WO2016111288A1 - Stratifié multicouche comprenant du carbone sous forme de diamant amorphe et son procédé de fabrication - Google Patents

Stratifié multicouche comprenant du carbone sous forme de diamant amorphe et son procédé de fabrication Download PDF

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Publication number
WO2016111288A1
WO2016111288A1 PCT/JP2016/050115 JP2016050115W WO2016111288A1 WO 2016111288 A1 WO2016111288 A1 WO 2016111288A1 JP 2016050115 W JP2016050115 W JP 2016050115W WO 2016111288 A1 WO2016111288 A1 WO 2016111288A1
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Prior art keywords
layer
carbon
dlc
substrate
diamond
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PCT/JP2016/050115
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English (en)
Japanese (ja)
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弘高 伊藤
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株式会社神戸製鋼所
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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
    • B21D—WORKING OR PROCESSING OF SHEET METAL OR METAL TUBES, RODS OR PROFILES WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
    • B21D37/00—Tools as parts of machines covered by this subclass
    • B21D37/01—Selection of materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
    • B21D—WORKING OR PROCESSING OF SHEET METAL OR METAL TUBES, RODS OR PROFILES WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
    • B21D37/00—Tools as parts of machines covered by this subclass
    • B21D37/20—Making tools by operations not covered by a single other subclass
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23B—TURNING; BORING
    • B23B27/00—Tools for turning or boring machines; Tools of a similar kind in general; Accessories therefor
    • B23B27/14—Cutting tools of which the bits or tips or cutting inserts are of special material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23B—TURNING; BORING
    • B23B27/00—Tools for turning or boring machines; Tools of a similar kind in general; Accessories therefor
    • B23B27/14—Cutting tools of which the bits or tips or cutting inserts are of special material
    • B23B27/18—Cutting tools of which the bits or tips or cutting inserts are of special material with cutting bits or tips or cutting inserts rigidly mounted, e.g. by brazing
    • B23B27/20—Cutting tools of which the bits or tips or cutting inserts are of special material with cutting bits or tips or cutting inserts rigidly mounted, e.g. by brazing with diamond bits or cutting inserts
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different 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
    • C23C14/06—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
    • 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 diamond-like carbon layer laminate and a method for producing the same.
  • the present invention relates to a laminate in which a diamond-like carbon layer is formed on a metal substrate with good adhesion.
  • the “diamond-like carbon layer” may be referred to as a DLC (Diamond Like Carbon) layer.
  • the “diamond-like carbon layer laminate” may be referred to as “DLC layer laminate” or simply “laminate”.
  • the DLC layer is applied in various fields including automobiles, machine parts, and medical devices.
  • the DLC layer has particularly low adhesion to a metal substrate, it is easy to peel off even if directly formed on the metal substrate and lacks practicality.
  • the metal substrate is simply referred to as “substrate”.
  • an intermediate layer is formed between the base material and the DLC layer in order to ensure adhesion with the base material.
  • a base layer-side first layer made of Cr and / or Al metal, and an outermost surface layer made of an amorphous layer containing Cr and / or Al metal and carbon.
  • An intermediate layer having a two-layer structure composed of a second layer on the side has been proposed.
  • Patent Document 2 as the intermediate layer, a first layer on the substrate side made of one or more metal layers selected from the group consisting of W, Ta, Mo and Nb, and W, Ta, Mo and Nb An intermediate layer having a two-layer structure composed of a second layer on the outermost surface layer side composed of an amorphous layer containing one or more metal elements selected from the group and carbon is proposed.
  • Patent Document 3 proposes an intermediate layer having a four-layer structure in which the following four layers (1) to (4) are formed in the described order from the base material side to the outermost surface layer side as the intermediate layer. ing.
  • First layer made of a metal layer of Cr and / or Al
  • Mixed layer of a metal of Cr and / or Al and one or more metals selected from the group consisting of W, Ta, Mo and Nb
  • the second layer (3) consisting of W, Ta, Mo and Nb selected from the group consisting of one or more metal layers (4) selected from the group consisting of W, Ta, Mo and Nb
  • a fourth layer comprising an amorphous layer containing one or more metals and carbon
  • Japanese Unexamined Patent Publication No. 2002-256415 Japanese Unexamined Patent Publication No. 2000-119843 Japanese Unexamined Patent Publication No. 2003-171758
  • the present invention has been made paying attention to the circumstances as described above, and its purpose is high adhesion between the base material and the DLC layer, particularly when the use environment is severe as described above or when the DLC layer is thick. Even so, the object is to realize a diamond-like carbon layer laminate that has high adhesion between the substrate and the DLC layer and that can be formed with high productivity without a complicated structure.
  • adheresion between the substrate and the DLC layer may be simply referred to as “adhesion”.
  • the diamond-like carbon layer laminate of the present invention that has solved the above problems is a laminate in which a diamond-like carbon layer is formed on a base material via an intermediate layer, and the intermediate layer comprises the base
  • the first layer provided on the material and the second layer provided on the first layer, the substrate is made of metal
  • the first layer is made of Cr
  • the second layer is made of Cr.
  • the ratio of carbon to the total of Cr and carbon is 80 atomic% or less.
  • the ratio of carbon to the total of Cr and carbon on the surface in contact with the diamond-like carbon layer of the second layer is preferably 40 atom% or more and 80 atom% or less.
  • the film thickness of the intermediate layer is preferably 0.05 ⁇ m or more and 1.0 ⁇ m or less.
  • the present invention also includes a sliding member provided with the diamond-like carbon layer laminate.
  • the present invention includes a method for producing the diamond-like carbon layer laminate.
  • the manufacturing method is characterized in that the intermediate layer is formed by a PVD method and the diamond-like carbon layer is formed by a PVD method or a CVD method.
  • a DLC layer laminate having a high adhesion between the substrate and the DLC layer, particularly when the use environment is severe or the DLC layer is thick, Can be provided.
  • This DLC layer laminate can be formed with high productivity since the intermediate layer is not a complicated structure as in Patent Document 3.
  • the present inventor conducted intensive studies to obtain a molded article having excellent adhesion between the base material and the DLC layer even in a severe use environment or when the DLC layer is thickened. Many techniques for providing a composition gradient layer between a substrate and a DLC layer have been proposed so far in order to improve adhesion. However, the present inventor refocused on the composition of the composition gradient layer and studied to further improve the adhesion between the substrate and the DLC layer.
  • the intermediate layer of the present invention has a laminated structure comprising a first layer provided on a substrate and a second layer provided on the first layer.
  • the first layer is made of Cr
  • the second layer is made of Cr and carbon.
  • the second layer has a composition gradient structure in which carbon increases from the base material side toward the DLC layer side and Cr decreases.
  • the bonding force with Cr constituting the first layer can be increased at the interface with the first layer, and the bonding force with the DLC layer at the interface with the DLC layer. Can be increased. Specifically, by setting the surface of the second layer in contact with the first layer to Cr 100 atomic%, a high bonding strength with the first layer can be obtained, that is, high adhesion with the metal substrate can be obtained. Further, as described above, the composition gradient structure in which carbon increases and Cr decreases as it goes from the substrate side to the DLC layer side increases affinity with the DLC layer.
  • the interface between the intermediate layer and the DLC layer is not increased to 100 atomic% of carbon, but the ratio of carbon to the total of Cr and carbon is suppressed to 80 atomic% or less.
  • the ratio of carbon to the total of Cr and carbon may be simply referred to as “carbon ratio”.
  • the reason why the adhesiveness is increased by suppressing the carbon ratio in this way is not clear enough, but can be considered as follows from the results of Examples described later. That is, when the carbon ratio is higher than 80 atomic%, there is no problem with the bonding force with the DLC layer, but a portion with low hardness is easily formed. For example, when used at a large surface pressure, cracks are likely to occur in the low hardness portion, and as a result, the DLC layer is likely to be peeled off.
  • the carbon ratio is preferably 75 atomic percent or less, and more preferably 70 atomic percent or less.
  • the carbon ratio is preferably 40 atomic% or more.
  • the carbon ratio is more preferably 45 atomic% or more, further preferably 50 atomic% or more, and still more preferably 55 atomic% or more.
  • middle layer becomes like this.
  • it is 0.01 micrometer or more, More preferably, it is 0.03 micrometer or more.
  • the thickness of the first layer is preferably 0.4 ⁇ m or less, more preferably 0.3 ⁇ m or less from the viewpoint of suppressing deformation in a high surface pressure environment. is there.
  • the film thickness of the second layer is preferably 0.02 ⁇ m or more, more preferably 0.1 ⁇ m or more, from the viewpoint of ensuring adhesion with the DLC layer.
  • the film thickness is thinner than 0.02 ⁇ m, the gradient of the gradient composition becomes steep, and cracks are generated starting from the gradient composition layer having a steep composition gradient, which may lead to peeling of the DLC layer.
  • the second layer since the second layer has an inclined structure, if the film thickness becomes too thick, the soft layer containing a large amount of Cr may increase and deform in a high surface pressure environment.
  • the thickness of the second layer is preferably 0.8 ⁇ m or less, and more preferably 0.6 ⁇ m or less.
  • the total film thickness of the first layer and the second layer that is, the film thickness of the intermediate layer is preferably in the range of 0.05 ⁇ m to 1.0 ⁇ m.
  • the film thickness is more preferably 0.10 ⁇ m or more, and still more preferably 0.20 ⁇ m or more.
  • the proportion of the intermediate layer made of a Cr layer or a Cr—C gradient composition layer having a lower hardness than the DLC layer tends to increase.
  • cracks may occur starting from this thick intermediate layer, which may lead to peeling of the DLC layer.
  • the film thickness is preferably 1.0 ⁇ m or less, more preferably 0.80 ⁇ m or less, and still more preferably 0.75 ⁇ m or less.
  • the total film thickness of the first layer and the second layer is referred to as “intermediate film thickness”.
  • DLC layer The present invention does not define the specific composition of the DLC layer, and various DLC layers can be used.
  • aC H which is amorphous hydrogenated carbon
  • aC which is amorphous carbon
  • ta-C H which is hydrogenated tetrahedral amorphous carbon
  • ta-C which is tetrahedral amorphous carbon
  • a DLC layer having a laminated structure of any two or more of the above can be used.
  • the DLC layer of the present invention may contain one or more elements X other than carbon and hydrogen in order to control the friction coefficient and wear resistance.
  • elements X include B, N, O, F, Al, Si, P, S, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, and Ru.
  • Ag, Sn, Sb, Ta, W, Ir, Pt, Au, Pb, Bi, etc. may be used alone or in combination of two or more, for example, within a range of 30 atomic% or less of the entire DLC layer.
  • the film thickness of the DLC layer is not particularly limited, and can be, for example, 0.5 ⁇ m or more and 50.0 ⁇ m or less. As described above, according to the configuration of the present invention, even when a relatively thick DLC layer is formed, the adhesion between the DLC layer and the substrate is excellent.
  • the thickness of the DLC layer is preferably 1.5 ⁇ m or more, more preferably 1.8 ⁇ m or more, and further preferably 2.0 ⁇ m or more. Thus, even when the film thickness of the DLC layer is thick, excellent adhesion to the substrate can be maintained, and the effects such as wear resistance of the DLC layer are fully exhibited. Of course, an extremely thin film can be formed as the DLC layer.
  • a low hardness layer may be provided as the conforming layer.
  • the low-hardness layer include a low-hardness DLC layer and a DLC layer containing the element X as described above.
  • the substrate is not particularly limited as long as it is a metal.
  • carbon steel for machine structure, alloy steel for structure, tool steel including high speed steel HSS, bearing steel, stainless steel, cast iron and the like can be used as the iron base material.
  • metals other than iron-based metals Al, Ti, Cu pure metals and alloys; W pure metals and alloys; WC-based cemented carbides can be used.
  • the substrate may be subjected to carburizing treatment, nitriding treatment, anodizing treatment, plating treatment, or the like in order to increase the strength of the substrate.
  • the present invention also includes a sliding member provided with the DLC layer laminate. It suffices that the DLC layer laminate of the present invention is provided on at least the sliding surface of the sliding member.
  • the DLC layer laminate of the present invention can be suitably used for various parts such as molds, cutting tools, wear-resistant mechanical parts, magnetic / optical parts and the like in addition to the sliding members.
  • the DLC layer laminate of the present invention is characterized in that the intermediate layer is formed by a PVD (Physical Vapor Deposition) method, and the DLC layer is formed by a PVD method or a CVD (Chemical Vapor Deposition) method.
  • PVD Physical Vapor Deposition
  • CVD Chemical Vapor Deposition
  • a substrate is prepared as an object to be processed, and is subjected to various cleaning processes such as degreasing, ultrasonic cleaning with acetone, ethanol, and the like, and drying of a cleaning liquid. Thereafter, the substrate is mounted in a vacuum chamber of the film forming apparatus, and evacuation is performed as necessary.
  • the degree of vacuum is preferably evacuated to a level of 10 ⁇ 2 Pa or less from the viewpoint of preventing the mixing of impurity components. However, depending on the object to be processed, the influence of impurities may not be considered. Not required.
  • ⁇ Ar ion bombardment is performed to clean moisture adsorbed on the surface of the metal substrate and components remaining in the cleaning process, such as impurities derived from rust preventive oil.
  • a step of heating the inside of the chamber or between 100 to 1200 ° C. may be provided in order to evaporate the moisture adsorbed on the inside of the chamber or the substrate surface.
  • the inert gas for bombardment is cheap and easily available Ar gas.
  • the purity of Ar gas is preferably 99.9% or more, but there is no problem even if it is less than that.
  • Ar gas is introduced into the vacuum chamber and waits until the gas pressure reaches a predetermined pressure of 0.2 Pa to 4 Pa. The pressure can be arbitrarily changed. After reaching a predetermined pressure, by applying a current of 2 to 20 A from an external power source to the tungsten filament installed in the vacuum chamber, the tungsten filament becomes red hot and emits thermoelectrons. Ar ions are ionized by collision of the thermal electrons with Ar gas.
  • the ionized argon is drawn into the substrate when a negative voltage is applied to the substrate, and the argon ion strikes the substrate surface to clean the substrate surface.
  • the above description is a method when a normal DC (Direct Current) voltage or a pulsed DC voltage is applied to the substrate.
  • the effect of argon ion bombardment on the substrate is enhanced, while a positive bias is applied to the other substrate, and the surface is modified by electron irradiation.
  • the surface is activated by electron beam irradiation to become a highly reactive surface. That is, according to this method, the substrate surface cleaning and modification effects can be sufficiently enhanced.
  • the negative bias and the positive bias described above are alternately applied, and the cleaning and reforming effects on the substrate surface are accelerated.
  • the above effect can be obtained by applying the applied voltage within the range of the power supply set value of 350V to 1600V.
  • middle layer is formed by PVD method as above-mentioned. This is because the Cr layer as the first layer cannot be formed by a CVD method in which a gas is decomposed to form a film. It is effective to use a Cr target having a purity of 99% or more for forming the Cr layer.
  • a sputtering method including an unbalanced magnetron sputtering (UBMS) method, an arc ion plating (AIP) method, a vacuum deposition method, or the like.
  • the gradient composition layer as the second layer can be formed by the following method.
  • a Cr target as the target and introducing a hydrocarbon gas such as methane, acetylene, benzene, toluene, etc. as the film forming gas, and gradually increasing the amount of introduction
  • the Cr—C gradient composition The method of forming a layer is mentioned.
  • a Cr target and a C target are used as targets.
  • Ar gas is used as an atmospheric gas, and the film formation rate of Cr is reduced.
  • a method of increasing the film formation rate of carbon specifically, for example, increasing the input power of the carbon target.
  • a film forming method using a Cr target and a C target as targets and also using a hydrocarbon gas as a carbon supply source can be considered. As described above, it is effective to use a Cr target having a purity of 99% or more as the Cr target.
  • the target component can be effectively adhered to the substrate by applying a negative bias to the substrate by a bias power source.
  • the density of the film can be controlled by controlling the bias voltage. Since the dense film has high deformation resistance, the possibility of breaking when an external force is applied is reduced. That is, adhesion is also improved.
  • the negative bias voltage is preferably smaller than ⁇ 40V, that is, a value having a large absolute value. On the other hand, if the value is smaller than ⁇ 1000 V, the effect of the bias is too strong, and the formed intermediate layer is easily etched, and the deposition rate is extremely reduced. As a result, the adhesion tends to decrease. Therefore, it is preferable that the negative bias voltage is larger than ⁇ 1000 V, that is, a value having an absolute value smaller than ⁇ 1000 V.
  • the film formation conditions of the first layer and the second layer can be as follows. That is, the substrate temperature can be in the range of room temperature to 200 ° C.
  • the total pressure can be in the range of 0.1 to 5.0 Pa, and the partial pressure can be adjusted so that the amount ratio of Ar is in the range of 100 to 30%.
  • the power applied to the target can be in the range of 0.1 to 5.0 kW.
  • Either the PVD method or CVD method may be sufficient as the formation method of a DLC layer.
  • the PVD method an AIP method, a sputtering method, or the like can be used.
  • a DLC layer not containing hydrogen can be formed.
  • a DLC layer containing hydrogen can be formed by introducing a hydrocarbon gas during film formation.
  • a target containing the element can be used.
  • a DLC layer is formed by decomposing the hydrocarbon gas by applying a voltage or electric power to the base material with the hydrocarbon gas as a main component and decomposing the hydrocarbon gas.
  • Any of DC, pulsed DC, and AC (Alternating Current) may be used as a method for applying voltage or power to the substrate.
  • a gas containing silicon, various metal components, or oxides thereof can be used. .
  • Examples of film forming conditions for forming by the CVD method include the following conditions.
  • the substrate temperature can be in the range of room temperature to 200 ° C. In general, the substrate is not heated, and the substrate is not heated in the examples described later, but the substrate temperature can rise to, for example, about 50 to 200 ° C. during film formation. However, when the substrate temperature exceeds 250 ° C., DLC softening occurs, which is not preferable.
  • the total pressure during film formation by the CVD method can be in the range of 0.5 to 20 Pa. Increasing the total pressure increases the film formation rate, but tends to cause problems such as a decrease in hardness and an increase in surface roughness.
  • the partial pressure may be adjusted so that the hydrocarbon gas such as acetylene and methane is in the range of 100 to 30%, and the rest is an inert gas such as Ar. When an inert gas is contained, the film formation rate decreases but the hardness tends to increase. On the other hand, an excessive amount of inert gas is not preferable because the film forming rate is extremely lowered.
  • the applied voltage during film formation by the CVD method can be in the range of 500V to 2000V. If this applied voltage is too low, plasma is not generated. On the other hand, if it is too high, abnormal discharge occurs frequently and the plasma is not stable.
  • the substrate temperature can be in the range of room temperature to 200 ° C. In general, the substrate is not heated, and the substrate is not heated in the examples described later, but the substrate temperature can rise to, for example, about 50 to 200 ° C. during film formation. However, when the substrate temperature exceeds 250 ° C., DLC softening occurs, which is not preferable.
  • the total pressure during film formation by the PVD method can be in the range of 0.1 to 2.0 Pa.
  • the partial pressure may be adjusted so that the amount ratio of Ar is in the range of 50% or more and less than 100%. More preferable conditions include, for example, a total pressure of 1.0 Pa, a hydrocarbon gas such as methane of 1 to 10% and the balance of Ar.
  • the voltage applied to the target during film formation by the PVD method can be 0.1 to 5.0 kW.
  • the negative bias voltage applied to the substrate can be in the range of 50 to 400 V in absolute value. By increasing the absolute value of this negative bias voltage, the hardness of the film can be increased and the wear resistance can be increased. On the other hand, if the absolute value of the negative bias voltage is too high, an etching effect occurs and the film formation rate tends to be extremely reduced.
  • the arc current can be in the range of 10 to 100 A, and the Ar gas can be in the range of 0 to 100%.
  • the intermediate layer was formed using an unbalanced magnetron sputtering apparatus manufactured by Kobe Steel, Ltd., trade name: UBMS202.
  • the substrate used was JIS SKH51 with a mirror polished surface and an HRC of 65.
  • the substrate was introduced into the chamber and then evacuated to 1 ⁇ 10 ⁇ 3 Pa or less. Thereafter, moisture in the chamber was removed by heat treatment at 300 ° C. for 10 minutes.
  • Ar ion bombardment for cleaning the substrate surface was performed using a DC power source or an AC power source under the following conditions. Ar ion bombardment conditions Ar gas purity: 99.9% Gas pressure: 1.0Pa Tungsten filament current: When using 5 ADC power supply Power supply: Kyosan Seisakusho HPK03ZI Bias voltage: -200 VAC when using power supply Power: Huttinger Tru-Plasma MF3010 Bias voltage: -200V
  • the intermediate layer was formed by a UBMS method using a Cr target with a purity of 99.9% and a C target with a purity of 99.9%.
  • Argon gas is used as the process gas and acetylene gas as the hydrocarbon-based gas.
  • argon gas is used, and when forming the carbon-containing layer, a mixed gas of argon gas and acetylene gas is placed in the chamber. Introduced.
  • the substrate temperature during film formation of the first layer and the second layer was 100 ° C., the total gas pressure was 1.0 Pa, and the substrate bias was constant at ⁇ 200V.
  • a power of 2.0 kW was applied to the Cr target to discharge it, and a Cr layer as the first layer was formed.
  • the voltage applied to the Cr target was decreased, and at the same time, the voltage applied to the C target was increased to 2.0 kW.
  • the Cr—C gradient composition layer as the second layer was formed by changing the flow ratio of argon gas and acetylene gas to control the ratio of Cr and carbon in the intermediate layer.
  • the film thickness of the intermediate layer was adjusted by the film formation time.
  • a DLC layer was formed.
  • a DLC layer having a film thickness shown in Table 1 was formed by a CVD method or a UBMS method as a PVD method.
  • the CVD method methane as a hydrocarbon gas is introduced into the chamber so that the total pressure becomes 2.0 Pa, 900 V is applied to the substrate holder from a pulsed DC power source manufactured by Kyosan Seisakusho, and the components of the hydrocarbon gas was decomposed to form a DLC film.
  • the PVD method specifically, the UBMS method, a power of 2.0 kW is applied to the carbon target, a mixed gas of methane and Ar is used as a process gas, the total pressure is 1.0 Pa, the negative bias voltage is 100 V, and the above DLC films having various film thicknesses shown in Table 1 were formed under the conditions of 5% methane and the balance Ar.
  • the component composition of the gradient composition layer of the second layer was determined from the depth profile of the AES (Atomic Emission Spectroscopy) method.
  • the carbon ratio at the interface of the DLC layer in the second layer was determined from the boundary with the DLC layer of the second layer.
  • Adhesion was performed by a peel determination test shown in the standard VDI3198 of the German Engineers Association. Specifically, the C scale evaluation of the Rockwell test, that is, a diamond cone having a tip angle of 120 degrees was driven at a load of 150 kg. And the peeling
  • Table 1 shows the following. No. 1 to 8 are configurations of the first layer and the second layer in the intermediate layer, the film thickness of the intermediate layer, the film formation method of the DLC layer, and the film thickness of the DLC layer, and the inclination of the second layer in the intermediate layer
  • the composition is changed.
  • no. In 1 and 2 the carbon ratio at the interface of the DLC layer of the second layer exceeded 80 atomic%, and thus the adhesion decreased.
  • no. 1 is an example in which the carbon concentration is increased from 0 atomic% on the substrate side to 100 atomic% on the DLC layer side, which is recommended in Patent Document 1 and Patent Document 2, but excellent adhesion is obtained in this example. There wasn't.
  • No. 7 and 8 are examples in which the carbon ratio at the DLC layer interface of the second layer is too small, in other words, the amount of Cr is too large. In this case, it is considered that the bond strength with the carbon constituting the DLC layer is weakened, the interface strength between the DLC and the second layer in the intermediate layer is weakened, and the adhesion is lowered.
  • No. 9 to 14 are the configurations of the first layer and the second layer in the intermediate layer, the gradient composition of the second layer in the intermediate layer, the film forming method of the DLC layer, and the film thickness of the DLC layer. This is an example in which only is changed. Of these examples, no. No. 9 was a gradient composition layer with a steep composition gradient because the intermediate layer was too thin, and good adhesion could not be obtained. This No. In No. 9, it is considered that cracks occurred starting from the steep gradient composition layer. On the other hand, no. No. 14, because the film thickness of the intermediate layer was too thick, good adhesion could not be obtained. This No. No. 14, it is considered that peeling occurred from the inside of the thick intermediate layer.
  • No. 15 to 18 are examples in which the thickness of the DLC layer is changed while the composition of the first layer and the second layer in the intermediate layer, the gradient composition of the second layer in the intermediate layer, and the thickness of the intermediate layer are made constant. is there.
  • No. 15 shows the result of forming the DLC layer by the UBMS method which is a kind of PVD method. From these results, it was found that good adhesion can be obtained even when the film forming method and film thickness of the DLC layer are changed.
  • No. No. 19 is an example in which the second layer in the intermediate layer is not a gradient composition but a single composition of Cr—C. In this way, when the inclined structure was not formed in the intermediate layer, the adhesion was remarkably lowered.
  • No. 20 is an example in which a laminated film is formed in the same manner as in the present invention except that tungsten is used instead of Cr. In this case, since the strength of the interface between tungsten and the substrate is insufficient, it is considered that the adhesiveness has decreased.
  • the DLC layer laminate of the present invention is useful as various parts such as sliding members, molds, cutting tools, wear-resistant mechanical parts, magnetic / optical parts, and the like.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Physical Vapour Deposition (AREA)
  • Chemical Vapour Deposition (AREA)
  • Cutting Tools, Boring Holders, And Turrets (AREA)
  • Mounting, Exchange, And Manufacturing Of Dies (AREA)
  • Laminated Bodies (AREA)

Abstract

La présente invention se rapporte à un stratifié dans lequel une couche de carbone sous forme de diamant amorphe (CDA) est formée sur un substrat métallique, une couche intermédiaire étant agencée entre eux, la couche intermédiaire comportant une première couche et une seconde couche dans cet ordre à partir du substrat, la première couche étant constituée de Cr et la seconde couche étant constituée de Cr et de carbone. En outre, la couche intermédiaire présente une structure à gradient de composition dans laquelle la teneur en carbone augmente et la teneur en Cr diminue, du substrat vers la couche de CDA, le rapport du carbone à la somme du Cr et du carbone à la surface de la seconde couche en contact avec la couche de CDA étant inférieur ou égal à 80 % at.
PCT/JP2016/050115 2015-01-09 2016-01-05 Stratifié multicouche comprenant du carbone sous forme de diamant amorphe et son procédé de fabrication WO2016111288A1 (fr)

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JP2015-003517 2015-01-09

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CN107881469A (zh) * 2017-12-25 2018-04-06 深圳先进技术研究院 类金刚石复合涂层及其制备方法与用途以及涂层工具
JP2018158355A (ja) * 2017-03-22 2018-10-11 新日鐵住金株式会社 チタン板のプレス用金型及びチタン板のプレス成形方法
CN113862613A (zh) * 2021-09-18 2021-12-31 美戈利(浙江)轨道交通研究院有限公司 非晶梯度结构超硬dlc刀具涂层及其制备方法和刀具

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JP7383908B2 (ja) * 2019-06-11 2023-11-21 株式会社豊田中央研究所 ベーン式オイルポンプおよびそのベーンの製造方法

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JP2018158355A (ja) * 2017-03-22 2018-10-11 新日鐵住金株式会社 チタン板のプレス用金型及びチタン板のプレス成形方法
CN107881469A (zh) * 2017-12-25 2018-04-06 深圳先进技术研究院 类金刚石复合涂层及其制备方法与用途以及涂层工具
CN107881469B (zh) * 2017-12-25 2023-11-14 深圳先进技术研究院 类金刚石复合涂层及其制备方法与用途以及涂层工具
CN113862613A (zh) * 2021-09-18 2021-12-31 美戈利(浙江)轨道交通研究院有限公司 非晶梯度结构超硬dlc刀具涂层及其制备方法和刀具

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