Sliding system

Abstract

[Technical Problem] An object is to provide a sliding system which can drastically reduce the friction coefficient on a sliding portion by means of a novel combination of a chromium nitride film and a lubricant oil. [Solution to Problem] The sliding system according to the present invention includes: a pair of sliding members having sliding surfaces that can relatively move while facing each other; and a lubricant oil that can be interposed between the sliding surfaces facing each other. At least one of the sliding surfaces is formed as a coating surface of a chromium nitride film, and the lubricant oil contains an oil-soluble molybdenum compound that has a chemical structure of a trinuclear of Mo. When the chromium nitride film as a whole is 100 at % (referred simply to as “%”), the chromium nitride film contains 40-65% of Cr and 35-55% of N, and the chromium nitride film has a relative surface area of 15-60% wherein the relative surface area is a surface area ratio of (111) plane to (200) plane obtained when analyzed using X-ray diffraction. The lubricant oil preferably contains 5-800 ppm of the oil-soluble molybdenum compound in a content mass of Mo to the lubricant oil as a whole.

Claims

1. A sliding system comprising: a pair of sliding members having sliding surfaces that can relatively move while facing each other; and a lubricant oil that can be interposed between the sliding surfaces facing each other, wherein at least one of the sliding surfaces comprises a coating surface of a chromium nitride film; wherein the lubricant oil contains an oil-soluble molybdenum compound that has a chemical structure of a trinuclear molybdenum compound, wherein, when the chromium nitride film as a whole is 100 at % (referred simply to as “%”), the chromium nitride film contains 40-65% of Cr and 35-55% of N, and the chromium nitride film has a relative surface area of 15-34% wherein the relative surface area is a surface area ratio of (111) plane to (200) plane obtained when analyzed using X-ray diffraction.

2. The sliding system as recited in claim 1, wherein Mo and S are present on the sliding surface of the chromium nitride film, and a ratio of a number of atoms of S to that of Mo is 2 or more when analyzed using X-ray photoelectron spectroscopy (XPS).

3. The sliding system as recited in claim 1, wherein the chromium nitride film further contains 2-15% of O.

4. The sliding system as recited in claim 1, wherein the chromium nitride film contains Cr.sub.2N in addition to CrN.

5. The sliding system as recited in claim 1, wherein the trinuclear molybdenum compound has a molecular structural skeleton of at least one of Mo.sub.3 S.sub.7 or Mo.sub.3S.sub.8.

6. The sliding system as recited in claim 1, wherein the lubricant oil contains the oil-soluble molybdenum compound with a mass ratio of Mo to the lubricant oil as a whole of 5-800 ppm.

7. The sliding system as recited in claim 1, wherein, when a detected amount by the XPS is 100 at % as a whole, 0.04 at % or more of Mo is present.

8. The sliding system as recited in claim 1, wherein, when a detected amount by the XPS is 100 at % as a whole, 0.06 at % or more of Mo is present.

9. The sliding system as recited in claim 8, wherein Mo and S are present on the sliding surface of the chromium nitride film, and a ratio of number of atoms of S to that of Mo is 2 or more when analyzed using X-ray photoelectron spectroscopy (XPS).

10. The sliding system as recited in claim 1, wherein the ratio of number of atoms of S to that of Mo is 4 or more when analyzed using X-ray photoelectron spectroscopy (XPS).

11. The sliding system as recited in claim 1, wherein the ratio of number of atoms of S to that of Mo is 5 or more when analyzed using X-ray photoelectron spectroscopy (XPS).

Description

BRIEF DESCRIPTION OF DRAWINGS

(1) FIG. 1A is a set of profiles obtained using X-ray diffraction of chromium nitride films according to the samples.

(2) FIG. 1B is an enlarged view of the X-ray diffraction profile according to Sample 3.

(3) FIG. 2 is a bar graph comparing friction coefficients of the samples.

(4) FIG. 3 is a bar graph comparing friction depths of the samples.

(5) FIG. 4 is a dispersion diagram showing a correlation between relative surface areas and friction coefficients of the samples.

(6) FIG. 5 is a set of 3d spectra of Mo obtained using XPS to analyze a sliding surface of each sample after friction test.

(7) FIG. 6 is a molecular structure diagram showing an example of Mo-trinuclear according to the present invention.

DESCRIPTION OF EMBODIMENTS

(8) One or more features freely selected from the description herein may be added to the above-described features of the present invention. The contents described herein may be applied not only to the sliding system as a whole according to the present invention but also to sliding members and lubricant oil which constitute the sliding system. Moreover, methodological features may also be features regarding a product. Which embodiment is the best or not is different in accordance with objectives, required performance and other factors.

(9) <<Lubricant Oil>>

(10) The lubricant oil according to the present invention is not limited in the type of a base oil and presence or absence of other additives, etc., as long as the lubricant oil contains a Mo-trinuclear. In general, lubricant oil such as engine oil contains various additives including S, P, Zn, Ca, Mg, Na, Ba, or Cu, etc. Even in such lubricant oil, the Mo-trinuclear according to the present invention preferentially acts on the sliding surface (coating surface) coated with the chromium nitride film and contributes to formation of a molybdenum sulfide compound (such as MoS.sub.2, Mo.sub.3S.sub.7, Mo.sub.3S.sub.8 and Mo.sub.2S.sub.6) which can reduce the friction coefficient.

(11) The lubricant oil according to the present invention may contain other Mo-based compounds (such as MoDTC) than the Mo-trinuclear, but the total amount of the contained Mo may preferably be small because Mo is a kind of rare metal.

(12) Unduly small amount of the Mo-trinuclear makes it difficult to exhibit the effect as the above, whereas unduly large amount of the Mo-trinuclear may not cause any problem. As described above, however, the usage of Mo may preferably be small. It is therefore preferred that the Mo-trinuclear according to the present invention has a mass ratio of Mo to the lubricant oil as a whole of 5-800 ppm in an embodiment, 10-500 ppm in another embodiment, 40-200 ppm in still another embodiment, and 60-100 ppm in a further embodiment. When the mass ratio of Mo to the lubricant oil as a whole is represented in ppm, it will be denoted by “ppmMo.” Note that, even when the lubricant oil contains other Mo-based compounds and the like than the Mo-trinuclear, the upper limit of the total amount of Mo of the other Mo-based compounds may preferably be 400 ppmMo in an embodiment, and 300 ppmMo in another embodiment, to the lubricant oil as a whole.

(13) <<Chromium Nitride Film>>

(14) Method of forming the chromium nitride film according to the present invention is not limited. For example, a desired chromium nitride film can be efficiently formed using a physical vapor deposition (PVD) method, such as an arc ion plating (AIP) method and a sputtering (SP) method (in particular, an unbalanced magnetron sputtering (UBMS) method).

(15) The AIP method is a method in which a metal target (vaporization source) is used as the cathode to cause arc discharge in a reactive gas (process gas) so that metal ions generated from the metal target react with the reactive gas particles to form a dense film on a surface to be coated to which a bias voltage (negative voltage) is applied. In an embodiment of the present invention, the target may be metal Cr, and the reactive gas may be N.sub.2 gas, for example. When forming a chromium nitride film that contains doped elements in addition to Cr and N, a target or a reactive gas that contains the doping elements may be used. The composition, structure and other properties of the chromium nitride film can be controlled by adjusting the components of the target and/or the reactive gas and/or adjusting the gas pressure of the reactive gas. For example, the gas pressure of N.sub.2 may be adjusted thereby to allow a single-layer film of CrN or a composite film of CrN and Cr.sub.2N to be obtained.

(16) The SP method is a method in which a voltage is applied between a target at the cathode side and a surface to be coated at the anode side, and inactive gas atom ions generated due to glow discharge are caused to collide with the target surface so that particles (atoms/molecules) released from the target are deposited to form a film on the surface to be coated. In an embodiment of the present invention, the sputtering is performed using metal Cr as the target and Ar gas as the inactive gas, for example, and the released Cr atoms (ions) can be reacted with N.sub.2 gas thereby to form the chromium nitride film on a sliding surface.

(17) <<Intended Use>>

(18) The sliding members according to the present invention are not limited in the type, form, sliding form, and other features as long as the sliding members have sliding surfaces that relatively moves while the lubricant oil is interposed therebetween. The sliding system provided with such sliding members is also not limited in its specific form and intended use, and can be widely applied to various machines, apparatuses, and the like which require reduction of the sliding resistance and reduction of the machine loss due to sliding. For example, the sliding system of the present invention may preferably be utilized for a drive system unit (such as engine and transmission) for vehicles such as cars. Examples of the sliding members that constitute such a sliding system include: components, such as cam, valve lifter, follower, shim, valve and valve guide, which constitute a dynamic valve system; piston; piston ring; piston pin; crankshaft; gear; rotor; and rotor housing.

Examples

(19) <<Overview>>

(20) Materials under test coated with various chromium nitride films (sliding members) were combined with a lubricant oil containing a Mo-trinuclear (oil-soluble molybdenum compound) (referred to as a “lubricant oil A”) or a lubricant oil free from a Mo-trinuclear (referred to as a “lubricant oil B) to perform a block-on-ring friction test. The present invention will be more specifically described with reference to the results of the friction test.

(21) <<Production of Samples>>

(22) (1) Base Material

(23) A plurality of block-like base materials (6.3 mm×15.7 mm×10.1 mm) were prepared, each comprising a quenched steel material (JIS SUS440C). A surface (surface to be coated) of each base material was mirror-finished (surface roughness Ra: 0.08 micrometers).

(24) A steel material (JIS SCM420) merely carburized was also prepared as a comparative sample not to be coated with a chromium nitride film (Sample C1 in Table 1). The carburized surface (hardness Hv of 700) was also mirror-finished to the same roughness.

(25) (2) Film Formation of Chromium Nitride Films

(26) Materials under test (Samples 1 to 5) were prepared by forming various chromium nitride films as listed in Table 1 on the surfaces of the above respective base materials. Formation of the chromium nitride films was performed using an arc ion plating (AIP) method or a sputtering (SP) method.

(27) Formation of films using the arc ion plating method was performed by generating arc discharge on a target of metal Cr in N.sub.2 gas (reactive gas) having an adjusted pressure of 0.3 to 6 Pa. Formation of an O-containing chromium nitride film was performed using a mixture gas of N.sub.2 gas and O.sub.2 gas as the reactive gas. During this operation, the ratio of the amount of O was 0.1 vol % to the mixture gas as a whole. Formation of a B-containing chromium nitride film was performed using a target of Cr—B alloy (Cr-5 mass % B).

(28) Formation of a film using the sputtering method was performed by sputtering a target of metal Cr with Ar gas to cause the released Cr atoms (ions) to react with N.sub.2 gas. During this operation, the pressure of the N.sub.2 gas was 0.5 to 6 Pa.

(29) (3) Comparative Samples

(30) Another comparative sample was also prepared as a material under test (Sample C2) by coating the surface of the above-described base material (SUS440C) with a commercially available hydrogen-free DLC film (available from NIPPON ITF, INC.) as substitute for the chromium nitride film.

(31) <<Measurement and Analysis of Chromium Nitride Films>>

(32) (1) Film Composition and Film Properties

(33) Film composition of each sample was quantified using an EPMA (JXA-8200 available from JEOL Ltd). Film hardness was measured using a nanoindenter tester (TRIBOSCOPE available from Hysitron Corporation). Film thickness was specified from a friction trace obtained using Calotest available from CSM Instruments SA. The film composition and the film properties thus obtained of each sample are also listed in Table 1. The surface profile (roughness) according to the present examples was measured using a white light interferometric non-contact surface profiler (NewView 5022 available from Zygo Corporation).

(34) (2) Film Structure

(35) The chromium nitride film of each sample was analyzed using X-ray diffraction. Respective profiles thus obtained are shown in FIG. 1A in a superimposed manner. As one example among them, the profile according to Sample 3 is shown in FIG. 1B in an enlarged manner. FIG. 1A and FIG. 1B may be collectively referred to as FIG. 1.

(36) The relative surface area of (111) plane to (200) plane was obtained according to the previously-described method on the basis of each profile shown in FIG. 1. The relative surface area thus calculated of each sample is also listed in Table 1. As found from the profiles of the samples, Cr was not detected in all of the samples, and CrN was primarily detected. Note, however, that Cr.sub.2N was detected in addition to CrN only in Sample 3. Presence or absence of detection of Cr.sub.2N is also listed in Table 1.

(37) <<Lubricant Oil>>

(38) Two types of engine oils listed in Table 3 were prepared as lubricant oils to be used in the friction test. Lubricant oil A was obtained by additionally compounding Mo trinuclear denoted as “Trinuclear” in the disclosed documentation “Molybdenum Additive Technology for Engine Oil Applications” available from INFINEUM INTERNATIONAL LIMITED (which may be referred simply to as “Mo-trinuclear”) to an engine oil as a base (motor oil SN OW-20 available from TOYOTA MOTOR CORPORATION) having a viscosity grade of OW-20 and corresponding to ILSAC GF-5 standard so that the Mo content in the oil as a whole would be 80 ppmMo equivalent. On the other hand, lubricant oil B is the base engine oil itself to which such an oil additive is not additionally compounded. Both lubricant oils are free from molybdenum dithiocarbamate (MoDTC).

(39) <<Block-on-Ring Friction Test>>

(40) (1) Friction Coefficient

(41) Block-on-ring friction test (referred simply to as “friction test”) was performed for a combination of each material under test and each lubricant oil to measure the friction coefficient (mu) of each sliding surface. The friction coefficient of each material under test when using the lubricant oil A containing the Mo-trinuclear is also listed in Table 1. A bar graph comparing these friction coefficients is shown in FIG. 2.

(42) The friction test was performed using each material under test as a block test piece having a sliding surface width of 6.3 mm and using a standard test piece S-10 (hardness HV of 800 and surface roughness Rzjis of 1.7 to 2.0 micrometers) of a carburized steel material (AISI4620) available from FALEX CORPORATION as a ring test piece (outer diameter of 35 mm and width of 8.8 mm). The friction test was performed for 30 minutes under the conditions of a test load of 133 N (Hertz contact pressure of 210 MPa), a sliding speed of 0.3 m/s, and an oil temperature of 80 degrees C. (fixed), and the average value of mu during one minute immediately before completion of the test was determined as the friction coefficient.

(43) (2) Friction Depth of Sliding Surface

(44) The sliding surface of each material under test after the friction test using the lubricant oil A was measured using the previously-described non-contact surface profiler to obtain a friction depth. Results thereof are also listed in Table 1. In addition, a bar graph comparing the friction coefficients is shown in FIG. 3 with indication of corresponding film hardness.

(45) (3) Surface Analysis of Sliding Surface

(46) The sliding surface of each material under test after the friction test using the lubricant oil A was analyzed using X-ray photoelectron spectroscopy (XPS). The ratio (at %) of an element detected on each sliding surface is listed in Table 2. In addition, results of state analysis using 3d spectra of Mo are shown in FIG. 5. As will be understood, the presence of oxide or sulfide of Mo can be determined by observing the 3d spectra of Mo.

(47) <<Evaluation>>

(48) (1) Friction Property

(49) First, as apparent from FIG. 2, when the lubricant oil B free from Mo-trinuclear was used, the friction coefficient was not much different among the samples provided with the chromium nitride films on the sliding surfaces, the sample provided with the H-free DLC film on the sliding surface, and the sample with the sliding surface of the carburized material itself. The friction coefficient was higher than 0.07 in all of the samples.

(50) It was found on the other hand that, when the lubricant oil A containing the Mo-trinuclear was used, the friction coefficient was drastically reduced only in Samples 2 to 4 provided with specific chromium nitride films on the sliding surfaces. Specifically, it was found that the friction coefficient was 0.05 or lower in all of Samples 2 to 4 and reduced by 40% or more to the friction coefficient (0.09) of Sample C1 with the sliding surface of the carburized material itself.

(51) Next, as apparent from FIG. 3, it was also confirmed that the friction depth was small, i.e., about 0.2 micrometers, in all of Samples 1 to 5 provided with the chromium nitride films and did not come to that of Sample C2 provided with the DLC film, but Samples 1 to 5 exhibited sufficient wear resistance compared with the friction depth (1 micrometer or more) of Sample C1. The chromium nitride film formed by the SP method and having the smallest amount of N was hardest, but the hardness was stable within 15 to 25 GPa in all of the chromium nitride films. It can thus be considered that special correlationship does not exist between the film hardness and the composition (e.g., N amount) or the production method, etc.

(52) (2) Structure of Chromium Nitride Films

(53) As described above, the chromium nitride films of Samples 2 to 4 are apparently different from those of Samples 1 and 5 in the sliding properties under the situation where the lubricant oil A is present. This appears to be because the film structure differs between Samples 2 to 4 and Samples 1 and 5. That is, the chromium nitride films of Samples 1 to 5 are primarily formed of CrN, but the relative surface area of (111) plane to (200) plane is significantly different between Samples 2 to 4 and Samples 1 and 5, as understood from FIG. 1 and Table 1.

(54) To clarify this aspect, FIG. 4 will now be referred which shows a relationship between the relative surface area and the friction coefficient in the presence of the lubricant oil A. As apparent from FIG. 4, it has been found that the friction coefficient is large in both of the chromium nitride film (Sample 1) having an unduly small relative surface area and strong orientation of (200) plane and the chromium nitride film (Sample 5) having an unduly large relative surface area and strong orientation of (111) plane. It has been found on the other hand that the friction coefficient is 0.05 or less in the chromium nitride films (Samples 2 to 4) having a relative surface area of 15-60% in an embodiment, and 20-45% in another embodiment in which (200) plane and (111) plane are mixed at an appropriate ratio, and these samples exhibit excellent low-friction properties.

(55) (3) Surface Analysis of Sliding Surfaces

(56) As found from Table 2, Mo was detected on the sliding surfaces of Samples 2 to 4 which exhibited low-friction properties in the presence of the lubricant oil A, whereas Mo was not detected on the sliding surfaces of Samples 1 and 5 which did not exhibit low-friction properties. Moreover, as apparent from FIG. 5, it was found that sulfide or oxide of Mo was generated on the sliding surfaces of Samples 2 to 4, whereas such a generated product was not confirmed on the sliding surfaces of Samples 1 and 5. Furthermore, it was also found that a larger amount of Mo sulfide (MoS.sub.2) than that of Mo oxide was detected on the sliding surfaces of Samples 2 and 3. In addition, as apparent from Table 2, an amount of S twice or more (or four times or more) that of Mo was detected in all of the samples in which 0.04 at % or more of Mo was detected.

(57) (4) Consideration

(58) In the light of the above results, it can be considered that a chromium nitride film having a specific structure in which (200) plane and (111) plane are mixed within a certain range is formed with a molybdenum sulfide compound, such as Mo.sub.3S.sub.7, Mo.sub.3S.sub.8 and MoS.sub.2, on the surface (sliding surface) due to adsorption or reaction of Mo-trinuclear in a situation where a lubricant oil that contains Mo-trinuclear is present. It can also be considered that the molybdenum sulfide having such a lamellar structure exhibits a low shear property, and the sliding surface of the chromium nitride film according to the present invention can thereby exhibit excellent low-friction property.

(59) TABLE-US-00001 TABLE 1 Film Structure Sliding Properties (X-ray diffraction) Friction Relative Friction Depth Film Properties Surface Presence Coefficient (μm) Film Composition Film Film Area or Lubri- Lubri- Lubri- Sample Production (at %) Hardness Thickness (111)/(200) Absence cant cant cant No. Name Method Cr N O B (GPa) (μm) (%) of Cr.sub.2N Oil A Oil B Oil A Note 1 B SP 62.4 37.6 — — 24.1 2 3.4 Absent 0.087 — 0.25 Method 2 T AIP 50.7 49.3 — — 16.9 13 34 Absent 0.05 0.077 0.25 Method 3 N 60.9 39.1 — — 21.5 8 24.7 Present 0.05 0.087 0.2 4 T-O 49.8 40.5 9.8 — 22.4 13 28.5 Absent 0.043 0.083 0.3 5 N-B 48.7 50.0 — 1.3 21.0 9 75.8 Absent 0.077 — 0.2 C1 (Carburized — — (HV700) — — 0.09 0.085 1.1 SCM420 Material) C2 (DLC) — 59.0 — 0.07 0.075 0.05 H-free DLC

(60) TABLE-US-00002 TABLE 2 Analyzed Composition on Sliding Surface Sample (at %) No. Name C N O Na P S Ca Fe Cr Zn Mo 1 B 32.8 6.14 33.4 0.00 7.27 1.89 4.14 0.45 9.60 4.25 0.00 2 T 37.0 2.61 36.4 0.00 6.52 2.61 8.45 0.60 2.41 2.87 0.55 3 N 30.2 5.15 36.1 0.00 7.77 2.08 4.91 0.71 8.47 4.57 0.08 4 T-O 32.2 3.35 37.8 0.00 7.58 1.89 7.77 0.65 4.89 3.58 0.25 5 N-B 31.9 7.41 33.6 0.00 7.06 1.99 4.30 0.62 8.50 4.60 0.00

(61) TABLE-US-00003 TABLE 3 Presence or Absence of Components of Lubricant Oil (The Balance: Base Oil) Mo Trinuclear (ppm) Name of Lubricant Oil Compound Mo S Zn P N B Ca Na Si Lubricant Oil A Present 80 2400 700 630 500 16 2000 0 4 (80 ppm) Lubricant Oil B Absent 130 1800 730 690 900 4 1760 360 4