WO2019172321A1 - Revêtement composite et procédé de formation d'un revêtement composite - Google Patents

Revêtement composite et procédé de formation d'un revêtement composite Download PDF

Info

Publication number
WO2019172321A1
WO2019172321A1 PCT/JP2019/008891 JP2019008891W WO2019172321A1 WO 2019172321 A1 WO2019172321 A1 WO 2019172321A1 JP 2019008891 W JP2019008891 W JP 2019008891W WO 2019172321 A1 WO2019172321 A1 WO 2019172321A1
Authority
WO
WIPO (PCT)
Prior art keywords
hard carbon
carbon film
film
layer
forming
Prior art date
Application number
PCT/JP2019/008891
Other languages
English (en)
Japanese (ja)
Inventor
慎也 藤井
森口　秀樹
Original Assignee
日本アイ・ティ・エフ株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 日本アイ・ティ・エフ株式会社 filed Critical 日本アイ・ティ・エフ株式会社
Priority to CN201980016129.2A priority Critical patent/CN111788328B/zh
Publication of WO2019172321A1 publication Critical patent/WO2019172321A1/fr

Links

Images

Classifications

    • 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
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • 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
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/24—Vacuum evaporation
    • C23C14/32—Vacuum evaporation by explosion; by evaporation and subsequent ionisation of the vapours, e.g. ion-plating
    • 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

Definitions

  • the present invention relates to a composite coating and a method for forming the composite coating, and more particularly to a composite coating including a hard carbon coating that has excellent durability and exhibits excellent adhesion, and a method for forming the composite coating.
  • Hard carbon (DLC: diamond-like carbon) film has excellent sliding characteristics such as low friction, high wear resistance, and low cohesion (seizure resistance). Widely used as sliding members for molds, cutting tools and automobile parts.
  • the hard carbon film 2 is made of a hydrogen-free hard carbon (aC) film.
  • a technique of developing a two-layer structure of a lower layer 22 and an upper layer 23 of a hydrogen-containing hard carbon (aC: H) film has been developed (for example, Patent Document 1).
  • a hydrogen-containing hard carbon film having a thickness of 2 to 10 times that of the hydrogen-free hard carbon film and a hydrogen content of 5 to 25 at% was formed on the hydrogen-free hard carbon film having a thickness of 0.5 to 200 nm.
  • a coating has been developed (for example, Patent Document 2).
  • Patent Document 2 describes that the adhesion between the base material and the hard carbon film is improved by forming an intermediate layer 21 of W, Ti, Nb or the like on the surface of the base material.
  • the hydrogenation tetrahedral has a Young's modulus higher than 200 GPa, an sp 3 ratio of 50 to 90%, a hydrogen content of 20 at% or less, and a film thickness of more than 1 ⁇ m.
  • ta—C H
  • the hard carbon film is applied to a member such as a bearing, a gear, or a roller used under more severe sliding conditions by taking advantage of these excellent sliding characteristics of the hard carbon film.
  • JP 2000-128516 A Japanese Patent Laid-Open No. 2003-026414 Japanese Patent No. 5503145
  • the present invention is excellent in fracture resistance and peel resistance, and can exhibit excellent adhesion even when used in applications where large contact stress is repeatedly generated during sliding, and has sufficient durability. It is an object to provide a film and a method for forming the film.
  • a composite coating coated on a substrate A hard carbon film A having a hydrogen content of less than 5 at% and a film thickness of 200 to 1000 nm is formed in the lower layer, In the upper layer, a hard carbon film B having a hydrogen content of 5 to 30 at%, a film thickness of 210 to 5000 nm, and a Young's modulus greater than 200 GPa is formed, The hard carbon film A and the hard carbon film B are directly laminated to form a composite coating.
  • the lower layer ta—C: H layer is hydrogenated and therefore has a low adhesion to the upper layer.
  • the ta-C: H layer has a high sp 3 ratio and high hardness, but the film thickness is thicker than 1 ⁇ m.
  • the residual stress of a hard carbon film increases as the hardness increases and the film thickness increases. Therefore, a hard carbon film having a film thickness thicker than 1 ⁇ m has a very large residual stress and is likely to break. For this reason, when a shocking stress is applied, the lower layer is easily broken, and the coating is peeled off from the base material, resulting in a decrease in adhesion.
  • the hard carbon film having a hydrogen content of less than 5 at% in the present claims has a low hydrogen content, the hard carbon film has a high hardness while having sufficient adhesion to the base material and other hard carbon films. For this reason, if the film thickness is too thin, it cannot withstand repeated contact stress and is easily deformed and broken, and if it is too thick, it cannot withstand the load of shocking stress and is broken, and the adhesion tends to be lowered. As a result of various experiments and studies, the present inventor has solved these problems by setting the film thickness of the lower hard carbon film (hard carbon film A) to 200 to 1000 nm, and has excellent adhesion. Has found that can be demonstrated.
  • the present inventor further directly has a hard carbon film (hard carbon film B) having a hydrogen content of 5 to 30 at%, a film thickness of 210 to 5000 nm, and a Young's modulus greater than 200 GPa on the hard carbon film A.
  • a hard carbon film having a hydrogen content of 5 to 30 at%, a film thickness of 210 to 5000 nm, and a Young's modulus greater than 200 GPa on the hard carbon film A.
  • the Young's modulus of the hard carbon film B is preferably 500 GPa or less from the viewpoint of preventing a drop in chipping resistance.
  • the hard carbon film A is formed by laminating a plurality of hard carbon layers having different ⁇ / ⁇ intensity ratios, The ⁇ / ⁇ intensity ratio of the hard carbon layer located in the uppermost layer is smaller than the ⁇ / ⁇ intensity ratio in the entire hard carbon layer located in the lower layer than the hard carbon layer located in the uppermost layer.
  • the hard carbon film A When the hard carbon film A is formed as a thick film with a single layer, the residual stress of the film tends to be high, and breakage or peeling tends to occur.
  • the hard carbon film A is a laminated body of a plurality of thin films having different ⁇ / ⁇ intensity ratios, and the ⁇ / ⁇ intensity ratio of the hard carbon layer located in the uppermost layer is in the entire hard carbon layer located in the lower layer.
  • positions so that it may become smaller than (pi) / (sigma) intensity ratio the residual stress can be restrained low, generation
  • the ⁇ / ⁇ intensity ratio in the entire hard carbon layer means an average value in consideration of the film thickness of each layer when the lower layer is composed of a plurality of layers.
  • the ⁇ / ⁇ intensity ratio is an index related to the ratio of sp 2 bonds to sp 3 bonds (sp 2 / sp 3 ratio) in the hard carbon film. When there are few sp 2 bonds and many sp 3 bonds, ⁇ When the / ⁇ intensity ratio is small and there are many sp 2 bonds and few sp 3 bonds, the ⁇ / ⁇ intensity ratio is large.
  • the hard carbon film A is formed by laminating a plurality of hard carbon layers having different ⁇ / ⁇ intensity ratios, a single layer of hard carbon having the same ⁇ / ⁇ intensity ratio throughout. Unlike the film, the residual stress can be reduced by relaxing the contact stress even between the hard carbon layers of each layer.
  • the ⁇ / ⁇ intensity ratio of the hard carbon layer positioned at the uppermost layer is made smaller than the ⁇ / ⁇ intensity ratio of the entire hard carbon layer positioned below the uppermost hard carbon layer, the uppermost hard carbon layer is sp 3. Since there are many bonds and the hydrogen content is low, tetrahedral carbon free of bonds is sufficiently formed, and excellent adhesion to the hard carbon film B formed in the upper layer can be ensured.
  • the invention according to claim 3 3.
  • the adhesion to the substrate and other hard carbon films is improved as the hydrogen content of the hard carbon film A is lower.
  • the hydrogen content is less than 1 at%, the adhesion to other hard carbon films can be more sufficiently ensured.
  • a metal intermediate layer of Cr, W or Ti is provided between the base material and the hard carbon film A,
  • the film thickness of the metal intermediate layer is preferably 30 to 500 nm in consideration that sufficient adhesion cannot be ensured if it is too thin, and sufficient fracture resistance cannot be ensured if it is too thick.
  • the hard carbon film B is When the cross section is observed with a bright field TEM image, it has a relatively white white hard carbon layer and a relatively black black hard carbon layer, The composite coating according to any one of claims 1 to 4, wherein the white hard carbon layer and the black hard carbon layer are alternately laminated at a nano level.
  • the relatively white white hard carbon layer has a low density, a large sp 2 / sp 3 ratio, and a low hardness.
  • the relatively black black hard carbon layer has a high density, a small sp 2 / sp 3 ratio, and a high hardness.
  • the hard carbon film B is configured by alternately laminating the white hard carbon layer and the black hard carbon layer having different hardness in this manner, it is possible to obtain larger stress relaxation. It is possible to exert higher fracture resistance and peel resistance and to ensure excellent adhesion.
  • the white hard carbon layer having a large sp 2 / sp 3 ratio is excellent in chipping resistance due to its low hardness but insufficient in abrasion resistance as described above, and a black having a small sp 2 / sp 3 ratio.
  • the hard carbon layer has high wear resistance due to its high hardness. For this reason, a hard carbon film in which white hard carbon layers and black hard carbon layers are alternately stacked can achieve both chipping resistance and wear resistance, and can exhibit excellent sliding characteristics.
  • the above-mentioned nano level is preferably 0.1 to 10 nm.
  • the hard carbon film A forming step is a step of forming by an arc vapor deposition method,
  • the method for forming a composite coating is characterized in that the step of forming the hard carbon film B is a step of forming by an arc vapor deposition method while introducing a hydrocarbon-based gas or a hydrogen gas.
  • the arc evaporation method is a film forming method using graphite as a film forming source, the hard carbon film A having a hydrogen content of less than 5 at% can be easily formed.
  • this arc vapor deposition method is performed while introducing hydrocarbon gas or hydrogen gas, carbon and hydrogen are combined to easily form a hard carbon film B having a hydrogen content of 5 to 30 at%. it can.
  • the invention according to claim 8 provides: 8. The method of forming a composite coating according to claim 7, wherein, in the step of forming the hard carbon film B, the hard carbon film B is formed while rotating the base material on which the hard carbon film A is formed. It is.
  • the hard carbon film B When the hard carbon film B is formed, by rotating the base material on which the hard carbon film A is formed, it is possible to periodically provide a time during which the carbon ions evaporated from the graphite are not irradiated on the base material.
  • a black hard carbon layer ta-C: H or aC: H
  • a white hard carbon layer aC: H
  • the present invention has excellent fracture resistance and peel resistance, and can exhibit excellent adhesion even when used for applications in which large contact stress is repeatedly generated during sliding, and has sufficient durability. It is possible to provide a film having the same and a method for forming the same.
  • FIG. 1 is a schematic cross-sectional view showing the configuration of the composite coating according to the present embodiment.
  • the composite coating 1 according to the present embodiment includes a metal intermediate layer 11, a lower hard carbon film (hard carbon film A) 12, and an upper hard carbon film (hard carbon) on a base material B.
  • Film B) 13 is laminated in this order.
  • Hard carbon film A The lower hard carbon film (hard carbon film A) is a hard carbon film having a hydrogen content of less than 5 at%.
  • the hydrogen content By setting the hydrogen content to less than 5 at%, it is possible to sufficiently ensure adhesion to the base material and other hard carbon films.
  • membrane can be improved, so that hydrogen content is low, it is more preferable in it being less than 1 at%.
  • a hard carbon film having a hydrogen content of less than 5 at% has a high hardness, if the film thickness is too thin, it cannot withstand repeated contact stress and is easily deformed and broken. Unbearable and easily destroyed. Therefore, in this embodiment, it is set to 200 to 1000 nm.
  • ta-C hydrogen-free tetrahedral carbon
  • the lower hard carbon film (hard carbon film A) is preferably formed by laminating a plurality of hard carbon layers having different ⁇ / ⁇ strength ratios.
  • FIG. 2 is a schematic cross-sectional view for explaining how the hard carbon film A is formed by laminating a plurality of hard carbon layers in the composite coating 1.
  • the lower layer hard carbon film (hard carbon film A) is configured by arranging a plurality of layers under the uppermost layer 12T.
  • ⁇ / ⁇ intensity ratio in the uppermost layer 12T it is preferable to make the ⁇ / ⁇ intensity ratio in the uppermost layer 12T smaller than the ⁇ / ⁇ intensity ratio in the entire hard carbon layer located in the lower layer below it.
  • the residual stress can be reduced in the uppermost layer 12T.
  • excellent adhesion with the substrate can be ensured.
  • ⁇ / ⁇ intensity ratio in the entire hard carbon layer located in the lower layer means that when the hard carbon layer located in the lower layer is composed of a plurality of layers, the thickness of each layer is considered. It means the calculated average value.
  • the small ⁇ / ⁇ intensity ratio indicates that there are many sp 3 bonds and a low hydrogen content, and as a result, sufficient tetrahedral carbon free of bonds is formed on the surface of the hard carbon layer. Thus, excellent adhesion with the upper hard carbon film (hard carbon film B) 13 can be ensured.
  • Hard carbon film B The upper hard carbon film (hard carbon film B) 13 is a hard carbon film having a hydrogen content of 5 to 30 at%, a film thickness of 210 to 5000 nm, and a Young's modulus greater than 200 GPa. Thereby, since a large load (stress) repeatedly applied at the time of sliding can be sufficiently relaxed, such a hard carbon film is used as an upper hard carbon film (hard carbon film B) 13 and a lower hard carbon film ( By directly laminating on the hard carbon film A) 12, sufficient fracture resistance and peel resistance can be exhibited and excellent adhesion can be ensured.
  • the upper hard carbon film (hard carbon film B) 13 is preferably formed by laminating a plurality of layers. Specifically, when a cross section of the upper hard carbon film (hard carbon film B) 13 is observed with a bright-field TEM image, a relatively white white hard carbon layer and a relatively black black hard carbon layer are alternately arranged. It is preferable that they are laminated.
  • FIG. 3 is a schematic cross-sectional view for explaining how the hard carbon film B is formed by laminating a plurality of hard carbon layers in the composite coating 1.
  • the upper hard carbon film (hard carbon film B) is formed by alternately laminating white hard carbon layers 13W and black hard carbon layers 13B.
  • the black hard carbon layer 13B Since the black hard carbon layer 13B has a high density and a small sp 2 / sp 3 ratio, it has a high hardness. On the other hand, since the white hard carbon layer 13W has a low density and a large sp 2 / sp 3 ratio, it has a low hardness. Thus, by alternately laminating the white hard carbon layer 13W and the black hard carbon layer 13B having different hardnesses, it is possible to obtain a greater stress relaxation, exhibiting higher fracture resistance and peel resistance, Excellent adhesion can be ensured.
  • the white hard carbon layer 13W include a hydrogenated amorphous carbon (aC: H) layer
  • examples of the black hard carbon layer 13B include a hydrogenated tetrahedral carbon (ta-C: H).
  • ta-C: H hydrogenated tetrahedral carbon
  • aC: H hydrogenated amorphous carbon
  • each of the white hard carbon layer 13W and the black hard carbon layer 13B is preferably laminated at a nano-level with a thickness of 0.1 to 10 nm.
  • the intermediate layer hard carbon film may be directly formed on the substrate, but depending on the type of the substrate, sufficient adhesion may not be ensured.
  • the base materials such as aluminum alloy, Mg alloy and cemented carbide do not have sufficient adhesion to the hard carbon film.
  • the base material B As shown in FIG. 1, it is preferable to appropriately provide the metal intermediate layer 11 on the base material B, whereby the base material B is interposed via the metal intermediate layer 11. And the composite coating 1 can be sufficiently adhered to each other.
  • the provided metal intermediate layer 11 is preferable because it contributes to improvement of wear resistance.
  • Examples of the metal element that can be used as such a metal intermediate layer include Cr, Ti, Si, W, and B. Among these, Cr, Ti, and W are preferable.
  • the thickness of the metal intermediate layer 11 is preferably 30 to 500 nm, more preferably 40 to 400 nm, and particularly preferably 50 to 300 nm.
  • the base material on which the composite film is formed is not particularly limited, and base materials such as non-ferrous metals, ceramics, and hard composite materials can be used in addition to iron-based materials. Examples include chromium molybdenum steel (SCM), carbon steel, alloy steel, hardened steel, high speed tool steel, cast iron, aluminum alloy, Mg alloy and cemented carbide, etc. Then, the base material whose characteristics do not deteriorate greatly at a temperature exceeding 200 ° C. is preferable.
  • SCM chromium molybdenum steel
  • carbon steel alloy steel
  • hardened steel high speed tool steel
  • cast iron aluminum alloy
  • Mg alloy and cemented carbide etc.
  • a base material B to be a target for forming a hard carbon film is prepared and set in a film formation tank.
  • a hard carbon film of the base material B is formed by introducing a rare gas such as Ar gas or hydrogen gas into the film formation tank to generate plasma and applying a bias voltage to the base material B. It is preferable to remove the dirt and oxide layer on the surface (the surface on which the hard carbon film is formed).
  • the metal intermediate layer and the metal intermediate layer 11 are formed on the hard carbon film forming surface from which the dirt and oxide layer have been removed, if necessary.
  • the metal intermediate layer 11 is preferably formed by an arc vapor deposition method (arc ion plating method) using a metal raw material such as Cr, W or Ti as an arc evaporation source.
  • the hydrogen content can be measured by HFS (Hydrogen Forward Scattering) analysis.
  • the lower layer hard carbon film (hard carbon film A) 12 it is preferable to stack the hard carbon layers having different ⁇ / ⁇ intensity ratios.
  • the voltage (bias voltage) applied to the substrate By appropriately adjusting the voltage (bias voltage) applied to the substrate, the ⁇ / ⁇ intensity ratio can be controlled, and hard carbon layers having different ⁇ / ⁇ intensity ratios can be laminated.
  • the ⁇ / ⁇ intensity ratio of the uppermost layer 12T is controlled to be smaller than the ⁇ / ⁇ intensity ratio of all the lower layers so that sp 3 bonds increase.
  • a hard carbon film in which tetrahedral carbon having free bonds is sufficiently formed on the uppermost layer 12T is formed, and sufficient adhesion to the hard carbon film (hard carbon film B) 13 formed in the upper layer is obtained. Can be secured.
  • the ⁇ / ⁇ intensity ratio is determined by measuring 1 s ⁇ ⁇ * intensity and 1 s ⁇ * intensity by EELS analysis (Electron Energy-Loss Spectroscopy), and measuring the measured ⁇ * intensity and ⁇ * intensity. It is a value obtained as a ratio, and it is known that there is a correlation with the ratio of sp 2 and sp 3 bonds (sp 2 / sp 3 ratio) in the hard carbon film.
  • sp 2 bonds less sp 3 bonds is often a [pi / sigma intensity ratio decreases in the hard carbon film, whereas, during the hard carbon film sp 2 bond many sp 3 bonds is small and [pi / Since the ⁇ intensity ratio increases, the sp 2 / sp 3 ratio can be grasped based on the value of the ⁇ / ⁇ intensity ratio.
  • hard carbon film B Formation of hard carbon film B
  • plasma is generated by introducing a hydrocarbon-based gas or hydrogen gas together with Ar gas into the film-forming vessel while using an arc evaporation method using a graphite cathode as an arc evaporation source.
  • a hydrogenated amorphous carbon (aC: H) film is formed on the lower hard carbon film (hard carbon film A) 12 as an upper hard carbon film (hard carbon film B) 13.
  • the lower hard carbon film (hard carbon film A) 12 is formed by using an arc vapor deposition method, and then a hydrocarbon-based gas or hydrogen gas is introduced to form the lower hard carbon film (hard carbon film A) 12.
  • the upper hard carbon film (hard carbon film B) 13 may be formed by forming a hard carbon film having a higher hydrogen content than the above.
  • the hard carbon film to be formed is a hydrogenated tetrahedral carbon (ta-C: H) film in both the upper layer and the lower layer.
  • the formation of the hard carbon film B may be performed using a film forming apparatus different from the film forming apparatus used for forming the hard carbon film A.
  • the surface of the hard carbon film previously formed is used. Is exposed to the atmosphere and dirt, and the adhesion of the hard carbon film B to the hard carbon film A may deteriorate. Therefore, after forming the hard carbon film A with the same apparatus, It is preferable to form B.
  • the film thickness is controlled to 210 to 5000 nm by appropriately adjusting the temperature in the film forming tank, the arc current, and the like.
  • the hydrogen content of the formed hard carbon film is controlled to 5 to 30 at%.
  • the Young's modulus of the hard carbon film is controlled to be larger than 200 GPa.
  • the Young's modulus can be measured by a nanoindentation method based on ISO14577, for example, using a dynamic hardness meter ENT1100a manufactured by Elionix (load 300 g).
  • hard carbon film B As described above, in forming the upper hard carbon film (hard carbon film B), it is preferable to stack hard carbon layers having different densities.
  • the hard carbon film B When the hard carbon film B is formed, by rotating the base material on which the hard carbon film A is formed, it is possible to periodically provide a time during which the carbon ions evaporated from the graphite are not irradiated on the base material.
  • a black hard carbon layer ta-C: H or aC: H
  • a hydrocarbon-based gas is used as a raw material.
  • a white hard carbon layer aC: H having a low density and a low hardness can be formed.
  • low density aC: H and high density ta-C: H can be alternately laminated.
  • the collision energy is large, so it tends to be black hard carbon with a high density and high hardness and a small sp 2 / sp 3 ratio.
  • These carbon ions are formed as a white hard carbon layer (aC: H) having a low density and low hardness and a large sp 2 / sp 3 ratio because of low collision energy.
  • the hard carbon film formed while rotating and revolving the base material has a structure in which white hard carbon and black hard carbon are laminated.
  • FIG. 6 is a schematic diagram of a main part of an arc PVD apparatus provided with a self-revolving jig used for forming a plurality of layers as described above.
  • this arc PVD apparatus includes a vacuum chamber 42, a plasma generator (not shown), a heater 43, a self-revolving jig 44 as a substrate support device, a thermocouple 45 as a temperature measurement device, and A bias power source (not shown) and a pressure adjusting device (not shown) for adjusting the pressure in the furnace are provided.
  • T is a target (carbon target), and 41 is a base material on which an intermediate layer is formed.
  • such a hard carbon film B has a laminated structure in which a hard carbon film B thinned using FIB (Focused Ion Beam) is clarified by, for example, an accelerating voltage of 200 kV using a TEM (Transmission Electron Microscope).
  • FIB Fluorous Ion Beam
  • TEM Transmission Electron Microscope
  • test piece A composite coating composed of a hard carbon film A and a hard carbon film B was formed on a substrate (SCM415 carburized) to prepare a test piece.
  • the composite coating has a two-layer structure in which a hydrogen-free hard carbon film (hard carbon film A) and a hydrogen-containing hard carbon film (hard carbon film B) having a plurality of layers having different ⁇ / ⁇ strength ratios are laminated, and hard carbon
  • the film A has a thickness of 6 levels of 0 nm, 100 nm, 200 nm, 500 nm, 1000 nm, and 1500 nm
  • the hard carbon film B has a thickness of 5 levels of 100 nm, 210 nm, 2500 nm, 5000 nm, and 7500 nm.
  • Test pieces on which 30 types of composite coatings were formed were prepared. Specifically, each test piece was prepared according to the following procedure.
  • the hydrogen content of the formed hard carbon film A was measured by HFS analysis, the hydrogen content was 0.1 at%.
  • dirt on the surface of the substrate was removed, and a Cr metal intermediate layer (thickness 200 nm) was provided by using an arc ion plating method.
  • Test method The test was performed using a thrust tester shown in FIG. Specifically, a steel ball 51 mounted on the raceway ring 52 is pressed with a constant load in the oil 53 against each test piece 54 on which the composite coating is formed, and the raceway ring 52 rolls along the same raceway. The rotation was performed by repeatedly applying a predetermined number of times to the circulating track portion of the steel ball 51. Details of the test conditions are shown in Table 1.
  • the film portion after repeated load application was observed, and the state was evaluated in five stages using the film adhesion evaluation index shown in Table 2.
  • the film adhesion evaluation index one having a low peel resistance is represented as 1, and one having a high peel resistance is represented as 5.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Physical Vapour Deposition (AREA)
  • Chemical Vapour Deposition (AREA)

Abstract

L'invention concerne un revêtement qui présente une excellente résistance à la rupture et résistance à la séparation, et qui peut générer une adhérence exceptionnelle et a une durabilité suffisante même quand il est utilisé dans des applications où une pression de contact substantielle se produit de manière répétée pendant le glissement. Un procédé de formation de revêtement est en outre décrit. Ce revêtement composite est formé sur un substrat, où : un film de carbone dur A de 200 à 1000 nm d'épaisseur ayant une teneur en hydrogène inférieure à 5 % at. est formé à titre de couche inférieure ; un film de carbone dur B de 210 à 5000 nm d'épaisseur ayant une teneur en hydrogène de 5 à 30 % at. et un module de Young supérieur à 200 GPa est formé à titre de couche supérieure ; et le film de carbone dur A et le film de carbone dur B sont directement stratifiés l'un sur l'autre.
PCT/JP2019/008891 2018-03-08 2019-03-06 Revêtement composite et procédé de formation d'un revêtement composite WO2019172321A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201980016129.2A CN111788328B (zh) 2018-03-08 2019-03-06 复合被膜及复合被膜的形成方法

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2018-041398 2018-03-08
JP2018041398A JP7162799B2 (ja) 2018-03-08 2018-03-08 複合被膜および複合被膜の形成方法

Publications (1)

Publication Number Publication Date
WO2019172321A1 true WO2019172321A1 (fr) 2019-09-12

Family

ID=67845574

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2019/008891 WO2019172321A1 (fr) 2018-03-08 2019-03-06 Revêtement composite et procédé de formation d'un revêtement composite

Country Status (3)

Country Link
JP (1) JP7162799B2 (fr)
CN (1) CN111788328B (fr)
WO (1) WO2019172321A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2024063157A1 (fr) * 2022-09-22 2024-03-28 日本ピストンリング株式会社 Élément coulissant, son procédé de fabrication et film de revêtement

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP7431150B2 (ja) * 2020-12-21 2024-02-14 トヨタ自動車株式会社 被膜及び被膜を有する複合材料

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009504448A (ja) * 2005-08-18 2009-02-05 ナムローゼ・フェンノートシャップ・ベーカート・ソシエテ・アノニム 四面体炭素層および軟質外層を備える層状構造によって被覆された基板
JP2009504919A (ja) * 2005-08-18 2009-02-05 ナムローゼ・フェンノートシャップ・ベーカート・ソシエテ・アノニム 四面体炭素膜を備える層状構造体により被覆した基板
WO2016042629A1 (fr) * 2014-09-17 2016-03-24 日本アイ・ティ・エフ株式会社 Film de revêtement, son procédé de fabrication, et dispositif de dépôt physique en phase vapeur
JP2017171988A (ja) * 2016-03-23 2017-09-28 日本アイ・ティ・エフ株式会社 被覆膜とその製造方法およびｐｖｄ装置
WO2018155385A1 (fr) * 2017-02-21 2018-08-30 日本アイ・ティ・エフ株式会社 Film de carbone dur, son procédé de fabrication et élément coulissant

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4988421A (en) * 1989-01-12 1991-01-29 Ford Motor Company Method of toughening diamond coated tools
JP4331292B2 (ja) 1998-10-30 2009-09-16 株式会社リケン 低摩耗性と優れた密着性を有する複合ダイヤモンドライクカーボン皮膜
JP4793531B2 (ja) 2001-07-17 2011-10-12 住友電気工業株式会社 非晶質炭素被膜と非晶質炭素被膜の製造方法および非晶質炭素被膜の被覆部材
JP4214931B2 (ja) 2004-03-18 2009-01-28 トヨタ自動車株式会社 摺動部材
JP4543373B2 (ja) 2004-06-03 2010-09-15 三菱マテリアル株式会社 非鉄材料の高速切削加工ですぐれた耐摩耗性を発揮する表面被覆超硬合金製切削工具の製造方法
CN101728449A (zh) * 2008-10-31 2010-06-09 宋健民 类钻碳电子装置及其制造方法
EP2587518B1 (fr) * 2011-10-31 2018-12-19 IHI Hauzer Techno Coating B.V. Appareil et procédé de dépôt de couches ta C dépourvues d'hydrogène sur des pièces de travail et pièces
CN107923533B (zh) 2015-08-10 2020-02-07 日本Itf株式会社 活塞环及其制造方法
JP6599251B2 (ja) 2016-01-25 2019-10-30 株式会社リケン 摺動部材及びその製造方法
EP3239349B1 (fr) * 2016-04-26 2022-06-22 IHI Ionbond AG Couche de carbone résistant à l'usure semblable à un diamant tétrahédrique

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009504448A (ja) * 2005-08-18 2009-02-05 ナムローゼ・フェンノートシャップ・ベーカート・ソシエテ・アノニム 四面体炭素層および軟質外層を備える層状構造によって被覆された基板
JP2009504919A (ja) * 2005-08-18 2009-02-05 ナムローゼ・フェンノートシャップ・ベーカート・ソシエテ・アノニム 四面体炭素膜を備える層状構造体により被覆した基板
WO2016042629A1 (fr) * 2014-09-17 2016-03-24 日本アイ・ティ・エフ株式会社 Film de revêtement, son procédé de fabrication, et dispositif de dépôt physique en phase vapeur
JP2017171988A (ja) * 2016-03-23 2017-09-28 日本アイ・ティ・エフ株式会社 被覆膜とその製造方法およびｐｖｄ装置
WO2018155385A1 (fr) * 2017-02-21 2018-08-30 日本アイ・ティ・エフ株式会社 Film de carbone dur, son procédé de fabrication et élément coulissant

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2024063157A1 (fr) * 2022-09-22 2024-03-28 日本ピストンリング株式会社 Élément coulissant, son procédé de fabrication et film de revêtement

Also Published As

Publication number Publication date
JP7162799B2 (ja) 2022-10-31
CN111788328B (zh) 2023-02-28
JP2019157156A (ja) 2019-09-19
CN111788328A (zh) 2020-10-16

Similar Documents

Publication Publication Date Title
CN108368602B (zh) 被覆膜与其制造方法、pvd装置及活塞环
CN108884552B (zh) 被覆膜与其制造方法
US8574715B2 (en) Laminated film and laminated film-coated member
US11293548B2 (en) Sliding member and coating film
JP5393108B2 (ja) 硬質多層膜成形体の製造方法
JP4400603B2 (ja) 硬質炭素被膜を有する部材
JP2007169698A (ja) 非晶質硬質炭素皮膜
JPH09133138A (ja) 軸受装置
JP2007070667A (ja) ダイヤモンドライクカーボン硬質多層膜成形体およびその製造方法
US9546425B2 (en) Member having hydrogen-containing, hard, amorphous carbon coating and its production method
WO2019172321A1 (fr) Revêtement composite et procédé de formation d'un revêtement composite
WO2005100810A1 (fr) Procede de finition des surfaces critiques d'un roulement
JP2013029190A (ja) ピストンリング
JP6453826B2 (ja) 摺動部材およびその製造方法
JP6533818B2 (ja) 摺動部材およびピストンリング
Oohira Characteristics and Applications of DLC films
JP2013014801A (ja) 軸受部品への硬質膜形成方法、転がり軸受
JP2011068941A (ja) 硬質膜の成膜方法および硬質膜
WO2016111288A1 (fr) Stratifié multicouche comprenant du carbone sous forme de diamant amorphe et son procédé de fabrication
WO2018181097A1 (fr) Film de revêtement en carbone dur
JP2018154873A (ja) 積層被覆膜とその製造方法およびピストンリング
WO2015186790A1 (fr) Segment de piston
Sagalovych et al. The Vacuum-plasma Nanotechnologies Avinit
JP2024029683A (ja) 積層硬質炭素膜及びその製造方法
CN116368259A (zh) 用于摩擦学应用的掺杂dlc

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 19763916

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 19763916

Country of ref document: EP

Kind code of ref document: A1