CN113502463A - Equipment for depositing diamond-like carbon film on inner wall of metal cylinder (or tube) with large length-diameter ratio - Google Patents

Equipment for depositing diamond-like carbon film on inner wall of metal cylinder (or tube) with large length-diameter ratio Download PDF

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CN113502463A
CN113502463A CN202110524166.3A CN202110524166A CN113502463A CN 113502463 A CN113502463 A CN 113502463A CN 202110524166 A CN202110524166 A CN 202110524166A CN 113502463 A CN113502463 A CN 113502463A
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anode
cylinder
diamond
tube
wire mesh
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CN113502463B (en
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郑锦华
刘青云
李志雄
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Henan Jinghua Film Technology Vacuum Technology Co ltd
Zhengzhou University
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Henan Jinghua Film Technology Vacuum Technology Co ltd
Zhengzhou University
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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
    • C23C16/22—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
    • C23C16/26—Deposition of carbon only
    • C23C16/27—Diamond only
    • C23C16/276—Diamond only 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
    • C23C16/44—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
    • C23C16/45559—Diffusion of reactive gas to substrate

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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)
  • Inorganic Chemistry (AREA)
  • Chemical Vapour Deposition (AREA)

Abstract

The invention relates to a device for depositing diamond-like film on the inner wall of a metal cylinder (or tube) with large length-diameter ratio (L/D) or small diameter, which adopts a cylinder (or tube) anode made of a metal wire mesh, takes the inner wall of the metal cylinder (or tube) as a cathode, forms a plasma electric field between the wire mesh anode and the inner wall of the metal cylinder (or tube), the central area of the wire mesh anode forms a reaction gas flow channel, meshes on the wire mesh anode form channels for uniformly distributing reaction gas, applies high voltage in the plasma electric field, and high-energy electrons in the electric field bombard the wire mesh anode and generate current. The bombardment of high-energy electrons and the current make the silk screen anode generate high temperature to radiate and heat the inner wall of the plated metal cylinder. The mesh anode can increase the flux of reaction gas and improve the uniformity of film deposition at a small electrode spacing. The device is internally provided with a thermocouple and a temperature display, and the mesh density (mesh size) and the wire diameter of the wire mesh anode are adjusted, so that the temperature of the wire mesh anode reaches the temperature required by the deposition of the diamond-like carbon film material. The technology effectively solves the problems that in a cylinder (or a tube) with a large length-diameter ratio or a small diameter, reaction gas flows in a closed space with a narrow polar distance to be blocked, so that the discharge is difficult, and the thin film is unevenly deposited and is difficult to form.

Description

Equipment for depositing diamond-like carbon film on inner wall of metal cylinder (or tube) with large length-diameter ratio
Technical Field
The invention relates to equipment for depositing a DLC (diamond-like carbon) film material on the surface of the inner wall of a metal cylinder (or tube), in particular to equipment for depositing the DLC film material on the inner wall of a cylinder body or a tube with a large length-diameter ratio.
Background
Diamond-Like Carbon films (DLC films for short) are solid lubricating film materials which have hardness and wear resistance similar to pure Diamond and have extremely low friction coefficient (0.1-0.3), have good optical, electrical and mechanical properties, are widely applied to the fields of machinery, electronics, chemistry, biomedicine, aerospace, military industry and the Like, and have wide application prospects. Especially in the aspects of friction reduction and low friction, the motion state of mechanical parts is greatly improved, the service life of the parts is prolonged, the operation reliability of machine equipment is improved, and the aims of energy conservation, consumption reduction and resource conservation are fulfilled.
At present, methods for preparing DLC diamond-like carbon film materials include a Physical Vapor Deposition (PVD) method and a Chemical Vapor Deposition (CVD) method, ion beam deposition, cathodic arc deposition, magnetron sputtering deposition, laser deposition, plasma enhanced chemical vapor deposition, hot wire plasma chemical vapor deposition and the like are derived from the PVD method, and although the deposition methods are numerous, a few technologies which can really realize industrial manufacturing are provided, half-productive industrialization level is realized abroad, China is still in a research and development stage, large-scale industrial production and market application are not realized, and a great number of technical problems which need to be solved exist for industrial production.
At present, the deposition of DLC film on the inner wall of a metal cylinder (or tube) is very difficult, and particularly, a good solution cannot be obtained by depositing the DLC film on the inner wall of a cylindrical or tubular part with a large length-diameter ratio (L/D), and the main problems are that: in a long and narrow cathode-anode plate, the flow area is narrow, the reaction gas is difficult to transport, the temperature field distribution and the electric field intensity distribution are uneven, the plasma is difficult to form, and the like, so that the thin film is difficult to grow on the surface of the inner wall of the cylinder with a large length-diameter ratio. The DLC-like diamond film material deposited on the inner wall of the cylinder or the inner wall of the pipe can be used for wear resistance strengthening of various cylinder body parts, such as an engine cylinder body, a hydraulic piston cylinder, a reciprocating compression cylinder and the like, and can solve the wear resistance problem of the inner wall of a pipeline, such as a slurry conveying pipe, an oil gas conveying pipe, a material conveying pipe and the like, and wear resistance strengthening of the inner surface of the pipe with friction wear; the result is greatly improved running stability of the engine and other equipment, and prolonged service life of relevant parts and pipelines.
There are also a number of reports on the patent literature relating to the production of DLC diamond-like thin film materials, for example: 1. the invention relates to an invention patent with the name of 'an apparatus and a method for depositing diamond-like carbon film in metal micropore', the invention patent with the application number of 201910322314.6, the invention is characterized in that the invention relates to an apparatus and a method for depositing diamond-like carbon film in metal micropore, the provided technical proposal is that: a device for depositing a diamond-like carbon film in a metal micropore comprises a vacuum chamber, a microwave source, a plasma source and a base, wherein a sample table is arranged on the base, a fixed seat is arranged on the sample table, a mounting plate is arranged on one side of the fixed seat, and a nozzle device is fixed on the mounting plate. The deposition method comprises the following steps: putting a sample with metal micropores in a fixed seat, wherein the metal micropores are coaxially arranged with a metal spray head of a nozzle device, applying negative bias on the metal spray head, communicating the sample with a power supply anode, and adopting microwave-excited high-density plasma to assist vapor deposition under the condition of given process parameters. 2. The invention has the application number of 201010132916.4 and the invention name of 'a method for preparing a metal sulfide diamond-like carbon composite film', and the invention is characterized in that the method combines ion beam etching, ion beam auxiliary deposition, ion beam deposition, magnetron sputtering and ion vulcanization to prepare a plurality of metal sulfide DLC composite films, and the method sequentially comprises the following steps: (1) firstly, removing a pollution layer on the surface of a substrate by utilizing an ultrasonic cleaning technology; (2) carrying out ion beam etching cleaning on the surface of the matrix by using inert gas ion beams generated by an ion source; (3) under the negative bias of a high workpiece, metal ions generated by a cathode arc source are utilized to etch and clean the surface of the substrate; (4) preparing a gradient transition layer by utilizing ion beam enhanced magnetron sputtering; (5) synthesizing the DLC film doped with tungsten, molybdenum or iron on the prepared gradient transition layer by using ion beam deposition and magnetron sputtering. (6) And preparing the metal sulfide/DLC composite film on the prepared DLC film doped with tungsten, molybdenum or iron by utilizing ion vulcanization.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: provides a device for depositing a DLC diamond-like carbon film on the inner wall surface of a metal cylinder (or tube) with a large length-diameter ratio. The invention can solve the problems that the DLC diamond-like carbon film can not be deposited on the inner wall of the metal cylinder (or tube) due to difficult circulation of hydrocarbon gas and uneven gas distribution in the metal cylinder (or tube) with large length-diameter ratio. By utilizing the technical scheme of the invention, the flow area of the reaction gas can be obviously increased, and the reaction gas can be uniformly distributed on the inner wall of the metal cylinder (or tube). The inner wall of the cylinder (or the pipe) is heated by controlling the temperature of the anode of the silk screen, so that the inner wall meets the deposition condition of the DLC-like carbon film material, and the continuous surface DLC film material with high interface bonding strength is prepared.
In order to solve the problems, the invention adopts the technical scheme that:
the invention provides a device for depositing a diamond film on the inner wall of a metal cylinder (or tube) with a large length-diameter ratio, which comprises a vacuum deposition chamber, a raw material inlet pipe and a vacuumizing device which are communicated with the deposition chamber, wherein the bottom in the deposition chamber is provided with a cathode plate connected with a cathode of a plasma generating source, the cathode plate is connected with a conducting ring to form a cathode object stage, a plated metal cylinder (or tube) is arranged on the conducting ring, and an anode cylinder is arranged on the periphery of the plated metal cylinder (or tube). An anode cover is arranged around the cathode plate in the deposition chamber and communicated with the anode cylinder to form an anode shield together. An electrically insulating ceramic plate is arranged below the cathode plate to isolate the cathode plate from the inner wall of the deposition chamber. The anode cover is electrically connected with the inner wall of the deposition chamber, the deposition chamber is connected with a ground wire, a silk screen anode cylinder is arranged in a plated metal cylinder (or pipe), and the silk screen anode cylinder is electrically connected with the anode cover to form a silk screen anode; a thermocouple is arranged on the wire mesh anode and is communicated with a temperature display outside the deposition chamber; the anode of the plasma generating source is grounded, the cathode of the generating source is connected with a vacuum electrode, and the vacuum electrode is connected with a cathode objective table.
The wire mesh anode is made of metal wires with smooth surfaces, such as 304 stainless steel or 316 stainless steel wires, or metal wires which can still maintain good rigidity and strength at about 300 ℃, such as tungsten wires, molybdenum wires, aluminum wires, steel wires and the like.
The wire mesh anode is a grid structure woven by metal wires in a certain shape, the grid shape can be any shape, such as round, square, rectangular, triangular, rhombic and the like, the grids form a flow passage of reaction gas, and the grid density and the wire diameter of the wires are determined according to the process requirements of depositing DLC diamond-like carbon films on the inner walls of metal cylinders (or tubes) with different calibers and length-diameter ratios.
The shape of the wire mesh anode is matched with that of the inner wall of the metal cylinder (or tube), the distance between the inner surface of the metal cylinder (or tube) and the outer surface of the wire mesh anode is 10-20 mm, and the distance between the inner surface of the metal cylinder and the outer surface of the wire mesh anode is kept consistent at any position.
The wire mesh anode is used as an electric field anode when depositing the DLC-like carbon film and is also used as a heating element for film deposition, and is arranged in a plated metal cylinder (or tube), the upper end of the wire mesh anode is higher than the metal cylinder (or tube) by more than 30mm, and the lower end of the wire mesh anode is lower than the lower end surface of the metal cylinder by more than 30mm (based on the distance between the conductive ring and the anode cover).
And the upper part of the wire mesh anode is provided with a thermocouple which is connected with a temperature display. The twin-core vacuum electrode is used as a medium for connecting the thermocouple and the temperature display, is isolated from the atmosphere and is electrically insulated from the deposition chamber.
The anode cylinder is made of SUS304 stainless steel, or SUS316 stainless steel, or vacuum metal materials such as aluminum, the shape of the anode cylinder is matched with the shape of the outer surface of the plated metal cylinder (or pipe), the interval between the inner surface of the anode cylinder and the outer surface of the plated metal cylinder (or pipe) is 2-5mm, and the interval between the inner surface of the anode cylinder and the outer surface of the plated metal cylinder (or pipe) is kept consistent at any position on the outer surface of the plated metal cylinder (or pipe).
The upper end of the anode cylinder is slightly higher than the plated metal cylinder (or tube), and the lower end surface is lower than the lower end surface of the plated metal cylinder (or tube) by more than 30mm (based on the distance between the conductive ring and the anode cover). The lower part of the anode cylinder is provided with a plurality of round hole-shaped channels, the diameter of the round hole is more than 20mm, but the round hole is positioned below the conducting ring.
The shape and size of the anode cylinder, the plated metal cylinder (or tube) and the wire mesh anode are not limited, and other metal cylinders (or tubes) with any shape can meet the requirements, such as a cylindrical cylinder, a square cylinder, a rectangular cylinder, a polygonal cylinder, an oval cylinder and the like.
The conducting ring is a metal ring, the shape and the size of the conducting ring are matched with those of a plated metal cylinder (or tube), and the conducting ring is matched and installed with the plated metal cylinder (or tube) to realize electric connection.
The plasma generating source is a DC direct current bias power supply, or a DC pulse bias power supply, or an RF power supply, or a high-frequency microwave power supply, or other high-voltage and low-current power supplies.
The vacuum pumping adopts a two-stage or three-stage vacuum system, the main vacuum pump adopts a molecular pump or a diffusion pump, and the secondary pump adopts a roots pump, a rotary vane pump or other mechanical vacuum pumps.
The invention carries out technical analysis and experimental research on the difficult problem of depositing DLC-like carbon film material on the inner wall of a metal cylinder (or tube) with large length-diameter ratio, when an anode cylinder (or rod) is arranged in the metal cylinder (or tube) with large length-diameter ratio, because the distance between the anode and the cathode is smaller (generally less than 50mm), a reaction gas flow passage for film deposition is long and narrow, and the flow area of gas is limited, so that the reaction gas flows difficultly, particularly, the distribution of the gas in the whole flow passage is extremely uneven, so that the plasma electric field intensity distribution is uneven, even effective plasma distribution is difficult to form, and the uniform DLC-like carbon film is difficult to form on the inner wall of the metal cylinder (or tube) with large length-diameter ratio. Especially, the DLC-like carbon film is deposited in a metal cylinder (or tube) with a smaller diameter, and a smaller cathode-anode spacing is necessary, so that the difficulty of depositing DLC-like carbon film materials on the inner wall of the metal cylinder (or tube) with the small diameter is further increased. Aiming at the problems, the mesh anode is adopted to replace the traditional anode cylinder (or rod), so that the problem of narrow area of a reaction gas flow channel is solved, the meshes of the mesh anode are uniformly distributed on the whole anode surface to form the flow channel of the reaction gas, and the problem of nonuniform distribution of the gas in a deposition electric field is solved; the high-voltage and low-current bias power supply is adopted, so that the energy of ionized atoms (or ions) can be greatly improved, the distance between the cathode and the anode can be further reduced, and the deposition of the DLC diamond-like carbon film material on the inner wall of the metal cylinder (or tube) with smaller diameter and larger length-diameter ratio becomes possible.
The invention adopts the wire mesh as the electric field anode for film deposition, the anode has a grid structure woven by metal filaments, and the anode hardly occupies the aperture section area of the metal cylinder (or tube) compared with the metal cylinder (or rod) anode, thereby greatly expanding the flow area of the reaction gas.
The silk screen anode divides the film deposition gas into two areas, the central area of the silk screen anode becomes a flow channel of the reaction gas, a gas ionization area is formed between the silk screen anode and the inner wall of the plated metal cylinder (or tube), and the gas is conveyed and ionized in different areas, thereby greatly reducing the flow resistance of the gas.
The metal filaments forming the wire mesh anode have larger specific surface area, and the distance between the anode and the cathode becomes smaller (10-20 mm), so that the electrode area difference corresponding to the anode and the cathode is small, the collision probability of atoms (or ions) in an ionization electric field is reduced under certain air pressure, the free path of ionized atoms (or ions) is increased, the atoms (or ions) have larger energy, the content of SP3 diamond structures in diamond-like carbon film materials is favorably improved, and the diamond-like carbon film with high wear resistance is obtained.
The invention adopts smaller distance between anode and cathode, can deposit film on the inner wall of metal cylinder (or tube) with smaller diameter, and simultaneously leads gamma to be in an ionization electric field-The hot electrons have more energy, so that the strong bombardment effect, gamma, is generated on the silk screen anode-The electrons are absorbed by the wire mesh anode to form anode current, so that the temperature of the wire mesh anode is rapidly increased, the wire mesh anode generates a hot filament effect, the radiation heating of the hot filament meets the requirement of DLC diamond-like carbon film materialThe required temperature conditions are established.
The uniform grid structure of the mesh anode adopted by the invention enables gas to be uniformly distributed on the surface of the inner wall of the whole metal cylinder (or tube) through the grid, thereby forming uniform electric field intensity and gas flow density on the inner wall of the whole metal cylinder (or tube).
The key technology of the invention is to adopt a wire mesh anode structure, and solve the problems that the film deposition on the inner wall surface of the metal cylinder (or tube) with large length-diameter ratio is uneven, and even a plasma electric field is difficult to form, so that DLC diamond-like carbon film material cannot be deposited on the inner wall of the metal cylinder (or tube).
Drawings
FIG. 1 is a schematic structural diagram of an apparatus for depositing a diamond-like carbon film on the inner wall of a metal cylinder (or tube) with a large length-diameter ratio.
Fig. 2 is a schematic structural diagram of a mesh anode cylinder and a photograph (partial) of a real mesh anode cylinder.
FIG. 3 is a photograph showing a diamond-like film deposited on the inner wall of a 20 carbon steel metal cylinder having an inner diameter of 200mm and a length of 800 mm.
FIG. 4 is an SEM scanning electron micrograph of a diamond-like film deposited on the inner wall of a 20 carbon steel metal cylinder with an inner diameter of 200mm and a length of 800 mm.
FIG. 5 is a Raman spectrum of a 20 # carbon steel metal cylinder with an inner diameter of 200mm and a length of 800mm on which a diamond-like carbon film material is deposited.
FIG. 6 is a photograph showing the outer shape of an SUS304 stainless steel cylinder having an inner diameter of 80mm and a length of 100 mm.
FIG. 7 is a photograph showing a real object obtained by depositing a diamond-like thin film on the inner wall of an SUS304 stainless steel cylinder having an inner diameter of 80mm and a length of 100 mm.
FIG. 8 is a Raman spectrum of a diamond-like thin film material deposited on the inner wall of an SUS304 stainless steel cylinder having an inner diameter of 80mm and a length of 100 mm.
FIG. 9 is a photograph showing the external shape of a cylinder tube made of spheroidal graphite cast iron having an inner diameter of 150mm and a length of 600 mm.
FIG. 10 is a photograph showing a diamond-like carbon film deposited on the inner wall of a cylinder made of nodular cast iron having an inner diameter of 150mm and a length of 600 mm.
FIG. 11 is a Raman spectrum of a nodular cast iron cylinder with an inner diameter of 150mm and a length of 600mm on which a diamond-like carbon film material is deposited.
In the figure, the reference numeral 1, a wire mesh anode (1-1, a wire mesh anode lower end fixing flange), 2, a plated metal cylinder, 3, an anode cylinder, 4, a vacuum deposition chamber, 5, an anode cover, 6, a cathode plate, 7, an insulating ceramic plate, 8, a vacuum electrode, 9, a vacuumizing system, 10, a plasma generating source, 11, a conducting ring, 12, a raw material gas source system, 13, a double-core vacuum electrode, 14, a temperature display, 15 and a thermocouple are marked.
Detailed Description
The following embodiments are merely intended to illustrate the present invention in further detail, and do not limit the content of the present invention.
The first embodiment is as follows:
an apparatus for depositing diamond-like carbon film on the inner wall of a metal cylinder (or tube) with large length-diameter ratio comprises:
referring to fig. 1, the device for depositing the diamond-like carbon film on the inner wall of the metal cylinder (or tube) with large length-diameter ratio comprises a vacuum deposition chamber 4, an air source air inlet pipe system 12 and a vacuum extractor 9 which are communicated with the deposition chamber, a cathode plate 6 connected with the cathode of a plasma generation source is arranged at the bottom in the deposition chamber, and a conducting ring 11 is connected on the cathode plate to form a cathode objective table. The plated metal cylinder (or tube) 2 is placed on the conductive ring 11, and the anode cylinder 3 is arranged on the periphery of the plated metal cylinder (or tube) 2. An anode cover 5 is arranged around a cathode plate 6 in the deposition chamber, and the anode cover 5 is communicated with the anode cylinder 3 to form an anode shield together. An electrically insulating ceramic plate 7 is provided beneath the cathode plate 6, separating the cathode plate 6 from the deposition chamber 4, forming a cathode electrical insulation. Wherein the anode cover 5 is electrically connected with the deposition chamber 4, the deposition chamber 4 is connected with the ground wire, the silk screen anode cylinder 1 is arranged in the plated metal cylinder (or pipe) 2, and the silk screen anode cylinder 1 is electrically connected with the anode cover 5 to form a silk screen anode; a thermocouple 15 is arranged on the silk screen anode 1, the thermocouple 15 is connected with the double-core vacuum electrode 13, the double-core vacuum electrode 13 is isolated from the atmosphere, so that the thermocouple 15 is communicated with a temperature display 14 outside the deposition chamber 4, and the temperature display 14 can measure and display the temperature of the silk screen anode 1; the anode of the plasma generating source 10 is grounded, the cathode of the generating source 10 is connected with the vacuum electrode 8 and isolated from the atmosphere, and the vacuum electrode 8 is connected with the cathode stage.
Referring to fig. 2, the present invention weaves a wire mesh anode 1 with SUS304 stainless steel wire, the wire mesh anode 1 in this embodiment is wound in a cylindrical shape, the wire mesh grid adopts a square structure, and a circular flange sheet 1-1 is welded at the bottom end of the wire mesh anode for fixed connection with an anode cover 5. The diameter (or size shape) of the screen anode 1 is matched with the shape of the inner wall of the plated metal cylinder (or tube) 2, the interval between the diameter (or size shape) of the screen anode 1 and the inner wall surface of the metal cylinder (or tube) 2 is 10-20 mm, and the diameter (or size) of the screen anode 1 is determined.
In this example, the distance between the anode cover 5 and the conductive ring 11 is 30mm, and the distance from the top end of the plated metal cylinder 2 to the anode cover 5 is 840mm, so that the total length of the manufactured wire mesh anode cylinder 1 is 870 mm. The diameter of the inner wall of the plated metal cylinder 2 is phi 200mm, and the interval between the inner wall of the plated metal cylinder 2 and the outer periphery of the screen anode cylinder 1 is 15mm, so that the screen anode cylinder 1 is a hollow screen cylinder with the outer diameter phi 170mm, the area in the hollow cylinder of the screen anode cylinder 1 is a flow channel of reaction gas, and the area between the outer periphery of the screen anode cylinder 1 and the inner wall of the plated metal cylinder 2 is an ionization electric field area. The square grids on the screen anode cylinder 1 become channels for conveying reaction gas to the ionization electric field, and the reaction gas is uniformly distributed on the surface of the inner wall of the whole metal-plated cylinder 2 to form uniform plasma electric field strength, thereby laying a foundation for depositing uniform DLC diamond-like carbon films on the inner wall of the metal-plated cylinder 1.
In this example, it is clear that the cathode of the plasma generating source 10 is connected to the vacuum electrode 8, the vacuum electrode 8 is connected to the cathode plate 6, the middle is isolated by the ceramic insulating plate 7, the cathode plate 6 is connected to the conductive ring 11 by the conductive rod, and the metallized cylinder 2 is fixed on the conductive ring 11, which together constitute the cathode portion. Anode cover 5 has surrounded negative plate 6 and insulating ceramic plate 7 to be connected with deposit chamber 4, interval 2 ~ 5mm and contactless between anode cover 5 and the negative plate 6, anode cylinder 3 by fixed connection on anode cover 5, anode cylinder 3 with by the plating between the metal cylinder 2 interval 2 ~ 5mm and contactless, anode cover 5 and anode cylinder 2 have surrounded negative pole portion jointly, have constituted positive pole portion, play electrical shielding's effect.
After reaction gas is introduced into the deposition chamber 4, the reaction gas enters the plated metal cylinder 2 and the screen anode cylinder 1, the plasma generating source 10 is opened, a plasma electric field is formed between the inner wall of the plated metal cylinder 2 and the outer wall of the screen anode cylinder 1, the reaction gas generates ionization reaction, a film is deposited on the inner wall of the plated metal cylinder 2, the consumed reaction gas is uniformly supplemented through meshes on the screen anode cylinder 1, the screen anode cylinder 1 is used as an anode part, is bombarded by hot electrons e-in the ionization electric field and is absorbed by the screen anode cylinder 1 to form anode current, the temperature of the screen anode cylinder 1 is increased, the heat is radiated on the inner surface of the plated metal cylinder 2 to play a role of heating a filament, and the improvement of the interface bonding strength of the film and the formation of a diamond-like film are facilitated.
The wire diameter of the metal wire for manufacturing the screen anode cylinder 1 is generally less than 1mm (according to the length-diameter ratio and the cylinder diameter size, the requirement of rigidity and strength at 300 ℃ is met, the smaller the wire diameter is, the better the wire diameter is), the arranged screen anode cylinder 1 hardly occupies the flowing space of the reaction gas, particularly, the cross section area of the inner diameter of the plated metal cylinder 1 is very small, and therefore, the flowing resistance of the reaction gas in the plated metal cylinder 1 is greatly reduced.
In the whole film deposition process, the temperature of the screen anode cylinder 1 is controlled to be about 300 ℃, and the softening temperature of most metals is far lower than the temperature, so that most metal wires can be used for manufacturing the screen anode 1, and the material selection range of the screen anode 1 is wide.
In the reaction gas source gas inlet pipe system 12, H is contained2、Ar、C2H2And Si (CH)3)4And the gas control valve can adjust corresponding gas flow according to the process requirements of each stage of film deposition in the manufacturing process of the film.
The vacuum-pumping device 9 adopts a two-stage or three-stage vacuum system, the main vacuum pump adopts a molecular pump or a diffusion pump, the secondary pump adopts a roots pump, a rotary vane pump or other mechanical vacuum pumps, and the ultimate vacuum degree of the system is ensured to reach 5 multiplied by 10-3Pa or above.
The equipment for depositing the diamond-like carbon film on the inner wall of the metal cylinder (or tube) with the large length-diameter ratio provided by the embodiment is specifically used by the following steps:
a. firstly, polishing the surface of the inner wall of a plated metal cylinder (or pipe) 2 to ensure that the surface roughness reaches Ra0.8, then putting the metal cylinder (or pipe) into an ultrasonic cleaning tank, cleaning the metal cylinder (or pipe) for 10min by using acetone, taking the metal cylinder (or pipe) out, and drying the metal cylinder (or pipe) by using clean dry air;
b. fixing a wire mesh anode cylinder 1 on an anode cover 5, placing a plated metal cylinder (or pipe) 2 on a conducting ring 11, installing an anode cylinder 3 on the peripheries of the plated metal cylinder (or pipe) 2 and the conducting ring 11, fixing the anode cylinder 3 on the anode cover 5, connecting a thermocouple 15 at the upper end of the wire mesh anode cylinder 1, and connecting the thermocouple 15 with a vacuum electrode 13 connected with a temperature display 14; the top lid of the upper end of the deposition chamber 4 was closed, and the vacuum pressure in the deposition chamber 4 was evacuated to 5x10 by the evacuation device 9 communicating with the deposition chamber 4-3Pa；
c. The temperature display 14 is firstly opened, then an Ar gas inlet valve communicated with the deposition chamber 4 is opened, and high-purity Ar gas is introduced. And adjusting the opening of the Ar gas inlet valve to enable the pressure in the deposition chamber 4 to reach 5-8 Pa and keep the flow of the Ar gas unchanged. The plasma generating source 10 is turned on to generate plasma between the screen anode cylinder 1 and the inner wall of the plated metal cylinder (or tube) 2, the output voltage of the DC plasma generating source 10 is adjusted, and when the temperature of the screen anode cylinder 1 is stabilized at about 300 ℃, the output voltage of the DC plasma generating source 10 is 4000V, the current is 0.6A, and the output power is 2.4 Kw. Performing Ar gas plasma bombardment on the inner wall of the plated metal cylinder (or tube) 2 for 20-30 min to remove pollutants on the surface of the inner wall of the metal cylinder (or tube) 2;
d. the deposition process of the intermediate bonding layer of a-Si, H and C comprises the following steps: the Ar gas inlet valve and the plasma generating source 10 were closed, and then tetramethylsilane Si (CH) was opened3)4Gas and H2Air inlet valve for introducing tetramethylsilane Si (CH)3)4Gas and H2Gas according to Si (CH)3)4：H2Adjusting inlet valves of tetramethylsilane and hydrogen at a ratio of 1:5 to keep the pressure in the deposition chamber 4 at 8-10 Pa; then the plasma generating source 10 is turned on to make the screen anode cylinder 1 and the plated metal cylinder (or tube) 2Plasma is generated between the inner walls, the output voltage of the DC plasma generating source 10 is adjusted, and when the temperature of the screen anode cylinder 1 is stabilized at about 300 ℃, the output voltage of the DC plasma generating source 10 is 3600V, the current is 0.8A, and the output power is 2.88 Kw. Depositing an a-Si, H and C intermediate bonding layer for 10-15 min;
e. deposition process of DLC diamond-like thin film material: tetramethylsilane Si (CH) is turned off3)4Gas and hydrogen inlet valves, and a plasma generating source 10. Then opening Ar gas and C2H2Gas and H2An air inlet valve for adjusting the flow of Ar to 10 sccm; adjustment C2H2The gas flow is 5 sccm; adjusting H2The flow rate was increased to 25sccm, and the flow rate ratio was maintained constant. Then, the plasma generation source 10 was turned on to generate plasma between the screen anode cylinder 1 and the inner wall of the plated metal cylinder (or tube) 2, and the output voltage of the DC plasma generation source 10 was adjusted so that when the temperature of the screen anode cylinder 1 was stabilized at about 300 ℃, the output voltage of the DC plasma generation source 10 was 2500V, the current was 0.6A, and the output power was 1.5 Kw. Depositing the DLC-like carbon film for 60-70 min. After the DLC-like carbon film deposition is finished, the plasma generating source 10 is firstly closed, and then Ar gas and C are respectively closed2H2Gas and H2And (3) air inlet valve, closing the switch of the temperature display, vacuum cooling for 30min, and finally obtaining the continuous surface diamond-like carbon film with high interface strength on the inner wall of the plated metal cylinder (or tube).
In the attached figure 3, the inner wall of the No. 20 carbon steel metal cylinder with the inner diameter of 200mm and the length of 800mm is deposited with a black film, and the surface is smooth and compact. As can be seen from the SEM of FIG. 4, the film thickness was 14 μm, and the a-Si: H: C bonding layer was about 1.5 μm thick. In the Raman spectrum of FIG. 5, at a wave number of 1580cm-1A single shoulder peak is nearby and is a graphite characteristic peak, and the wave number is 1350cm-1Another shoulder peak is nearby and is a characteristic peak of diamond, which shows that the film is a characteristic peak of the DLC diamond-like carbon film material.
Example two: basically the same as the first embodiment, except that:
in this example, the distance between the anode cover 5 and the conductive ring 11 is 30mm, and the distance from the top end of the plated metal cylinder 2 to the anode cover 5 is 135mm, so that the total length of the manufactured wire mesh anode cylinder 1 is 165 mm. The diameter of the inner wall of the plated metal cylinder 2 is phi 80mm, and the interval between the inner wall of the plated metal cylinder 2 and the periphery of the screen anode cylinder 1 is 15mm, so that the screen anode cylinder 1 is a hollow screen cylinder with the outer diameter phi 50 mm.
In the attached figures 6 and 7, the obtained product has the advantages that the continuous surface diamond-like carbon film with high interface strength is obtained on the inner wall of an SUS304 stainless steel cylinder with the inner diameter of 80mm and the length of 100mm, the film is deposited to be black, and the surface is smooth and compact. In the Raman spectrum of FIG. 8, at a wave number of 1580cm-1A single shoulder peak is nearby and is a graphite characteristic peak, and the wave number is 1350cm-1Another shoulder peak is nearby and is a characteristic peak of diamond, which shows that the film is a characteristic peak of the DLC diamond-like carbon film material.
Example three: basically the same as the first embodiment, except that:
in this example, the distance between the anode cover 5 and the conductive ring 11 is 30mm, and the distance from the top end of the plated metal cylinder 2 to the anode cover 5 is 640mm, so that the total length of the manufactured wire mesh anode cylinder 1 is 670 mm. The diameter of the inner wall of the plated metal cylinder 2 is phi 150mm, and the interval between the inner wall of the plated metal cylinder 2 and the periphery of the screen anode cylinder 1 is 20mm, so that the screen anode cylinder 1 is a hollow screen cylinder with the outer diameter phi 110 mm.
In the attached figures 9 and 10, the continuous surface diamond-like carbon film with high interface strength is obtained on the inner wall of the nodular cast iron cylinder barrel with the inner diameter of 150mm and the length of 600mm, the film is black in deposition, and the surface is smooth and compact. In the Raman spectrum of FIG. 11, at a wave number of 1580cm-1A single shoulder peak is nearby and is a graphite characteristic peak, and the wave number is 1350cm-1Another shoulder peak is nearby and is a characteristic peak of diamond, which shows that the film is a characteristic peak of the DLC diamond-like carbon film material.

Claims (11)

1. The equipment for depositing diamond film on the inner wall of metal cylinder (or tube) with large length-diameter ratio includes vacuum deposition chamber, raw material gas inlet pipe and vacuum extractor communicated with the deposition chamber, negative plate connected to negative pole of plasma generating source and connected to the negative plate to constitute negative pole stage, plated metal cylinder (or tube) on the negative plate, and anode cylinder around the plated metal cylinder (or tube). An anode cover is arranged around the cathode plate in the deposition chamber and communicated with the anode cylinder to form an anode shield together. An electrically insulating ceramic plate is arranged under the cathode plate to isolate the cathode plate from the deposition chamber. The anode cover is electrically connected with the deposition chamber, the deposition chamber is connected with a ground wire, a wire mesh anode cylinder is arranged in the plated metal cylinder, and the wire mesh anode cylinder is electrically connected with the anode cover to form a wire mesh anode; the thermocouple is arranged on the mesh anode and is communicated with a temperature display outside the deposition chamber, and the device is characterized in that: the plasma deposition anode adopts a wire mesh structure, a certain distance is reserved between the wire mesh anode and the inner wall of a plated metal cylinder (or tube), the wire mesh anode is woven by high-melting-point metal wires with smooth surfaces, wire mesh grids form a gas channel and form a hot filament heating effect, and a temperature display can measure and display the temperature of the wire mesh anode; the anode of the plasma generating source is grounded, the cathode of the generating source is connected with a vacuum electrode, and the vacuum electrode is connected with a cathode objective table.
2. The diamond-like thin film deposition apparatus of claim 1, wherein: the metal wires of the mesh anode still have good rigidity and strength at 300 ℃, for example, the metal wires of stainless steel wires, tungsten wires, molybdenum wires and the like.
3. The diamond-like thin film deposition apparatus of claim 1, wherein: the mesh shape of the mesh anode is any shape (diamond, round, rectangular, square, special-shaped and the like).
4. The diamond-like thin film deposition apparatus of claim 1, wherein: the silk screen anode is not provided with a heating power supply for power input, but forms anode current in the metal silk screen by bombarding and absorbing electrons through hot electrons in a plasma electric field, so that the temperature of the silk screen anode is increased.
5. The diamond-like thin film deposition apparatus of claim 1, wherein: the distance between the anode cover and the anode cylinder and the plated metal cylinder, the distance between the cathode plate and the distance between the anode cover and the plated metal cylinder and between the anode cover and the conductive ring are 2-5 mm.
6. The diamond-like thin film deposition apparatus of claim 1, wherein: the conducting ring and the cathode plate are separated by an anode cover and are connected by a cathode rod penetrating through a round hole on the anode cover, and the cathode rod is spaced from the inner wall of the round hole on the anode cover by 2-5mm to form electrical insulation between a cathode and an anode; the distance between the conductive ring and the anode cover is more than 30 mm.
7. The diamond-like thin film deposition apparatus of claim 1, wherein: the plasma generating source is a DC direct current plasma generating source, or a DC direct current pulse plasma generating source, or an RF radio frequency plasma generating source, or a microwave plasma generating source.
8. The diamond-like thin film deposition apparatus of claim 1, wherein: the thermocouple and the temperature display are connected with the screen anode, and whether the wire diameter and the grid density of the metal wires forming the screen anode can enable the screen anode temperature to reach the deposition temperature of the diamond-like thin film material or not can be determined.
9. The diamond-like thin film deposition apparatus of claim 1, wherein: the shape and the size of the anode cylinder, the anode cover, the wire mesh anode and the conducting ring are matched with those of a plated metal cylinder (or pipe), and the plated metal cylinder (or pipe) is a circular cylinder, a square cylinder, an oval cylinder, a polygonal cylinder, a rectangular cylinder or any other cylinder.
10. The diamond-like thin film deposition apparatus of claim 1, wherein: the size of the inner wall of the plated metal cylinder (or tube) is more than 50 mm.
11. The diamond-like thin film deposition apparatus of claim 1, wherein: the vacuum degree of the plasma generating chamber is not lower than 5 multiplied by 10 by the vacuum pumping device-3Pa。
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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6042900A (en) * 1996-03-12 2000-03-28 Alexander Rakhimov CVD method for forming diamond films
US20040055870A1 (en) * 2002-09-25 2004-03-25 Ronghua Wei Method and apparatus of plasma-enhanced coaxial magnetron for sputter-coating interior surfaces
CN1851045A (en) * 2006-05-31 2006-10-25 大连理工大学 Slender metal pipe inner wall diamond-film-like deposition method using DC glow discharge

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6042900A (en) * 1996-03-12 2000-03-28 Alexander Rakhimov CVD method for forming diamond films
US20040055870A1 (en) * 2002-09-25 2004-03-25 Ronghua Wei Method and apparatus of plasma-enhanced coaxial magnetron for sputter-coating interior surfaces
CN1851045A (en) * 2006-05-31 2006-10-25 大连理工大学 Slender metal pipe inner wall diamond-film-like deposition method using DC glow discharge

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