Reacts with its chloro-functional group and produces four parts of hydrochloric acid (HCl), so that the surface structure becomes (-O-Ta(OH) 3 ); 5) then the same unreacted nitrogen gas will bring excess unreacted water vapor go.
  • the above steps 1), 2), 3), 4) and 5) are referred to as a cycle, and one cycle will provide a layer of Ta 2 O 5 on the surface of the stainless steel which grows to a thickness of about 0.03 nm. 6) After 50 cycles of the operation control, the thickness of the surface cerium oxide Ta 2 O 5 was controlled so that the thickness of the zirconia film reached 1.5 nm, and the film growth was completed in the above 50 cycles.
  • the specific embodiment of the atomic layer vapor deposition technique (ALD) of the present invention is characterized in that the processed metal product is stainless steel and the film is an indium oxide (In 2 O 3 ) film, and indium trichloride InCl 3 and water H 2 O are used. As a raw material for its reaction.
  • ALD atomic layer vapor deposition technique
  • the stainless steel product is placed in a vacuum chamber heated at 300 ° C, and the vacuum chamber is evacuated to a vacuum state (pressure is about 0.1 Torr); 2) the indium trichloride vapor is introduced into the vacuum chamber, trichloro The indium vapor will chemically react with the OH group on the surface of the stainless steel product, releasing hydrochloric acid (HCl) and forming (-O-InCl 2 ) on the surface; 3) passing nitrogen into the vacuum chamber to react the excess with the surface The indium trichloride is pumped away, leaving only a single molecular layer of indium trichloride on the surface of the stainless steel; 4) the water vapor is introduced into the vacuum chamber, and the indium trichloride on the surface of the water vapor will rapidly Reacts with its chloro-functional group and produces two parts of hydrochloric acid (HCl), so that the surface structure becomes (-O-In(OH) 2 ); 5) then the same unreacted nitrogen gas will bring
  • steps 1), 2), 3), 4) and 5) are referred to as a cycle, and one cycle will provide a layer of In 2 O 3 on the surface of the stainless steel which grows to a thickness of about 0.03 nm.
  • the low surface energy of 1H, 1H, 2H, 2H perfluorodecyl triethoxysilane is chemically etched by vacuum evaporation or liquid immersion coating.
  • the structural formula is as shown in the chemical formula (A), and is plated on the surface of the atomic layer vapor-deposited alumina film to make the oxysilane group of 1H, 1H, 2H, 2H perfluorodecyltriethoxysilane and the aluminum oxide film layer.
  • the hydroxyl group (-OH) is reacted, and the chemical structure of the aluminum oxysilane (Al-O-Si-7) is removed by removing the ethanol.
  • the reaction was finally completed by baking at 100 ° C for 3 hours to form an anti-fingerprint fluorinated film layer of about 5 nm.
  • the low surface energy trimethoxysilane fluorocarbide is chemically cooled by vacuum evaporation or liquid immersion coating, and the chemical structure is as shown in the chemical formula (B).
  • the methoxysilane group of the trimethoxysilane-based fluorocarbon is reacted with the hydroxyl group (-OH) of the titanium oxide thin film layer, and the methanol is removed to form titanium oxysilicon ( The chemical structure of Ti-O-Si-.).
  • the reaction was finally completed by baking at 150 ° C for 1.5 hours to form an anti-fingerprint fluorinated film layer of about 10 nm.
  • the low surface energy of 1H, 1H, 2H, 2H perfluorodecyltrichlorosilane is carried out by vacuum evaporation or liquid immersion coating, and its chemical structure is as follows.
  • the chemical formula (C) is plated onto the surface of the silicon oxide film deposited by atomic layer vapor deposition to make the chlorosilane group of 1H, 1H, 2H, 2H perfluorodecyltrichlorosilane and the hydroxyl group (-OH) of the silicon oxide thin film layer
  • the reaction is carried out to remove hydrogen chloride to form a chemical structure of silicon siloxane (Si-O-Si-.).
  • the reaction was finally completed by baking at 60 ° C for 2 hours to form an anti-fingerprint fluorinated film layer of about 5 nm.
  • the low surface energy trimethoxysilane fluorocarbon is subjected to vacuum evaporation or liquid immersion coating, and its chemical structure is as shown in the chemical formula (D).
  • the methoxysilane group of the trimethoxysilane fluorocarbon is reacted with the hydroxyl group (-OH) of the zinc oxide thin film layer, and the methanol is removed to form zinc oxysilicon (Zn). -O-Si-....) chemical structure.
  • the reaction was finally completed by baking at 80 ° C for 3 hours to form an anti-fingerprint fluorinated film layer of about 12 nm.
  • the low surface energy of 1H, 1H, 2H, 2H perfluorodecyltrimethoxysilane is chemically evaporated by vacuum evaporation or liquid immersion coating.
  • the chemical formula (E) is plated on the surface of the ruthenium oxide film deposited by atomic layer vapor deposition to make the methylsilane group of 1H, 1H, 2H, 2H perfluorodecyltrimethoxysilane and the hydroxyl group of the ruthenium oxide thin film layer.
  • (-OH) The reaction was carried out to remove methanol to form a chemical structure of silicon oxide (Ta-O-Si-.).
  • the reaction was finally completed by baking at 100 ° C for 1.5 hours to form an anti-fingerprint fluorinated film layer of about 5 nm.
  • the low surface energy of 1H, 1H, 2H, 2H perfluorooctyltrichlorosilane is carried out by vacuum evaporation or liquid immersion coating, and its chemical structure is as follows.
  • Chemical formula (F) plated to the surface of the atomic layer vapor deposited indium oxide film, the chlorosilane group of 1H, 1H, 2H, 2H perfluorooctyltrichlorosilane and the hydroxyl group (-OH) of the indium oxide thin film layer
  • the reaction is carried out to remove hydrogen chloride to form a chemical structure of indium oxysilicon (In-O-Si-.).
  • the reaction was finally completed by baking at 100 ° C for 1.5 hours to form an anti-fingerprint fluorinated film layer of about 4 nm.
  • the low surface energy of 1H, 1H, 2H, 2H perfluorodecyltrimethoxysilane is chemically structured by vacuum evaporation or liquid immersion coating.
  • the chemical formula (G) is plated on the surface of the ruthenium oxide film deposited by atomic layer vapor deposition to make the methylsilane group of 1H, 1H, 2H, 2H perfluorodecyltrimethoxysilane and the hydroxyl group of the ruthenium oxide thin film layer ( -OH)
  • the reaction is carried out to remove methanol to form a chemical structure of silicon oxyhydroxide (Hf-O-Si-.).
  • the reaction was finally completed by baking at 100 ° C for 1.5 hours to form an anti-fingerprint fluorinated film layer of about 5 nm.
  • the stainless steel product of the above examples (I-1, I-2, I-3, I-4, I-5, I-6, I-7) and the oxysilane-based fluorocarbon are placed in a vacuum chamber.
  • the pressure in the vacuum chamber is pumped to below 1 torr, and the oxysilane-based fluorocarbon is heated by electron beam or electric heating wire to vaporize, and the vacuum chamber is heated to 150 ° C and the pumped pipe is closed to allow vacuum.
  • the groove exhibits a state of being sealed and filled with oxysilane-based fluorocarbon vapor.
  • oxysilane-based fluorocarbon Dissolving the oxysilane-based fluorocarbon in a fluoroether solvent, adjusting the weight concentration to about 0.8%, and then applying the liquid to the above embodiment (I-1, by conventional spraying, conventional application or conventional immersion).
  • the oxysilane-based fluorocarbon in solution contacts the hydroxyl group (-OH) on the surface of the product to form a chemical bond, forming a chemical structure of aluminum oxysilane (Al-O-Si-.).
  • the chemical structure of the oxysilane-based fluorocarbon can be divided into two parts, the first part being a fluorinated anti-fouling water-transporting group and the second part being a reaction-substituting group.
  • the structure of the fluorinated anti-fouling water-transporting group is as follows (I-1):
  • a is 0 to 20
  • Y can be H, F, C n F 2n+1 or C n H 2n+1
  • n is a positive integer, preferably n is 1-20
  • X can be H or F
  • K is 0 to 20
  • r is 0 to 20
  • h is 0 to 20.
  • the main function of this group is to use the low surface energy characteristics of fluorine atoms or hydrocarbon molecules to achieve the effect of anti-fouling water.
  • n in the structure (1) may be 1-20.
  • the oxysilane-based fluorocarbon When the oxysilane-based fluorocarbon is applied to the metal surface of the alumina Al 2 O 3 plating, the oxysilane-based fluorocarbon may be covered with a hydroxyl group (-OH) by vacuum evaporation or liquid immersion coating. The surface of alumina Al 2 O 3 is then baked at 60-150 ° C.
  • a chemical reaction occurs between them, and the structure (1) is
  • the oxyalkyl-OC n H 2n+1 will combine with the hydrogen H atom of the hydroxyl group (-OH) to form the alcohol C n H 2n+1 OH leaving the surface, and the remaining groups form a surface.
  • Chemical bonding the chemical reaction is shown in the figure below.
  • the surface of the surface of the metal covered by the atomic layer vapor-deposited oxide and oxysilane-based fluorocarbon will be affected by the low surface energy fluorination group, which will reduce the surface energy of the entire surface. Further, the surface properties of hydrophobic, oleophobic, and antifouling are achieved. In addition, since the surface, the alumina and the oxysilane-based fluorocarbon are bonded by chemical bonding, the film has excellent resistance to solvent, acid and alkali resistance and mechanical strength.
  • the invention uniformly coats an oxide film on the surface of the metal product by using an atomic layer vapor deposition technique, and the oxide film is used as an adhesive layer of the oxysilane fluorocarbon, so that the oxysilane fluorocarbon can be chemically bonded. Attached to the metal surface to provide a high degree of film strength.
  • the contact angle test, the abrasion resistance test, the artificial sweat, the detergent resistance, the acid resistance and the alkali resistance were carried out by the oxide film layer prepared in Example I-4 and the anti-fingerprint fluorinated film layer prepared in Example II-2.
  • the performance test of glare, high temperature, high humidity and hot water gives the following experimental results (see Table 1).
  • the above test data shows that the nano-surface coating on the metal of the invention has excellent performances of mechanical properties, chemical resistance, solvent resistance and high temperature resistance, and completely improves the defects of the existing metal nano anti-fouling coating.
  • the film is chemically bonded for surface adsorption to achieve such excellent physical and chemical properties.
  • the film plated on the metal surface by atomic layer deposition gas phase is an alumina Al 2 O 3 film.
  • the alumina Al 2 O 3 film can also be titanium oxide (TiO 2 ), silicon oxide (SiO 2 ), zinc oxide (ZnO), zirconium oxide (ZrO 2 ), indium oxide (In 2 O 3 ), or antimony oxide.
  • a thin film that can be grown by atomic layer deposition techniques such as (Ta 2 O 5 ) and hafnium oxide (HfO 2 ).
  • Titanium oxide (TiO 2 ) is grown by using titanium tetrachloride (TiCl 4 ) and water at a temperature of 300 ° C vacuum; silicon oxide (SiO 2 ) using silicon tetrachloride (SiCl 4 ) and water at a temperature of 300 ° vacuum Film growth; zinc oxide (ZnO) using diethylzinc (Zn(C 2 H 5 ) 2 ) and water at a temperature of 100 ° vacuum for film growth; zirconium oxide (ZrO 2 ) using zirconium tetrachloride (ZrCl 4 Film growth with water at a vacuum of 300 degrees Celsius; indium oxide (In 2 O 3 ) using indium trichloride (InCl 3 ) and water at a temperature of 300 ° vacuum for film growth; yttrium oxide (Ta 2 O 5 ) Film growth was carried out using ruthenium pentachloride (TaCl 5 ) and water at a vacuum of 300

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Abstract

La présente invention concerne un procédé de revêtement utilisé pour un nano-revêtement de surface d'un métal de forme irrégulière, comprenant les étapes consistant à : 1) disposer le métal de forme irrégulière dans une cavité sous vide; introduire, dans la cavité sous vide, une vapeur de composé organométallique qui est amenée à générer une adsorption physique ou chimique avec une surface; alimenter en azote gazeux pour éliminer une quantité excédentaire de composé organométallique; acheminer de la vapeur d'eau ou de l'ozone dans le vide; introduire l'azote gazeux pour éliminer la vapeur d'eau excédentaire n'ayant pas réagi de façon à constituer une boucle et former une couche atomique d'un film d'oxyde sur la surface métallique; 2) répéter la boucle 50 fois de sorte que les couches atomiques de films d'oxyde sont empilées couche sur couche pour former une couche dense couche de film d'oxyde de 5 nm; et 3) revêtir une surface de la couche de film d'oxyde à l'aide de fluorocarbone à base de silane à base d'oxygène qui est cuit à une température de 60 à 150 °C pour revêtir et générer une couche de film fluoré de protection contre les empreintes digitales. L'épaisseur du revêtement selon l'invention est seulement de 10 nanomètres, ce qui n'affecte pas l'apparence d'un produit, il présente une dureté élevée et une bonne résistance à la pollution, aux acides, aux alcalis et à l'abrasion, et une bonne durabilité.
PCT/CN2014/000863 2014-04-18 2014-09-23 Procédé de revêtement pour nano-revêtement de surface d'un métal de forme irrégulière Ceased WO2015157880A1 (fr)

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WO2019151445A1 (fr) * 2018-02-02 2019-08-08 ダイキン工業株式会社 Appareil électronique
JP2019131808A (ja) * 2018-02-02 2019-08-08 ダイキン工業株式会社 電子機器
CN113437248A (zh) * 2021-06-26 2021-09-24 宁德时代新能源科技股份有限公司 负极极片的处理方法、钠金属负极极片与电化学装置
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CN114045492B (zh) * 2021-12-28 2024-02-27 金宏气体股份有限公司 一种用于电子级羰基硫存储容器的界面处理工艺及应用
CN115369403A (zh) * 2022-09-06 2022-11-22 森科五金(深圳)有限公司 一种pvd与ald复合涂层及其制备方法
CN115948721A (zh) * 2023-03-15 2023-04-11 杭州幄肯新材料科技有限公司 一种cvd法制备碳化钽涂层的方法
CN115948721B (zh) * 2023-03-15 2023-05-30 杭州幄肯新材料科技有限公司 一种cvd法制备碳化钽涂层的方法
CN116949413A (zh) * 2023-03-16 2023-10-27 无锡中科德芯感知科技有限公司 铟柱制备装置、制备方法、系统、电子设备及存储介质
CN116949413B (zh) * 2023-03-16 2024-04-12 无锡中科德芯感知科技有限公司 铟柱制备装置、制备方法、系统、电子设备及存储介质

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