JP2006206960A - Sliding member coated with hard film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a sliding member coated with a hard film which is excellent in wear resistance and lubrication characteristic, capable of reducing the residual compressive stress in a hard film to increase the thickness of the hard film, and capable of reducing wear and seizure of the member and attackability of a counter member even under a severe sliding environment. <P>SOLUTION: In the sliding member coated with the hard film, at least one layer of a hard film is indicated by (Cr<SB>(100-α)</SB>Si<SB>α</SB>)(N<SB>(100-γ-η)</SB>B<SB>γ</SB>G<SB>η</SB>), and inequalities 0.5≤α≤20, 0<γ<45 and 0≤η≤55. G has at least one kind selected from C, O and S, and has the X-ray diffraction peak intensity in (200) plane of rock salt structure type, the half peak width is ≥0.5° and ≤2.0°. while having at least one kind to be selected from a nitride phase, an oxide phase and a metallic phase of Si and/or B. The hard film has the concentration modulation of the Si content, and the thickness of the hard film is ≥1 μm and <60 μm. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a mold or a engine used for an internal combustion engine or a die used for cold working, drawing, extrusion, cold forging, compression, bending, drawing, shearing, etc. The present invention relates to a hard film-coated sliding member such as a ring and a supercharging pressure control component for an internal combustion engine.

Surface treatments with excellent sliding characteristics are formed on sliding parts such as automobile engine parts and various machine parts in order to extend the life of the members. Studies have been made to improve wear resistance and seizure resistance by coating a hard film such as TiN, TiC, CrN, etc. by physical vapor deposition, and techniques related thereto are disclosed in the following Patent Documents 1 and 2. Yes.
Patent Document 1 discloses the technology of a piston ring coated with a hard coating of Cr—N, Cr—N—O, Cr—B—N, Cr—B—N—O, or Ti—N. ing.
Patent Document 2 has a composition of chromium: silicon: nitrogen = 1: 0.05 to 1.2: 0.1 to 1.2 in terms of atomic ratio of constituent elements, and at least chromium nitride and silicon nitride. There is disclosed a sliding material characterized in that a substrate is coated with a film in which is present. By adding silicon to the Cr-based film, high hardness is achieved, which contributes to improvement of wear resistance. However, in addition to the hard film becoming brittle, the lubricity is not sufficiently improved, and there are problems such as occurrence of seizure and increased attack of the counterpart material.

JP-A-5-195196 Japanese Patent No. 3311767

  The invention of the present application is a hard coating coated sliding member, which has excellent wear resistance and lubrication characteristics, and further reduces the residual compressive stress in the hard coating, enabling a thick coating of the hard coating, even under severe sliding environments It is an object of the present invention to provide a hard coating member that can reduce the wear, seizure, and aggressiveness of a mating member.

The present invention relates to a hard film-coated sliding member coated with a hard film, wherein at least one layer of the hard film is (Cr _(100-α) Si _α ) (N _(100-γ-η) B _γ G _η ). Where α, γ, and η represent atomic percent, where 0.5% α ≦ 20, 0 <γ <, where atomic percent of the metal component alone is 100 and atomic percent of the nonmetallic component is 100. 45, 0 ≦ η ≦ 55, G has at least one selected from C, O, and S, and the hard coating has an X-ray diffraction peak intensity on the (200) plane of the rock salt structure type The half width of the X-ray diffraction peak intensity is not less than 0.5 degrees and not more than 2.0 degrees, and at least one selected from the nitride phase, oxide phase, and metal phase of at least Si and / or B The hard coating has a concentration modulation of the Si content, and the thickness of the hard coating is 1 μm or more, 60 μm. A hard-coated sliding member and less than. By adopting the above configuration, it has excellent wear resistance and lubrication characteristics, and further reduces the residual compressive stress in the hard coating, enabling thick coating of the hard coating, and even in severe sliding environments It is possible to provide a hard coating member that can reduce wear, seizure, and aggressiveness of the counterpart material.

  The hard film-coated sliding member of the present invention preferably has a laminated structure with another hard film in addition to the CrSi-based film. Here, the other hard coating preferably has at least one selected from 4a, 5a, 6a and Al, Si and at least one selected from C, N, O, B, S. The uppermost layer of the hard film is preferably a hard film and / or a laminated film including a hard carbon film. Alternatively, the uppermost layer of the hard film is preferably a laminated film including a hard film mainly composed of sulfide and / or a hard film mainly composed of sulfide. When a laminated film is employed, the lamination period of the hard film is preferably 100 nm or more and less than 500 nm, and the lamination period is more preferably 0.5 nm or more and less than 30 nm. By adopting the laminated film, the life of the sliding member can be greatly improved. The hard coating preferably has a residual compressive stress gradient or periodicity in the layer thickness direction. In this case, it is effective for peeling resistance and enables the hard film to be thickened. It is preferable that the concentration of at least one element selected from C, O, S, and B is maximized in a region less than 200 nm in the film thickness direction from the uppermost layer of the hard coating. In this case, sliding characteristics can be improved. The hard coating preferably has a nitride layer at the interface between the sliding member and the substrate. In this case, the member life can be further increased. It is preferable that the hard coating mechanically smoothes the interface between the sliding member and the substrate. In this case, local wear can be reduced and the hard coating can be effectively utilized. The hard film-coated sliding member of the present invention is preferably applied to a mold, a piston ring, or a supercharging pressure control part for an internal combustion engine. In this case, the lifetime as a sliding member can be significantly improved. Here, the components for controlling the boost pressure of the internal combustion engine include, for example, a compressor, a turbine, a wastegate, etc., which are components for a turbocharger control device of the internal combustion engine. The hard coating of the present invention is preferably coated by applying a physical vapor deposition method. In particular, a coating method using an ion plating method or a sputtering method is effective.

  By applying the hard film coated sliding member of the present invention, it becomes possible to reduce the wear, seizure of the member, and the aggressiveness of the mating material even under severe sliding environment, and the long life hard film coated sliding A member could be provided.

The hard film of the present invention can solve the problem by controlling the hard film to an optimal composition, laminated structure, structure, and mechanical properties. Accordingly, at least one layer of the hard coating of the present invention is represented by (Cr _(100-α) Si _α ) (N _(100-γ-η) B _γ G _η ), where α, γ, and η are atoms. %, 0.5 ≦ α ≦ 20, 0 ≦ β <60, 0 <γ <45, 0 ≦ η ≦ 55, and G is a film having at least one selected from C, O, and S The composition. Here, (Cr (100-α) Siα) in the film composition formula is a metal component element, and (N _(100-γ-η) B _γ G _η ) is a non-metal component element. The composition of the hard coating does not necessarily indicate that the atomic ratio of the nonmetallic component to the metallic component is 1: 1, but describes the metallic component and the nonmetallic component separately. When the α value is less than 0.5% in atomic%, the hard film is not sufficiently cured by Si and the wear resistance is poor. On the other hand, when the content exceeds 20%, the hard coating is significantly embrittled and the peel resistance is lowered. Moreover, the aggression property to the counterpart material when functioning as a sliding member becomes extremely high. Therefore, it is limited to the above range. Here, the aggressiveness to the mating material is a phenomenon in which the mating material is worn away due to wear, for example, by sliding.
The γ value is 0 <γ <45. By using B element as an essential component, hardness and lubricity can be improved at the same time, which is effective for improving the life of the sliding member. It has also been confirmed that the addition of Si at the same time is more effective in increasing the hardness of the hard coating than when adding Si alone. In the case of a small amount, for example, γ <5%, an improvement in hardness due to the B element can be expected to increase the hardness by promoting the crystallization of the hard film. In the case of more than that, for example, when γ ≧ 5% is added, a lubrication effect due to the formation of the h-BN phase can be expected in the film forming process or in a wear environment. However, in the case of γ ≧ 45%, it is inconvenient because it is confirmed that the film hardness is lowered and the wear resistance is rapidly lowered. By optimizing the γ value, the hardness and lubricity can be increased at the same time, which is effective for improving the life of the sliding member. The improvement in hardness due to the B element is due to the c-BN phase. The improvement in lubricity is due to the h-BN phase. By optimizing the content ratio of both, it is possible to simultaneously increase the hardness and lubricity. The content ratio of the c-BN phase and the h-BN phase can be controlled by the bias voltage value applied during film formation.
When G contains at least one selected from C, O, and S, an excellent member life can be obtained. C can simultaneously increase hardness and lubricity. If O is an appropriate amount, it effectively acts to reduce the residual compressive stress in the hard coating. The preferable content of O is less than 25%. S can improve lubricity in particular and has an effect of reducing wear of the mating member during sliding. The addition method of S can also be added by an ion plating method or a sputtering method. The η value is 0 ≦ η ≦ 55. If the η value exceeds 55%, it is inconvenient because the wear resistance decreases rapidly.
The hard coating of the present invention has an X-ray diffraction peak intensity on the (200) plane of the rock salt structure type, and the half width of the X-ray diffraction peak intensity needs to be 0.5 degrees or more and 2.0 degrees or less. is there. The peak intensity is obtained by X-ray diffraction measurement by the θ-2θ method. The X-ray diffraction peak intensity is obtained on the (200) plane, and the balance of the residual compressive stress and the crystal grain size are controlled by controlling the crystal structure within a range where the half width is not less than 0.5 degrees and not more than 2.0 degrees. The balance of the film hardness that depends is optimal.
The hard film of the present invention needs to have at least one selected from a nitride phase, an oxide phase, and a metal phase of at least Si and / or B. The presence or absence of a nitride phase, an oxide phase, or a metal phase can be confirmed, for example, by X-ray photoelectron spectroscopy. When Si and / or B in the hard coating exists as a nitride phase, hardness and lubricity can be improved at the same time. Further, when it is present as an oxide phase in addition to the nitride phase, it is particularly effective for reducing lubricity. The case where the nitride phase and the oxide phase coexist is particularly preferable. In addition to this, when a metal phase coexists, it is particularly effective for reducing the residual compressive stress in the hard coating.
The hard coating of the present invention requires the presence of Si content concentration modulation. Due to the presence of concentration modulation, the hardness and lubricity of the hard coating can be improved simultaneously. When Si exists as a solid solution phase with Cr, the lubrication characteristics deteriorate as the film hardness increases. However, the presence of density modulation can improve both characteristics simultaneously. Specifically, there is a case where Si concentration modulation exists in the same crystal grain of the hard coating and a case where the Si concentration differs between crystal grains. In particular, the latter is more effective for improving the life of the sliding member.
The film thickness of the hard coating of the present invention needs to be 1 μm or more and less than 60 μm. By coating the hard film by an ion plating method or a sputtering method, the control of the hard film composition is facilitated, the wear resistance is excellent, and the life of the sliding member can be extended.

  The metal component of the hard coating of the present invention contains M component in addition to Cr and Si as a content β, and the M component has at least one selected from V, Mo, W, and Al, and has a β value. Preferably satisfies 0 ≦ β <60 in atomic percent. When M contains at least one selected from V, Mo, W, and Al, an excellent member life can be obtained. In particular, when V, Mo, and W are contained, the lubrication characteristics can be enhanced among the sliding characteristics, which is preferable. Further, when Al is contained, it is preferable because it is effective in improving wear resistance and heat resistance. The β value is less than 60% in atomic%. This is because when the content is 60% or more, the excellent slidability, lubricity and wear resistance characteristics of the hard coating are greatly different and inferior. Thereby, the lifetime as a sliding member will fall significantly. On the other hand, even when the β value is 0%, a satisfactory effect can be obtained in terms of slidability, lubricity and wear resistance.

  The characteristics of the hard coating of the present invention can be further improved by laminating hard coatings having different compositions. Another hard film has 1 or more types chosen from 4a, 5a, 6a and Al, Si as a metal component, and 1 or more types chosen from C, N, O, B, and S. The improvement of the characteristics here means, for example, increasing the adhesion strength between the substrate and the hard film. This can be realized by adopting a nitride film such as Cr or Ti and a laminated structure with a relatively hard Si-containing film. Abrasion resistance is improved by a laminated structure of nitrides such as Ti, Al, Cr, Zr, Si, Nb, Mo, Hf, and W, or carbonitrides and a relatively hard Si-containing coating. can do. In order to reduce the residual compressive stress of the entire hard coating, it is effective to use a metal rich layer.

  Covering the hard carbon film on the uppermost layer of the hard film of the present invention and / or forming a laminated film containing the hard carbon film is effective for extending the life of the sliding layer member. The hard carbon film has a low coefficient of friction and a fine crystal grain size, and is excellent in adhesion strength with the hard film of the present invention. It is preferable to use a hard carbon film and / or a laminated film containing a hard carbon film in the uppermost layer because it is effective for improving the lubrication characteristics and effectively acts to reduce the wear amount of the counterpart material during sliding.

  It is also effective to extend the life of the sliding member by covering the uppermost layer of the hard film of the present invention with a hard film mainly composed of sulfide and / or a laminated film including a hard film mainly composed of sulfide. It is. A hard film mainly composed of sulfide has a low friction coefficient and a fine crystal grain size, and is excellent in adhesion strength with the hard film of the present invention. A laminated film including a hard film mainly composed of sulfide in the uppermost layer is preferable because it is effective in improving the lubrication characteristics and effectively acts in reducing the wear amount of the counterpart material during sliding.

  By setting the laminating cycle of the hard coating of the present invention to 100 nm or more and less than 500 nm, the residual compression of the entire hard coating is reduced, ensuring adhesion in thickening the hard coating and extending the life of the sliding member. Effective and preferred.

  By setting the laminating cycle of the hard coating of the present invention to 0.5 nm or more and less than 30 nm, it is particularly effective in increasing the hardness of the entire hard coating and effective in improving the wear resistance, which is a more preferable embodiment.

  In the hard coating of the present invention, it is preferable to make the hard coating thicker by adopting a form having a gradient or periodicity of residual compressive stress in the layer thickness direction. When the gradient is applied so that the residual compressive stress increases toward the surface of the hard coating, the wear resistance of the hard coating can be improved. In addition, a laminated structure having periodicity so that a layer having a large residual compressive stress and a layer having a small residual compressive stress alternately in the layer thickness direction is effective in securing adhesion particularly when the film is thickened.

  It is preferable that the concentration of at least one element selected from C, O, S, and B is maximized in the region of less than 200 nm in the film thickness direction from the uppermost layer of the hard coating of the present invention. As a result, the lubricity can be improved, and at the same time, the aggressiveness of the mating material can be reduced during sliding. In particular, when the concentrations of C and B are maximized, wear resistance and lubricity can be improved. When the concentrations of O and S are maximized, it is possible to reduce the aggression on the counterpart material.

  When a nitride layer is provided at the interface between the hard coating of the present invention and the substrate of the sliding member, it is preferable that the effect of the hard coating is easily exhibited.

  The interface between the hard coating of the present invention and the base of the sliding member is preferably mechanically smoothed. As a result, the sliding member tends to wear uniformly, which is preferable because the effect of the hard coating is easily exhibited.

  When the hard film-coated sliding member of the present invention is applied as a mold, a piston ring or a supercharging pressure control part for an internal combustion engine, the effect of the hard film of the present invention is exhibited. In any of these, sliding characteristics are extremely important, and are optimal in these applications.

The composition quantitative analysis of the hard coating of the present invention was determined by electron probe X-ray microanalysis, Auger electron spectroscopy, or X-ray photoelectron spectroscopy. The analysis of the bonding state of the hard film was performed by X-ray photoelectron spectroscopy. The analysis apparatus used was a 1600S type X-ray photoelectron spectroscopic analyzer manufactured by PHI, and the analysis conditions were such that the X-ray source was 400 K using MgKα, and the analysis region was analyzed inside a circle having a diameter of 0.4 mm. For sample preparation, the surface was etched using an Ar ion gun for 5 minutes in a vacuum apparatus after thoroughly degreasing and cleaning. The treated sample was measured for a wide spectrum, etched for 30 seconds, and then measured for a narrow spectrum. The etching rate by Ar ion gun was 1.9 nm / min in terms of SiO ₂ . The half width was measured by X-ray diffraction by the θ-2θ method. Hereinafter, based on an Example, this invention is demonstrated concretely.

Example 1
In order to evaluate the Si content in the CrSi-based film and its wear characteristics, a disk material having a diameter of φ20 mm, a thickness of 10 mm, and a material equivalent to SKD61 was prepared. In order to ignore the influence of the irregularities of the disk material on the friction characteristics, mirror polishing was performed with alumina paste, and then gas nitriding treatment was performed at 520 ° C. for 10 hours. Thereafter, in order to remove the brittle nitride phase formed on the surface, the surface was removed by about 10 μm. And the CrSi type | system | group film | membrane from which various Si content differs was coat | covered. As a coating method, degreasing and washing were sufficiently performed, and fixed in an arc discharge ion plating (hereinafter referred to as AIP) apparatus container.
While maintaining the coated substrate in the container at 450 ° C., evacuation was performed until the pressure in the container reached 5 × 10 ⁻⁴ Pa. Ar gas was introduced into the container, and the pressure in the container was set to 5 × 10 ⁻¹ Pa. The coated substrate fixed to the substrate holder in the container has a rotation mechanism having at least two axes. Ar ionization was performed with an electrode placed in the container, and a negative bias voltage was applied to the coated substrate to remove the activated surface of the coated substrate and oxides. A current was supplied to the Cr metal target installed in the AIP evaporation source, and the coated substrate was further cleaned. The supply of Ar was stopped, nitrogen was introduced into the container, the pressure in the container was set to 9 × 10 ⁻¹ Pa, current was supplied to the CrSi-based metal target installed in the AIP evaporation source, and discharge was started. At this time, a negatively applied bias voltage was applied to the coated substrate, and a CrSi-based film was formed on the coated substrate. The coating thickness was set to 5 μm. All of the coated CrSi-based films satisfied the constituent elements of claim 1 except for the Si content. In order to evaluate the wear characteristics of the CrSi-based film, a ball-on-disk wear test was performed. The abrasion test conditions are shown below. Evaluation was made by measuring the friction coefficient after 4 hours of sliding, the wear depth of the disk material, and the wear depth of the ball material.
(Wear test conditions)
Disk material: Equivalent to SKD61 (diameter: φ20mm, thickness: 10mm)
Ball material: FC250 (JIS gray cast iron)
Load: 50N
Ball diameter: φ6mm
Turning radius: 8mm
Rotation speed: 100 rev / min Environmental setting: In air, 200 ° C, no lubrication

  The evaluation result of the friction coefficient is shown in FIG. 1, the relationship between the wear depth of the disk material is shown in FIG. 2, and the relationship between the wear depth of the ball material is shown in FIG. The coated hard coating is shown in Tables 1 and 2.

  From FIG. 1, the influence of the friction coefficient exerted by the Si content showed a lower friction coefficient when Si was contained in an appropriate amount as in Invention Examples 1 to 5 than in Conventional Example 23 not containing Si. However, Comparative Examples 19 and 20 having a Si content of 20 atomic% or more showed a higher friction coefficient than that of Conventional Example 23. From FIG. 2, the influence of the wear depth of the disk material on the Si content was lower than that of the conventional example 23 not containing Si. When the Si content of Invention Example 5 showing the lowest value was 5 atomic%, the wear depth was about 1/3 of that of Conventional Example 23. From this, it can be said that the wear resistance is excellent by setting the optimum Si content. From FIG. 3, the influence of the wear depth of the ball material on the Si content was about ½ of the wear amount of the present invention examples 2 to 4 containing the appropriate amount of Si compared to the conventional example 23. From this, it was confirmed that the CrSi-based film containing an appropriate amount of Si is good against the aggressiveness of the counterpart material. From the above results, the Si content is preferably 0.5 atomic% or more and 20 atomic% or less.

(Example 2)
In order to evaluate the seizure resistance of the hard coating of the present invention, test pieces of Invention Examples 6 to 16, Comparative Examples 21 and 22, and Conventional Example 24 shown in Tables 1 and 2 were manufactured. A test piece base corresponding to 5 mm square SKD61 was manufactured, and gas nitriding treatment was performed at 520 ° C. for 10 hours. In order to remove the brittle nitride phase formed on the surface, the surface of the test piece was removed by about 10 μm. And the CrSi-type film | membrane from which various compositions differ was coat | covered. The coating method is the same as in Example 1 unless otherwise noted. As the hard coating, an AIP evaporation source in which a sputtering evaporation source or another composition target was fixed as required was used. The composition of the hard film, the base film, and the uppermost layer are shown in Tables 1 and 2. In addition, the film thickness was set to 30 ± 2 μm for any test piece. In order to evaluate the wear characteristics of the obtained specimens, an anti-seizure resistance was evaluated using an ultra-high pressure frictional wear tester. Test conditions are shown below.
(Friction and wear test conditions)
Friction speed: 8 m / sec Frictional surface pressure: Initial pressure, 2 MPa, increase by 1 MPa every 3 minutes Lubricating oil: Motor oil # 30
Oil temperature: 80 ° C
Opponent material: FC250
An outline of the evaluation method will be described. The test piece was slidably mounted on the surface of the disk A to form a pin-projection sliding surface. The disk A can be rotated at a predetermined speed by a driving device. On the other hand, a disc B serving as a sliding counterpart material was detachably attached to the holder. The surface of the disk B was polished. The holder has a mechanism capable of lubricating. The holder also has a mechanism that can apply a pressing force in a direction perpendicular to the disk surface by a hydraulic device. Here, the disk A of the test piece and the disk B of the sliding partner material were set to face each other, and pressure was applied to the holder in this state. Therefore, at this time, the pin-projection sliding surface of the test piece and the surface of the counterpart disk B were brought into contact with each other by pressure. With this state as the initial state, the disk A was rotated at a predetermined speed while lubricating. The torque was changed by the friction generated between the test piece and the counterpart material due to the rotation. This situation was detected with a load cell and a dynamic strain meter. Then, the time at which the torque increased rapidly was regarded as the time of occurrence of seizure and evaluated. Lubricating was 400 ml / min from the center of the halter.
The evaluation results are shown in Table 3. The numerical values in Table 3 are shown as the seizure resistance ratio and the wear resistance ratio, respectively, as the ratios based on the measured value and the wear amount at the time of seizure in Conventional Example 24.

As shown in Table 3, the hard coatings of Invention Examples 6 to 16 were excellent in seizure resistance ratio by 1.22 to 1.55 times compared to Conventional Example 24. The wear resistance ratio of the present invention example was also reduced from 0.28 to 0.58 compared to the conventional example, indicating excellent wear resistance. Invention Example 6 is a case of a CrSi-based coating single layer. Excellent seizure resistance and wear resistance. Invention Example 7 shows a case where oxygen is contained in a CrSi-based coating single layer. By containing oxygen, the seizure resistance was further improved. Invention Example 8 shows a case where a hard carbon film is coated on the uppermost layer. Similarly, excellent characteristics were exhibited. In Invention Example 9, the CrSi-based film was coated with an AIP evaporation source and the molybdenum disulfide was coated with a sputtering method at the same time, and the film was formed while forming a constant lamination cycle by the rotating mechanism of the coated substrate. Furthermore, the uppermost layer was coated with molybdenum disulfide. With this configuration, the seizure resistance ratio can be significantly improved. Invention Example 10 shows a case of a laminated film of a CrSi film and a Cr film. In Invention Example 10, two types of AIP evaporation sources equipped with a CrSi-based target and a Cr target were discharged at the same time, and a film was formed while forming a constant lamination period on a coated substrate having a rotating mechanism. This showed excellent seizure resistance. Invention Example 11 is a laminated film of a CrSi-type film and a Cr-type film, and shows a case where the lamination period is 200 nm. In this case as well, excellent characteristics were exhibited. Invention Example 12 is a case where two types of AIP evaporation sources equipped with a CrSi-based target and a Cr-based target and a sputter evaporation source equipped with a CrB2 ceramic target are used and coated in combination. For example, a CrSi-based film and a Cr-based film, a CrSi-based film and a CrB2-based film were coated at the same time, and the films were formed while constituting a constant lamination cycle. In this case, particularly excellent seizure resistance and wear resistance were exhibited. Invention Example 13 shows a case where a Cr-based film is coated as an underlayer. Also in this case, the wear resistance was excellent. Invention Example 14 shows a case where the oxygen concentration is maximized on the hard coating outermost surface. Also in this case, the wear resistance was excellent. In Invention Example 15, a Cr-based film was used as the underlayer, and a Cr-based film and a CrSi-based film were used as the laminated film. Also in this case, the wear resistance was excellent. Invention Example 16 used a Cr-based film as the underlayer, and used a CrAlSi-based film and a Cr-based film as the laminated film. In this case, the seizure resistance and the particularly excellent wear resistance were exhibited.
On the other hand, Comparative Example 21 shows the case of a CrSi-based film. The Si content was 30% in terms of atomic percent of the metal element. In this case, effective improvement was not confirmed about seizure resistance and abrasion resistance. Comparative Example 22 shows a case where the CrSi-based film is configured so that there is no Si concentration modulation. In this case, effective improvement was not confirmed about seizure resistance and abrasion resistance. This indicates that the presence state of Si in the CrSi-based film is important. In order for Si concentration modulation to be present in the CrSi-based film, it can be controlled by gas pressure, bias voltage, film forming temperature, and target supply current in the film forming process.

(Example 3)
Example 3 is a case where the hard coatings of Invention Example 17, Application Example 18 and Conventional Example 25 shown in Tables 1 and 2 were coated on a punching mold made of alloy tool steel. The coating method was the same as in Example 2 and the film thickness was 6 μm. The tip shape of the punching die was 60 μm wide and 10 mm long assuming punching of the lead frame. For the evaluation, a test was performed under the following processing conditions, and it was evaluated whether the punching die could pass through the specified number of 50k shots.
(Processing conditions)
Processing method: Slit punching Work material: 42Ni, plate thickness 150μm
Invention Example 17 and Invention Example 18 were not damaged by the hard coating, and could be processed by punching a predetermined number of 50k shots. On the other hand, the conventional example 25 has reached the end of its service life because the accuracy of the workpiece is greatly deteriorated after punching for punching 8k shots.

FIG. 1 shows the measurement results of the friction coefficient of the hard coating. FIG. 2 shows the wear depth of the hard-coated disc. FIG. 3 shows the wear depth of the hard coated ball material.

Claims (14)

In hard-coated sliding member hard film is coated, at least one layer of the hard coating represented by _{(Cr (100-α) Si} α) (N (100-γ-η) B γ G η), However, α, γ, and η represent atomic percent, where 0.5 ≦ α ≦ 20, 0 <γ <45, 0 ≦ when the atomic percent of the metal component alone is 100 and the atomic percent of the nonmetallic component is 100. η ≦ 55 is satisfied, G has at least one selected from C, O, and S, the hard coating has an X-ray diffraction peak intensity on the (200) plane of the rock salt structure type, and the X-ray The half width of the diffraction peak intensity is not less than 0.5 degrees and not more than 2.0 degrees, and has at least one selected from a nitride phase, oxide phase, and metal phase of at least Si and / or B The hard coating has a concentration modulation of Si content, and the thickness of the hard coating is 1 μm or more and less than 60 μm. Hard-coated sliding member and said and. The hard film-coated sliding member coated with the hard film according to claim 1 or 2, wherein the metal component of the hard film contains Cr, Si and M component as a content β, and the M component is V, A hard film-coated sliding member having at least one selected from Mo, W, and Al, wherein the β value satisfies 0 ≦ β <60 in atomic percent. In the hard film-coated sliding member coated with the hard film according to any one of claims 1 to 3, the other hard film of the hard film is one or more selected from 4a, 5a, 6a, Al, Si, and A hard film-coated sliding member comprising at least one selected from C, N, O, B, and S. 4. The hard film-coated sliding member according to claim 1, wherein the uppermost layer of the hard film is a hard carbon film and / or a laminated film containing a hard carbon film. Moving member. 4. The hard film-coated sliding member according to claim 1, wherein the uppermost layer of the hard film is a laminated film including a hard film mainly composed of sulfide and / or a hard film mainly composed of sulfide. There is a hard film-coated sliding member. The hard film-coated sliding member according to any one of claims 1 to 5, wherein a lamination cycle of the hard film is 100 nm or more and less than 500 nm. The hard film-coated sliding member according to any one of claims 1 to 5, wherein the lamination period of the hard film is 0.5 nm or more and less than 30 nm. 8. The hard film-coated sliding member according to claim 1, wherein the hard film-coated sliding member has a gradient or periodicity of residual compressive stress in the film thickness direction of the hard film. The hard film-coated sliding member according to any one of claims 1 to 8, wherein at least one element selected from C, O, S, and B in a region of less than 200 nm in the film thickness direction from the uppermost layer of the hard film. A hard film-coated sliding member having a maximum concentration. 10. The hard film-coated sliding member according to claim 1, further comprising a nitride layer at an interface between the hard film and the base of the sliding member. 11. The hard film-coated sliding member according to claim 1, wherein an interface between the hard film and the base of the sliding member is mechanically smoothed. Element. The hard film-coated sliding member according to claim 1, wherein the hard film-coated sliding member is a mold. The hard film-coated sliding member according to any one of claims 1 to 11, wherein the hard film-coated sliding member is a piston ring. A hard film-coated sliding member according to any one of claims 1 to 11, wherein the hard film-coated sliding member is a supercharging pressure control component for an internal combustion engine.

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