JP4831428B2 - Method for forming amorphous hard carbon film on compressor sliding member, compressor sliding member formed by the method, and apparatus for manufacturing the same - Google Patents

Description

  The present invention relates to a method for forming an amorphous hard carbon film on a compressor sliding member at atmospheric pressure, a compressor sliding member formed by the method, and an apparatus for manufacturing the same.

  Amorphous hard carbon films have characteristics of high hardness, low wear, low friction, and excellent surface smoothness, and are used by being coated on dies, tools, sliding parts, and the like. An amorphous hard carbon film is an amorphous hard carbon film containing a relatively large number of carbon atoms in the same bonding state as diamond, and is generally called a diamond-like carbon (DLC) film. It is known that the properties of the DLC film differ depending on the raw materials used and the film forming method. As a method for forming a DLC film, plasma CVD or sputtering is generally used. However, in the film formation method using the plasma CVD method or the sputtering method, a uniform plasma cannot be obtained over a wide range, and a region where a homogeneous film can be formed is limited and it is difficult to increase the area. In addition, the film forming speed is low because it is performed in a low pressure environment, and there is a problem that productivity is difficult because it is a batch type using a vacuum vessel.

  Although it is not disclosed as a film formation method for DLC film, a film formation method by discharge plasma treatment in the vicinity of atmospheric pressure is proposed as a method to improve the difficulty of other film formation methods using plasma CVD or sputtering. Has been. However, the diffusion of the mixed gas introduced into the discharge space in the vicinity of the atmospheric pressure tends to cause a bias of the mixed gas as compared with the diffusion of the mixed gas in a low pressure environment, and the formed film tends to be non-uniform.

  Patent Document 1 discloses a plasma processing apparatus in which a plasma processing space is formed between a pair of upper and lower electrodes under atmospheric pressure, and plasma processing is performed on an object to be processed placed on the lower electrode.

Patent Document 2 discloses a swash plate type compressor having a sliding member on which a DLC film is formed using a CVD method or a PVD method. Patent Document 2 discloses nothing about the method of forming the DLC film except that the CVD method or the PVD method is used.
JP 2005-5107 A JP 2002-5013 A

  As described above, various methods for forming an amorphous hard carbon film have been studied. However, no film forming method near atmospheric pressure is disclosed as a method for forming an amorphous hard carbon film on a compressor sliding member.

  The present invention has been made in view of such circumstances, and a method for forming an amorphous hard carbon film in the vicinity of the atmospheric pressure of a compressor sliding member, and a compressor sliding formed by the method. It aims at providing a member and its manufacturing apparatus.

Means for Solving the Problems and Effects of the Invention

  Therefore, the present inventors have intensively studied to solve this problem, and as a result of repeated trial and error, the sliding member is attached to the holding electrode that holds the sliding member, and the sliding surface of the sliding member and the electrode surface of the holding electrode Are formed so that they are substantially flush with each other, and the amorphous hard carbon film is formed with optimized productivity in the vicinity of atmospheric pressure by optimizing the film forming conditions of the amorphous hard carbon film. The inventors have found what can be done and have completed the present invention.

(Method for forming amorphous hard carbon film on compressor sliding member)
That is, the method for forming an amorphous hard carbon film on a compressor sliding member of the present invention is a method for forming an amorphous hard carbon film on a compressor sliding member comprising a housing step and a film forming step. Te, the receiving step is to accommodate the sliding member of the compressor so that the sliding surface and the electrode surface of the storage electrode of the sliding member is substantially coplanar to the holding electrode and the deposition body The film forming step is arranged on at least both sides of the film-forming body, a material gas supply port for supplying a material gas to the surface of the film-forming body, and the material gas supply port in the relative movement direction. A shape in which the exhaust port provided and the film-forming body at the time of film formation are arranged opposite to each other and the surface on the side of the holding electrode is covered with a dielectric, and a discharge gap distance is provided along the surface. while the gas supply electrode body consisting of the application electrode of the moved relative, deposition pressure: mixing of near atmospheric pressure, the raw material gas : Inert gas / hydrocarbon-based gas = 0/100 to 99/1, discharge gap distance between the applied electrode and the holding electrode: 0.5 mm to 10 mm, raw material gas flow rate: 1 mm / sec to 1000 mm / sec in conditions, wherein the AC voltage to the gas supply electrode member a sign pressurized to the applied electrode by generating a glow discharge plasma between the surface of the deposition material, the amorphous hard at least on the sliding surface It is a process for forming a carbon film.

  By setting the mixing ratio of the raw material gases as the inert gas / hydrocarbon gas = 0/100 to 99/1 as the conditions for the film forming process, the plasma can be stabilized and high-speed processing can be performed.

  In addition, by setting the discharge gap distance between the application electrode and the holding electrode to be 0.5 mm to 10 mm, a stable gas flow can be created and generation of unnecessary discharge can be suppressed.

  By setting the raw material gas flow rate to 1 mm / sec to 1000 mm / sec, it is possible to constantly supply raw materials necessary for processing, and to perform stable film formation.

  By combining these film forming conditions, a uniform amorphous hard carbon film can be formed efficiently on the sliding surface of the compressor sliding member near atmospheric pressure.

  Also, by providing a source gas supply port and exhaust ports on at least both sides of the source gas supply port in the gas supply electrode body, the source gas is relatively easy even under atmospheric pressure where convection of source gas is less likely to occur than under low pressure. Thus, the source gas is uniformly diffused, and an amorphous hard carbon film can be uniformly formed on the sliding member.

  The sliding member is accommodated in the holding electrode so that the sliding surface of the sliding member and the electrode surface of the holding electrode are substantially in the same plane. The term “substantially the same plane” means that the sliding member is accommodated in a shape along the plane or curved surface of the electrode surface of the holding electrode. Such a holding electrode in which a sliding member is accommodated is referred to as a film formation target. In this case, the film-forming body at the time of film formation and the application electrode surface opposite to each other have a shape along which the discharge gap distance is along. If the surface of the film formation body is flat, the electrode surface of the application electrode also has a flat shape. If the surface of the film formation body is curved, the electrode surface of the application electrode also has a curved surface along the film formation body. .

  Since the sliding surface of the sliding member and the electrode surface of the holding electrode are accommodated in substantially the same plane, it is possible to suppress the generation of unnecessary discharge by creating a stable gas flow in the discharge space. .

  The relative movement between the film formation body and the gas supply electrode body may be a parallel movement in one direction or a rotational movement. By relatively moving the film formation body and the gas supply electrode body so as to match the shape of the sliding member for forming the amorphous hard carbon film, a uniform film can be formed efficiently.

  By using such an amorphous hard carbon film forming method, plasma discharge is stably performed, and a uniform amorphous hard carbon film can be formed efficiently on the compressor sliding member.

  Moreover, it is preferable that the second dielectric is covered except for the sliding surface of the film formation target. By covering the portion other than the sliding surface of the film formation body with the second dielectric, the discharge becomes more stable and the portion other than the sliding surface can be masked.

  The sliding member can be a swash plate or a shoe of a swash plate compressor.

  Still further, the sliding member is a disc-shaped swash plate having a convex portion in the center, the sliding surface is an annular sliding plane surrounding the convex portion, and the relative movement in the film forming step is The gas supply electrode body opposed to the annular sliding plane may rotate relative to the periphery of the convex portion. By doing so, it is possible to form a uniform amorphous hard carbon film on the swash plate that could not be formed because the convex portion at the center of the swash plate was hindered.

  Further, when the sliding member is a shoe of a swash plate compressor, the accommodating step can be a plural accommodating step in which a plurality of shoes are accommodated in the holding electrode. By accommodating a plurality of shoes, a uniform amorphous hard carbon film can be formed efficiently.

  The sliding surface has a first sliding surface and a second sliding surface, and the holding electrode accommodates the first sliding surface and the second sliding surface on both sides in an open state. The body comprises a first gas supply electrode body and a second gas supply electrode body disposed on both sides of the holding electrode, and the first sliding surface faces the first gas supply electrode body during the film formation process. In addition, the second sliding surface faces the second gas supply electrode body, and an amorphous hard carbon film is formed on the first sliding surface and the second sliding surface almost simultaneously. It can be a process. Efficient film formation can be achieved by forming the film from both sides substantially at the same time. The first sliding surface and the second sliding surface may be the same sliding member sliding surface or different sliding member sliding surfaces.

  The hydrocarbon gas is preferably acetylene, and the inert gas is preferably nitrogen. In that case, the discharge gap distance between the application electrode and the holding electrode is 0.5 mm or more and less than 5 mm. By using acetylene as the hydrocarbon gas, it becomes a film forming method that is easy to turn into plasma and easily discharge, and by using nitrogen as the inert gas, it can be formed at low cost.

(Compressor sliding member)
The compressor sliding member of the present invention is a compressor sliding member having a base material forming the compressor sliding member and an amorphous hard carbon film coated on the sliding surface of the base material. The amorphous hard carbon film is formed by any one of the film forming methods described above.

  Compressor sliding member having a uniform amorphous hard carbon film formed by using the compressor sliding member formed by the amorphous hard carbon film forming method of the compressor sliding member. It can be.

(Filming device for amorphous hard carbon film of compressor sliding member)
Further, in the film forming apparatus for the amorphous hard carbon film of the compressor sliding member of the present invention, the sliding surface of the compressor is arranged so that the sliding surface of the sliding member and the electrode surface are substantially in the same plane. A holding electrode to be held, an exhaust port provided on at least both sides of the source gas supply port in the relative movement direction of the source gas supply port and the holding electrode, and an opposite side to the holding electrode at the time of film formation A gas supply electrode body having a surface on the side of the holding electrode coated with a dielectric, and having a discharge gap distance and a shape of an application electrode that faces the deposition target body, and voltage application means for applying to the application electrode; , A moving means for relatively moving the holding electrode and the gas supply electrode body, film forming pressure: near atmospheric pressure, mixing ratio of source gases: inert gas / hydrocarbon gas = 0/100 to 99/1, Discharge gap distance between the application electrode and the holding electrode: 0.5 mm to 10 m , The raw material gas flow rate: characterized by having a a deposition control means capable of controlling between 1mm / sec~1000mm / sec the holding electrode and the indicia pressurized electrode deposition conditions.

  By using the amorphous hard carbon film forming apparatus for the compressor sliding member having the above-described configuration, a uniform amorphous hard carbon film can be formed on the compressor sliding member.

(Method for forming amorphous hard carbon film on compressor sliding member)
The film forming method of the amorphous hard carbon film of the compressor sliding member of the present invention includes a housing process and a film forming process.

  Of these, the accommodating step is a step in which the sliding member of the compressor is accommodated in the holding electrode and the sliding surface of the sliding member and the electrode surface of the holding electrode are accommodated in substantially the same plane to form a film formation target. .

  The sliding member of the compressor is not particularly limited as long as it is a sliding member used in a positive displacement compressor. Examples of the compressor include a reciprocating compressor and a rotary compressor (scroll compressor, rotary compressor). The sliding member has an important role in the reciprocating compressor. Among the reciprocating compressors, there are a swash plate compressor, a crank compressor, and a wapple compressor.

  For example, a swash plate compressor has a disk-like swash plate fixed to a rotating shaft at a fixed angle or a variable angle, a pair of shoes moored to the swash plate, and a piston connected to the swash plate via the shoe. It is provided. In the case of this swash plate compressor, examples of the sliding member include a swash plate, a shoe, a piston, and a bearing. In particular, the swash plate and the shoe have sliding planes that slide relative to each other. The sliding surface of the disk-shaped swash plate is an annular plane that is a sliding surface with the shoe and is spaced a certain distance from the center of the disk. Since the swash plate is sandwiched between the pair of shoes, the sliding surface of the swash plate exists on both sides of the swash plate.

  Further, the swash plate may be a disk-shaped swash plate having a convex portion at the center.

  The method for forming an amorphous hard carbon film of the present invention is a method used for a sliding member of a compressor, but this method is not limited to a compressor, and is applied to a sliding member for a vehicle having a sliding surface. Can be used. For example, it can be used for sliding members such as engines and transmissions.

  As the material of the sliding member, an iron-based material such as cast iron or an aluminum-based metal can be used. The sliding surface of the sliding member preferably has a small surface roughness, but may have irregularities with a surface roughness Ra of 1 μm or less in order to improve the adhesion of the amorphous hard carbon film. Also, an amorphous hard carbon film may be formed directly on the sliding surface of the sliding member, or an intermediate layer for improving adhesion is formed between the sliding member and the amorphous hard carbon film. May be. The intermediate layer may be a metal film of Ti, Cr or the like having a thickness of several nm to several μm.

  The holding electrode is an electrode that can hold the sliding member of the compressor. The material of the holding electrode is not particularly limited as long as it is made of a conductor. Examples of the material include metal materials such as aluminum, copper, and brass, and carbon materials. The holding member may hold the sliding member by forming a recess, may hold the sliding member between a plurality of divided holding electrodes, or may form a through hole in the holding electrode. The sliding member may be clamped. Also, a plurality of recesses may be formed to hold a plurality of sliding members, or the sliding members may be held with both sides open from both sides. When the sliding surface of the sliding member is a curved surface, the shape of the holding electrode may be a curved surface that is substantially the same surface. Among these, a shape having a parallel flat portion between the application electrode and the holding electrode is more preferable, and it is preferable that both electrodes have a substantially planar shape. The holding electrode only needs to be grounded and does not need to be applied by a power source or the like.

  Further, the surface of the sliding member and the surface of the holding electrode other than the film-forming portion of the amorphous hard carbon film of the sliding member may be covered with a dielectric (second dielectric). The dielectric (second dielectric) is preferably thin enough not to disturb the gas flow. By covering with a dielectric, abnormal discharge at the time of voltage application can be reduced, and the portions other than the film formation can be masked.

  Examples of the material of the second dielectric material include plastics such as polytetrafluoroethylene and polyethylene terephthalate, glass, metal dioxide such as silicon dioxide, aluminum oxide, zirconium dioxide, and titanium dioxide, and double oxide such as barium titanate. .

  The material of the dielectric (second dielectric) can be the same as the material of the dielectric described later. The material of the dielectric and the second dielectric may be the same or different.

  Glow discharge plasma can be generated more stably by covering the surface of the sliding member other than the formation position of the holding electrode and the amorphous hard carbon film with the dielectric (second dielectric). .

  In the film forming step, an AC voltage is applied to the gas supply electrode body while relatively moving the film formation body and the gas supply electrode body, so that a glow occurs between the application electrode and the surface of the film formation body. In this step, discharge plasma is generated to form an amorphous hard carbon film on at least the sliding surface.

  The gas supply electrode body includes a source gas supply port for supplying a source gas to the surface of the deposition target body, exhaust ports disposed on at least both sides of the source gas supply port in the relative movement direction, An application electrode disposed opposite to the film formation body and having a surface covered with a dielectric.

  The shape of the gas supply electrode body is not particularly limited as long as the source gas supply port, the exhaust port, and the application electrode can be held. The source gas supply port and the exhaust port may have a slit shape. The width of the slit is preferably about twice the discharge gap distance. The slit length may be long enough to cover the sliding surface on which the amorphous hard carbon film is formed.

  The source gas supply port is connected to a cylinder for supplying source gas, and the flow rate is controlled by a control valve. The exhaust port is connected to an exhaust pump or the like, and is sucked by the exhaust pump to exhaust the source gas.

  The application electrode is not particularly limited as long as it is formed of a conductor. For example, metal materials such as aluminum, copper, and brass can be used as the material.

  The application electrode is covered with a dielectric. The dielectric is preferably 0.5 mm or more in thickness and smaller than the discharge gap distance. Within this range, discharge plasma can be generated without requiring a high voltage, and it is possible to suppress the occurrence of arc discharge due to dielectric breakdown during voltage application. Examples of the dielectric material include plastics such as polytetrafluoroethylene and polyethylene terephthalate, glass, metal dioxide such as silicon dioxide, aluminum oxide, zirconium dioxide, and titanium dioxide, and double oxide such as barium titanate.

  The shape of the application electrode is not particularly limited as long as it has a length corresponding to the film formation method. A power source is connected to the application electrode and applied. The power source may be an AC power source having a frequency of several kHz or more, which is generally used for atmospheric pressure plasma discharge, and an AC pulse power source or an RF power source can be used as the power source.

  Although the gas supply electrode body is installed relative to the holding electrode, two gas supply electrode bodies may be installed on both sides of the holding electrode.

  The film forming step is performed under the following conditions.

  Film formation is performed under a pressure near atmospheric pressure. The pressure in the vicinity of atmospheric pressure refers to the pressure when film formation is performed in an atmospheric pressure open environment, and includes the range of pressure fluctuation due to gas supply and exhaust. Specifically, the pressure range is 0.1 atm or more and 2 atm or less.

  As the source gas, a mixed gas of an inert gas as an atmospheric gas and a hydrocarbon-based gas as a reactive gas is used at a mixing ratio of 0/100 to 99/1. That is, it may be a hydrocarbon-based gas alone or a mixed gas of a hydrocarbon-based gas and an inert gas. More preferably, the mixing ratio of the mixed gas is used in the range of 10/90 to 90/10, and more preferably in the range of 25/75 to 75/25. When used in this range, the stable discharge by the atmospheric gas and the improvement of the deposition rate due to the high plasma density of the reactive gas can be obtained.

  In addition to the hydrocarbon-based gas, other component gases may be added as the reaction gas. For the purpose of enhancing the function of the film, a gas containing a metal or Si component can be added simultaneously.

  The mixing ratio of the source gases may be a constant ratio during the amorphous hard carbon film forming process, or may be changed during the film forming process. Since the inert gas has a role for exciting active species at the time of plasma generation, the mixing ratio of the inert gas may be lowered if plasma is generated.

  As the inert gas, helium, argon, or nitrogen can be used alone or as a mixture of two or more thereof. Nitrogen gas is preferable because of lower cost. The hydrocarbon gas can include saturated hydrocarbons such as methane, ethane, and propane, and unsaturated hydrocarbons such as ethylene and acetylene. Among them, it is preferable to use acetylene having high reactivity.

  Such source gas is supplied at a source gas flow rate of 1 mm / sec to 1000 mm / sec. More preferably, the raw material gas flow rate is 10 mm / sec to 100 mm / sec, and the exhaust is performed under the same flow rate as that of the raw material gas. By exhausting at a speed equal to or higher than the raw material gas flow rate, the raw material gas is uniformly convected and the raw material gas is evenly diffused.

  The discharge gap distance between the application electrode and the holding electrode is preferably 0.5 mm to 10 mm. More preferably, the thickness is from 1 mm to 3 mm, and if it is within this range, it is easy to obtain a stable gas flow and a uniform discharge in the gap space. The discharge gap distance can be made larger when helium or argon is used than when nitrogen is used as the inert gas.

  For example, when nitrogen is used as the inert gas and acetylene is used as the hydrocarbon-based gas, the discharge gap distance is preferably less than 5 mm.

  By setting the discharge gap distance within the above range and applying a frequency and voltage at which glow discharge is generated by an AC power source to the application electrode, glow discharge plasma is generated between the application electrode and the holding electrode. An amorphous hard carbon film is formed on the sliding surface by supplying and exhausting the source gas while generating glow discharge plasma under such conditions.

  At this time, the holding electrode and the gas supply electrode body are moved relative to each other. The relative movement is performed by moving means. The moving means can be a general moving means that can move in a certain direction, and is not particularly limited. This moving speed is controlled by the moving means, and may be further controlled by a control means for controlling the whole.

(Film-formed compressor sliding member)
The compressor sliding member of the present invention has a base material and an amorphous hard carbon film formed on the sliding surface of the base material by any one of the film forming methods described above.

  The base material forms a compressor sliding member, and the same can be said for the sliding member described in the film forming method. As the material of the base material, iron-based materials such as cast iron or aluminum-based metals can be used. Although it is preferable that the surface of the sliding surface of the base material has a small surface roughness, the surface roughness Ra = 1 μm or less may be provided to improve the adhesion of the amorphous hard carbon film. Further, an amorphous hard carbon film may be formed directly on the surface of the substrate, or an intermediate layer for improving adhesion may exist between the substrate and the amorphous hard carbon film. . The intermediate layer may be a metal film such as Ti or Cr.

  The amorphous hard carbon film may be any film formed by any of the film forming methods described in the above film forming method. The amorphous hard carbon film formed by the above film forming method is composed of a carbon element like diamond and graphite, and has a structure partially bonded to hydrogen. In addition, the bonding state between the carbon atoms is composed of a diamond structure and a graphite structure, and in the order of long distance, there is no regular crystal structure but an amorphous structure.

  Moreover, it is good also as a film | membrane containing a metal and Si component for the purpose of highly functional film | membrane other than a hydrocarbon type.

(Filming device for amorphous hard carbon film of compressor sliding member)
The amorphous hard carbon film forming apparatus for the compressor sliding member of the present invention includes a holding electrode, a gas supply electrode body, a voltage applying means, a moving means, a film forming condition, the holding electrode and the Film forming control means capable of controlling the space between the application electrodes.

  The holding electrode and the gas supply electrode body are the same as those described in the film forming method. The voltage application means corresponds to a power source applied to the application electrode.

  The power source connected to the application electrode may be an AC power source having a frequency of several kHz or more, which is generally used in atmospheric pressure plasma discharge, and an AC pulse power source or an RF power source can be used as the power source. Since the holding electrode is grounded, no power source is particularly required on the holding electrode side.

  The moving means moves the holding electrode and the gas supply electrode body relative to each other. The moving means is not particularly limited as long as it can perform the relative movement described in the film forming method. For example, the holding electrode or the gas supply electrode body may have a moving means, or the holding electrode or the gas supply electrode body may be installed in the moving means. The moving direction can be selected as appropriate, such as parallel movement or rotational movement. Further, the moving means may be controlled by the film forming control means.

  Next, a preferred embodiment will be described, and the present invention will be described in more detail with reference to FIGS. Each example describes a method for forming an amorphous hard carbon film. At the same time, a compressor sliding member formed by the film forming method and an amorphous hard carbon film for a compressor sliding member are described. This also serves as an explanation of the film forming apparatus.

[First embodiment]
FIG. 1 is a schematic explanatory view showing a first embodiment of a method for forming an amorphous hard carbon film of a compressor sliding member of the present invention in a side section. FIG. 2 is a schematic plan view showing a first embodiment of a method for forming an amorphous hard carbon film on a compressor sliding member of the present invention.

The first embodiment of the method for forming an amorphous hard carbon film of the compressor sliding member of the present invention shown in FIGS. 1 and 2 is formed with a recess 400 that accommodates the disk-shaped swash plate 12. A glow discharge plasma is generated between the holding electrode 4 and the gas supply electrode body 10, and the holding electrode 4 is moved in the direction of the arrow shown in FIG. It is a method of forming.
The swash plate 12 has a disk shape, and the sliding surface is an annular flat surface on both sides of the swash plate 12.

  In the first embodiment of FIG. 1, a method for forming an amorphous hard carbon film on one sliding surface of the swash plate 12 is described. The holding electrode 4 has a flat plate shape, and has a concave portion 400 large enough to accommodate one swash plate 12. The swash plate 12 is accommodated in the concave portion 400 so as to have substantially the same height as the surface of the holding electrode 4. Yes.

  The surface of the swash plate 12 and the surface of the holding electrode 4 other than the portion where the amorphous hard carbon film of the swash plate 12 is formed are covered with a dielectric coating 13. The dielectric coating 13 has a thickness of 0.01 mm to 0.1 mm.

  The gas supply electrode body 10 includes a source gas supply port 1, an exhaust port 2, and an application electrode 3 covered with a dielectric 5.

  The source gas supply port 1 and the exhaust port 2 are slit-shaped. The width of the slit is 2 to 6 mm. The slit length may be long enough to cover the sliding surface on which the amorphous hard carbon film is formed. In FIG.1 and FIG.2, the source gas supply port 1 and the exhaust port 2 are the slit shape of width 2mm and length 200mm.

  Although not shown, the source gas supply port 1 is connected to a cylinder for supplying source gas, and the flow rate is controlled by a control valve. The exhaust port 2 is connected to an exhaust pump (not shown) and is sucked by the exhaust pump to exhaust the source gas. In FIG. 1, the flow of the source gas is shown by dotted arrows. The source gas blown out from the source gas supply port 1 to the holding electrode 4 side is sucked up from the exhaust ports 2 provided on both sides of the source gas supply port 2, and a new source material is always provided between the application electrode 3 and the holding electrode 4. Gas flows in a certain direction.

  The application electrode 3 is made of a conductor. For example, a metal material such as aluminum, copper, or brass, or a carbon material can be used as the material. The application electrode 3 is covered with a dielectric 5. The dielectric 5 is preferably 0.5 mm or more in thickness and smaller than the discharge gap distance. The material of the dielectric 5 can be the same as that of the dielectric coating 13. The materials of the dielectric 5 and the dielectric coating 13 may be the same or different.

  The application electrode 3 has a plate shape, and the length is preferably longer than the diameter of the swash plate 12, and the width and height are not particularly limited. The surface of the application electrode 3 is covered with a dielectric 5 with a thickness of 1 mm on the surface on the holding electrode 4 side. The two application electrodes 3 are disposed at a position sandwiched between the slit-shaped source gas supply port 1 and the two discharge ports 2 on both sides. A power source 6 is connected to the application electrode 3 and applied. The power source 6 is an AC power source having a frequency of several kHz or more, which is generally used for atmospheric pressure plasma discharge. For example, the power source 6 can be an AC pulse power source or an RF power source.

  The discharge gap distance between the application electrode and the holding electrode can be appropriately set to 0.5 mm to 10 mm.

  Next, a film forming method will be described. As a source gas from the source gas supply port 1, an inert gas / hydrocarbon gas is supplied at a mixing ratio = 0/100 to 99/1 and a source gas flow rate of 1 mm / sec to 1000 mm / sec. At the same time, exhaust from the exhaust port 2 is performed at a speed equal to or higher than that of the raw material gas. By doing so, the source gas is uniformly convected and the source gas is evenly diffused. Next, the application electrode 3 is applied by the power source 6, and glow discharge plasma is generated between the application electrode 3 and the holding electrode 4.

  By supplying and exhausting the source gas while performing plasma discharge under such conditions, an amorphous hard carbon film is formed on the sliding surface. As shown by the arrows in FIGS. 1 and 2, the gas supply electrode body 10 is fixed and the holding electrode 4 is moved. In addition, the film forming reaction on the sliding surface can be promoted by heating the sliding member, whereby the coating film can be enhanced.

  By sliding the holding electrode 4 relative to each other, sliding surfaces are sequentially formed.

  In the first embodiment, the swash plate 12 formed by the film forming method described above corresponds to the compressor sliding member of the present invention. Further, the film forming apparatus for the amorphous hard carbon film of the compressor sliding member of the present invention includes the holding electrode 4, the gas supply electrode body 10, the power source 6 corresponding to the voltage applying means, the holding electrode 4 and the gas. It comprises a moving means (not shown) for relatively moving the supply electrode body 10 and a film forming control means for controlling the film forming conditions described above. The moving means is not particularly limited as long as it is a means for horizontally moving the holding electrode without changing the discharge gap distance. Although not shown, the film formation control means corresponds to means for controlling the above-described conditions such as voltage, supply air, and exhaust.

[Second Example]
FIG. 3 is a schematic explanatory view showing a second embodiment of the film forming method of the amorphous hard carbon film of the compressor sliding member of the present invention in a side section. FIG. 4 is a schematic plan view showing a second embodiment of the method for forming an amorphous hard carbon film on the compressor sliding member of the present invention.

  The second embodiment of the method for forming an amorphous hard carbon film on the compressor sliding member of the present invention shown in FIGS. 3 and 4 is a concave portion 410 for accommodating a disk-shaped swash plate 121 having a convex portion 122. Is generated on the sliding surface of the swash plate 121 by generating glow discharge plasma between the holding electrode 41 and the gas supply electrode body 10, and moving the holding electrode 41 in the rotation direction of the arrow shown in FIG. This is a method of forming an amorphous hard carbon film.

  Only the parts different from the first embodiment will be described below. The gas supply electrode body 10 faces an annular sliding surface formed around the convex portion 122 and relatively rotates around the convex portion 122. In FIG. 4, the gas supply electrode body 10 is fixed, and the holding electrode 41 is rotated in the direction of the arrow. The convex part 122 is a cylindrical convex part with a height of 2 mm. The swash plate 121 has a hole in the convex portion 122. As shown in FIG. 4, the swash plate 121 and the holding electrode 41 are covered with a dielectric coating 13 except for the sliding surface and the convex portion 122 and the hole.

  A uniform film can be formed by relatively moving the holding electrode 41 and the gas supply electrode body 10. Other explanations are the same as in the first embodiment.

  In the second embodiment, the swash plate 121 formed by the film forming method described above corresponds to the compressor sliding member of the present invention. In the second embodiment, the moving means is means for rotating and moving horizontally without changing the discharge gap distance of the holding electrode 41.

[Third embodiment]
FIG. 6 is a schematic explanatory view showing a third embodiment of the film forming method of the amorphous hard carbon film of the compressor sliding member of the present invention in a side section. FIG. 7 is a schematic plan view showing a third embodiment of the method for forming an amorphous hard carbon film on the compressor sliding member of the present invention. FIG. 5 shows a schematic view of a shoe which is an example of a compressor sliding member.

  The third embodiment of the method of forming the amorphous hard carbon film on the compressor sliding member of the present invention shown in FIGS. 6 and 7 is based on the amorphous hard carbon on the sliding surface 123 of the shoe 7 shown in FIG. This is a method of forming a carbon film. Glow discharge plasma is generated between the holding electrode 42 in which a plurality of recesses 420 for accommodating a plurality of shoes 7 are formed and the gas supply electrode body 10, and the holding electrode 42 is shown in FIG. 6 is a method of forming an amorphous hard carbon film on the sliding surface 123 of the shoe 7 by moving in the arrow direction shown in FIG.

  A plurality of recesses 420 are formed in the holding electrode 42, and the sliding surface 123 of the plurality of shoes 7 is held in substantially the same plane as the electrode surface of the holding electrode 42. It is the same.

  In the third embodiment, the shoe 7 formed by the film forming method described above corresponds to the compressor sliding member of the present invention. The amorphous hard carbon film forming apparatus for the compressor sliding member of the third embodiment is the same as that of the first embodiment except for the holding electrode 42.

[Fourth embodiment]
FIG. 8 is a schematic explanatory view showing a fourth embodiment of the film forming method of the amorphous hard carbon film of the compressor sliding member of the present invention in a side section. The fourth embodiment of the method for forming the amorphous hard carbon film of the compressor sliding member of the present invention shown in FIG. 8 uses the gas supply electrode body 10 and the second gas supply electrode body 11 from both sides. In this method, an amorphous hard carbon film is formed at the same time.

  Glow discharge plasma is generated between the holding electrode 43 formed with a plurality of recesses 430 for accommodating a plurality of shoes 7 on both sides, the gas supply electrode body 10 and the second gas supply electrode body 11, and the holding electrode 43 is This is a method of forming an amorphous hard carbon film on both sides of the holding electrode 43 by moving in the direction of the arrow shown in FIG.

  The gas supply electrode body 10 and the second gas supply electrode body 11 are the same, and other than that is the same as in the third embodiment.

  In the fourth embodiment, the shoe 7 formed by the film forming method described above corresponds to the compressor sliding member of the present invention. Further, the amorphous hard carbon film forming apparatus for the compressor sliding member of the fourth embodiment is the same as that of the third embodiment except that the gas supply electrode body is the gas supply electrode body 10 and the second gas supply electrode body 11. It is the same thing.

[Test example]
An amorphous hard carbon film was formed using the method shown in FIG.

  A swash plate having a diameter of 100 mm and a thickness of 6 mm made of cast iron was used, the dielectric was alumina, and the dielectric coating was a fluororesin tape.

  The holding electrode is a copper flat plate having a length of 200 mm and a thickness of 8 mm.

  The gas supply electrode body 10 has a plate shape with a length of 100 mm, a width of 250 mm, and a thickness of 2 mm, and holds an application electrode 3, a source gas supply port 1 and two discharge ports 2 on both sides.

  The application electrode 3 has a rod shape with a length of 200 mm and a width of 10 mm. The surface of the application electrode 3 is covered with an alumina dielectric 5 with a thickness of 1 mm on the surface on the holding electrode side. The two application electrodes 3 are disposed at a position sandwiched between the slit-shaped source gas supply port 1 and the two discharge ports 2 on both sides.

  Both the raw material gas supply port 1 and the discharge port 2 have a slit shape with a width of 2 mm and a length of 200 mm. The source gas supply port 1 is connected to a gas cylinder that supplies source gas. The two discharge ports 2 are connected to an exhaust pump.

  A power source 6 is connected to the application electrode 3 and applied. The power source 6 is a pulse AC power source. The holding electrode 4 is grounded.

  A uniaxial movable stage is disposed below the holding electrode 4, and the uniaxial movable stage is moved without changing the discharge gap distance to move the holding electrode 4 in the direction of the arrow in FIG.

  Performed under the conditions of a discharge gap distance of 1 mm, an applied AC power supply voltage of 20 kV, an applied AC power supply frequency of 10 kHz, a raw material mixed gas ratio, nitrogen gas: acetylene gas = 25: 75 constant, a gas flow rate of 50 mm / sec, and a holding electrode moving speed of 40 mm / min. It was. The film thickness of the amorphous hard carbon film could be controlled by controlling the moving speed. These series of film forming methods were performed under an atmospheric pressure release environment, and film formation was performed under an environment of approximately 1 atm.

  As a result, an amorphous hard carbon film having a smooth 3 μm surface could be uniformly formed on the sliding surface.

  FIG. 9 shows a SEM observation photograph of a swash plate on which an amorphous hard carbon film is formed under the above conditions. In FIG. 9, 500 is a cross section of the cast iron substrate, 600 is a cross section of the amorphous hard carbon film, and 610 is the surface of the amorphous hard carbon film. It was confirmed that an amorphous hard carbon film having a smooth surface of 3 μm was formed on the surface of the substrate.

  Further, film formation was performed under the same conditions except that the above conditions and the discharge gap distance were set to 5 mm. At this time, atmospheric pressure glow discharge could not be generated and film formation was not possible. This is presumably because nitrogen gas was used as the inert gas. When helium or argon is used as the inert gas, stable glow discharge can be performed even if the gap distance is 5 mm or more. For example, when helium is used as the inert gas, the gap distance may be 10 mm.

It is a schematic explanatory drawing which shows the 1st Example of the film-forming method of the amorphous | non-crystalline hard carbon membrane | film | coat of the compressor sliding member of this invention in a side cross section. It is a plane schematic explanatory drawing which shows the 1st Example of the film-forming method of the amorphous | non-crystalline hard carbon film of the compressor sliding member of this invention. It is a schematic explanatory drawing which shows the 2nd Example of the film-forming method of the amorphous | non-crystalline hard carbon membrane | film | coat of the compressor sliding member of this invention in a cross section. It is a plane model explanatory drawing which shows the 2nd Example of the film-forming method of the amorphous | non-crystalline hard carbon film of the compressor sliding member of this invention. It is a schematic diagram of a shoe which is an example of a compressor sliding member. It is a schematic explanatory drawing which shows the 3rd Example of the film-forming method of the amorphous | non-crystalline hard carbon membrane | film | coat of the compressor sliding member of this invention in a cross section. It is a plane schematic explanatory drawing which shows the 3rd Example of the film-forming method of the amorphous | non-crystalline hard carbon film of the compressor sliding member of this invention. It is a schematic explanatory drawing which shows the 4th Example of the film-forming method of the amorphous | non-crystalline hard carbon film of the compressor sliding member of this invention in a cross section. The SEM observation photograph of the sliding surface formed into a film by the test example is shown.

Explanation of symbols

1, source gas supply port, 2, exhaust port, 3, application electrode, 4, holding electrode, 41, holding electrode,
42, holding electrode, 43, holding electrode, 5, dielectric, 6, power supply, 7, shoe,
10, gas supply electrode body 11, 11, second gas supply electrode body 12, swash plate 121, swash plate,
122, convex portion, 13, dielectric coating, 123, sliding surface, 400, concave portion, 410, concave portion,
420, recessed part, 430, recessed part, 500, cross section of cast iron base material, 600, cross section of amorphous hard carbon film, 610, surface of amorphous hard carbon film.

Claims (10)

A method for forming an amorphous hard carbon film of a compressor sliding member comprising a housing process and a film forming process,
It said receiving step is to accommodate the sliding member of the compressor so that the sliding surface and the electrode surface of the storage electrode of the sliding member is substantially coplanar to the holding electrode process to the deposition body And
The film forming step includes
The film formation body, a material gas supply port for supplying a material gas to the surface of the film formation body, an exhaust port disposed on at least both sides of the material gas supply port in the relative movement direction, and the film formation film during the film formation A gas supply electrode body which is arranged opposite to the film formation body and is formed of an application electrode having a shape in which the surface on the holding electrode side is covered with a dielectric, and has a discharge gap distance along the film formation body. , While moving the relative
Deposition pressure: near atmospheric pressure,
Mixing ratio of raw material gases: inert gas / hydrocarbon-based gas = 0/100 to 99/1
Discharge gap distance between the application electrode and the holding electrode: 0.5 mm to 10 mm,
The raw material gas flow rate: 1mm / sec~1000mm / under the conditions of sec by generating a glow discharge plasma between said gas an alternating voltage supply electrode body mark pressure and the applied electrode wherein the deposition surface of, A step of forming an amorphous hard carbon film on at least the sliding surface;
An amorphous hard member of a compressor sliding member characterized in that an applied electrode surface facing the film formation body at the time of film formation has a shape that is opposed to the discharge gap distance. Carbon film formation method.   2. The method for forming an amorphous hard carbon film on a compressor sliding member according to claim 1, wherein portions other than the sliding surface of the film formation target are covered with a second dielectric.   The method for forming an amorphous hard carbon film on a compressor sliding member according to claim 1, wherein the sliding member is a swash plate of a swash plate compressor.   The method for forming an amorphous hard carbon film on a compressor sliding member according to claim 1 or 2, wherein the sliding member is a shoe of a swash plate compressor. The sliding member is a disc-shaped swash plate having a convex portion at the center,
The sliding surface is an annular sliding plane surrounding the convex portion,
4. The compressor sliding member amorphous according to claim 3, wherein the relative movement in the film forming step is such that the gas supply electrode body facing the annular sliding plane relatively rotates around the convex portion. 5. A method for forming a hard carbon film.   The method for forming an amorphous hard carbon film on a compressor sliding member according to claim 4, wherein the accommodating step is a plural accommodating step of accommodating a plurality of the shoes in the holding electrode. The sliding surface has a first sliding surface and a second sliding surface;
The holding electrode accommodates the first sliding surface and the second sliding surface on both sides in an open state,
The gas supply electrode body comprises a first gas supply electrode body and a second gas supply electrode body disposed on both sides of the holding electrode,
In the film forming step, the first sliding surface is opposed to the first gas supply electrode body and the second sliding surface is opposed to the second gas supply electrode body during the film formation. The amorphous hard carbon of the compressor sliding member according to claim 1 or 2, which is a double-sided film forming step in which the amorphous hard carbon film is formed on the surface and the second sliding surface at substantially the same time. Carbon film formation method.   The hydrocarbon gas is acetylene, the inert gas is nitrogen, and a discharge gap distance between the application electrode and the holding electrode is 0.5 mm or more and less than 5 mm. A method for forming an amorphous hard carbon film on the compressor sliding member according to claim 1. A base material forming a compressor sliding member;
An amorphous hard carbon film coated on the sliding surface of the substrate;
A compressor sliding member having
The compressor sliding member formed by the film forming method according to claim 1, wherein the amorphous hard carbon film is formed. A holding electrode the sliding member of the compressor and the sliding surface and the electrode surface of the sliding member held so as to be substantially coplanar,
An exhaust port provided on at least both sides of the source gas supply port in the relative movement direction of the source gas supply port and the holding electrode, and a surface on the side of the holding electrode provided facing the holding electrode during film formation A gas supply electrode body that has an application electrode that is covered with a dielectric and has a shape that faces the deposition target body at a discharge gap distance ;
Voltage application means for applying to the application electrode;
Moving means for relatively moving the holding electrode and the gas supply electrode body;
Deposition pressure: near atmospheric pressure, mixing ratio of source gases: inert gas / hydrocarbon gas = 0/100 to 99/1, discharge gap distance between the applied electrode and the holding electrode: 0.5 mm to A film forming control means capable of controlling a space between the holding electrode and the applied electrode under a film forming condition of 10 mm and a raw material gas flow rate of 1 mm / sec to 1000 mm / sec;
A film forming apparatus for forming an amorphous hard carbon film on a compressor sliding member.

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