WO2023074868A1

WO2023074868A1 - Sliding member

Info

Publication number: WO2023074868A1
Application number: PCT/JP2022/040472
Authority: WO
Inventors: 滋鈴木; 和亮 ▲高▼田; 幸祐入倉
Original assignee: パーカー加工株式会社
Priority date: 2021-10-29
Filing date: 2022-10-28
Publication date: 2023-05-04

Abstract

The present invention addresses the problem of providing a combination sliding member which has low impact on the environment, which can be produced via a simple method, and which has excellent antifriction properties and durability.　This problem is solved by a combination sliding member. Specifically, the problem is solved by a combination sliding member comprising a first sliding part that is made from aluminum or an aluminum alloy and a second sliding part that is made from a steel material, said combination sliding member being characterized in that: a surface of the second sliding part that slides on the first sliding part has a manganese phosphate coating that contains copper; in the manganese phosphate coating, the manganese content is not less than 1.5 g/m² and the copper/manganese content ratio is 0.02-2.56; and the surface roughness Ra of a surface of the first sliding part that slides on the second sliding part is not more than 2.9 μm.

Description

sliding member

The present invention relates to a sliding member, and more particularly to a combination sliding member including a plurality of sliding members that slide against each other. Combination sliding members include, for example, rolling bearings and housings.

Conventionally, a combination sliding member including members formed of materials with different hardness, such as a valve and a valve body, has been used. As such a combined sliding member, for example, a first sliding component made of an aluminum alloy having an alumite layer formed on the sliding surface, and a sliding surface of the first sliding component that slides on the sliding surface to provide a predetermined A combined sliding member (Patent Document 1) is known that includes a second sliding component made of polymer resin, reinforcing fibers, and solid lubricant.

In addition, from the viewpoint of energy saving, there is a demand for downsizing of equipment in various industrial fields, and along with this, for example, there is a tendency for bearings in sliding members that combine rolling bearings and housings to be thinner. In thin-walled bearings such as rolling bearings, there is a possibility that a creep phenomenon may occur in which a fixed side component such as an outer ring rotates with respect to a housing depending on the sliding environment. The creep phenomenon accelerates housing wear and can cause failure of rotating equipment.

JP 2016-114075 A

As in the prior art described above, a sintering step is required to form a layer of polymeric resin containing a solid lubricant or the like. Therefore, from the viewpoint of global warming, for which countermeasures are required these days, there is a problem of reducing the amount of greenhouse gases generated in the life cycle assessment.
For example, in order to prevent abrasion of the housing due to creep phenomenon in a sliding member combining a rolling bearing and a housing, a polymer resin layer containing a solid lubricant or the like is formed on the sliding surface in contact with the housing. A firing process is required, which complicates the manufacturing process of the bearing and produces greenhouse gases.
In addition, in order to form an alumite layer as shown in Patent Document 1, a relatively complicated process such as an anodizing treatment using an acidic treatment liquid is required, and power consumption increases. do.

The present invention has been made in view of these points, and according to the present invention, a combined sliding surface that has low environmental load, can be manufactured by a simple method, and is excellent in wear resistance, durability, etc. It is possible to provide a member, for example, a combined sliding member capable of suppressing housing wear due to rolling bearing creep.

The above problems have been solved by the present invention. The present invention includes the following.
[1] A combined sliding member comprising a first sliding component made of aluminum or an aluminum alloy and a second sliding component made of steel,
A surface of the second sliding part that slides against the first sliding part has a copper-containing manganese phosphate coating, and the manganese phosphate coating contains 1.5 g/m ² of manganese. above, the copper/manganese content ratio is 0.02 to 2.56,
A combination sliding member, wherein a surface roughness Ra of a surface of the first sliding part that slides on the second sliding part is 2.9 μm or less.
[2] Valves/valve bodies, rocker arms/rocker shafts, pistons/piston rings, pistons/piston pins, pistons/cylinders, housings/bearings, and electric steering columns as the first sliding parts/second sliding parts / The combination sliding member according to the above [1], which is either a pipe.
[3] The combined sliding member according to [2] above, wherein the first sliding component is a housing and the second sliding component is a rolling bearing.
[4] The rolling bearing as the second sliding component is
An outer ring, an inner ring, and a plurality of rolling elements arranged to be rollable between the outer ring and the inner ring,
The combination according to [3] above, wherein at least one of the outer diameter surface of the outer ring and the inner diameter surface of the inner ring, the surface sliding on the housing as the first sliding component has the manganese phosphate coating. sliding member.
[5] A combined sliding member comprising a first sliding component made of aluminum or an aluminum alloy and a second sliding component made of steel,
A surface of the second sliding part that slides on the first sliding part has a copper-containing manganese phosphate coating, and the manganese phosphate coating has a manganese content of 2.1 g/m ^{2 .} above, the copper/manganese content ratio is 0.04 to 0.62,
A combination sliding member, wherein a surface roughness Ra of a surface of the first sliding part that slides on the second sliding part is 2.9 μm or less.
[6] The combined sliding member according to [5] above, wherein the second sliding component is an SUJ material defined in JIS G4805:2008.
[7] The combined sliding member according to [1] or [5] above, wherein the manganese phosphate coating has a thickness of 1 to 25 μm.

According to the present invention, it is possible to provide a combination sliding member that has a low environmental load and is excellent in wear resistance, durability, etc., by a simple method.

FIG. 10 is a diagram showing an example of an SEM enlarged observation image of a copper-containing manganese phosphate coating in Example 2; It is a figure which shows roughly about the method of a sliding performance test (abrasion resistance test). FIG. 4 is a partial cross-sectional view showing an example of a combined sliding member of a rolling bearing and a housing;

The present invention will be described in detail below.

[1. Sliding member]
The combined sliding member of the present invention includes at least a first sliding component and a second sliding component, wherein the sliding surfaces of the first sliding component and the second sliding component are in contact with each other and slide. is configured as
Each member will be described below.

(1-1. First sliding component)
1-1a. Material of First Sliding Part The first sliding part is made of aluminum or an aluminum alloy. Specific examples of aluminum and aluminum alloys contained in the first sliding component include the following alloy symbols defined in JIS H4000:2017.
In other words, 1085, 1080, 1060, 1060 ,1050 ,1200, 1N00, 1N00, 1N30, 1230, 2017, 2017, 2219, 2219, 2219, 2219, 3103, 3203, 3204, 3104, 3105, 3003, 3003, 3003, 3003, 3003, 3003, 3003, 3003, 3003. 5, 5052, 5110, 5021, 5042, 5050, 5052, 5154, 5254, 5454, 5754, 5456, 5082, 5182, 5083, 5086, 5N01, 6101, 6061, 6082, 7204, 7N01, 7204, 7010, 7050, 7 075, It is represented by an alloy symbol such as 7072, 7475, 7178, 8011, 8021, 8079.
Further, specific examples of aluminum and aluminum alloys contained in the first sliding part include AC1B, AC1C, AC2A, AC2B, AC3A, and AC4A among JIS symbols in Japanese Industrial Standards such as JIS H5302:2006 and JISH5202:2010. , AC4B, AC4C, AC4CH, AC4D, AC5A, AC7A, AC8A, AC8B, AC8C, AC9A, AC9B, ADC1, ADC3, ADC5, ADC6, ADC10, ADC10Z, ADC12, ADC12Z, and ADC14.

The first sliding component may contain only one of the aluminum and aluminum alloys described above, or may contain more than one.

1-1b. Surface that slides with the second sliding component (first sliding surface)
The first sliding component has a sliding surface (first sliding surface) in contact with the second sliding component. The surface roughness is adjusted on the first sliding surface.
That is, the value of the arithmetic mean roughness Ra conforming to JIS B 0601-2001 on the first sliding surface is 2.9 μm or less. In addition, the Ra value of the first sliding surface is preferably 2.5 μm or less, more preferably 2.2 μm or less, still more preferably 2.0 μm or less, and particularly preferably 1.8 μm or less. , 1.5 μm or less, 1.2 μm or less, 1.0 μm or less, or 0.8 μm or less.

Since it is preferable that the surface roughness of the first sliding surface is small, the lower limit of the Ra value is not particularly important. It is 2 μm or more, 0.3 μm or more, or 0.4 μm or more.
A method for measuring the value of the arithmetic mean roughness Ra will be described later.

(1-2. Second sliding component)
1-2a. Material of Second Sliding Part The second sliding part contains at least steel. As a specific example of the steel material contained in the second sliding part, steel base material symbols SUJ1, SUJ2, SUJ3, SUJ4, SUJ5 (SUJ material: high carbon chromium bearing steel material), SCr415, SCr420, SCr435 (SCr material: chrome steel material), SCM415, SCM418, SCM420, SCM421, SCM425, SCM430, SCM432, SCM435, SCM440, SCM445, SCM822 (SCM material: chromium molybdenum steel material), SNCM220 , SNCM420, SNCM815 (SNCM material: nickel-chromium-molybdenum steel), SUS440, SUS403, SUS410, SUS410J1, SUS410F2, SUS416, SUS420J1, SUS420J2, SUS420F, SUS420F2, SUS431, SUS440A, SUS440B, SUS4 40C, SUS440F, SUS405, SUS410L, SUS430 , SUS430F, SUS434, SUS447J1, SUSXM27, SUS329J1, SUS329J3L, SUS329J4L, SUS201, SUS202, SUS301, SUS302, SUS303, SUS303Se, SUS303Cu, SUS304, SUS304L, SUS304N1, SUS304N2, SUS304LN, SUS304J3, SUS305, SUS309S, SUS310S, SUS316, SUS316L , SUS316N, SUS316LN, SUS316Ti, SUS316J1, SUS316J1L, SUS316F, SUS317, SUS317L, SUS317LN, SUS317J1, SUS836L, SUS890L, SUS321, SUS347, SUSXM7, SUSXM15J1, SUS63 Those represented by 1 etc., AISI etc. that generally correspond to the above JIS standards and those stipulated by other standards.
The steel material described above can be used regardless of the type of the second sliding component, and is preferably used in bearings such as rolling bearings, for example.
Further specific examples of the steel material contained in the second sliding part include carbon steel, cold-rolled steel plate (SPCC), carbon steel pipe for machine structural use (STKM material), carbon tool steel (SK material), alloy tool steel (SKS materials), sintered materials for machine structural parts, and other structural special steels. These steel materials can also be employed regardless of the type of the second sliding component, and are preferably used for components other than bearings, for example.

Further, the steel material of the second sliding part may be subjected to a predetermined heat treatment such as quenching and tempering, carburizing or carbonitriding, quenching and tempering.
The second sliding component may contain only one of the steel materials described above, or may contain more than one.

1-2b. Copper-containing manganese phosphate coating (phosphate coating)
A copper-containing manganese phosphate coating is formed on the sliding surface (second sliding surface) of the second sliding component that is in contact with the first sliding component. The manganese phosphate coating is arranged on the surface of the second sliding surface so as to be in contact with the first sliding surface.

Manganese phosphate coatings contain copper and manganese. As a manganese phosphate coating containing copper, specifically, there is a form in which the copper compound added during the formation of the manganese phosphate coating co-deposits in the manganese phosphate coating as shown in FIG. In the manganese phosphate coating, the manganese content (content based on the unit area of the coating) is 1.5 g/m ² or more, preferably 1.7 g/m ² or more, more preferably , 2.0 g/m ² or more, or 2.1 g/m ² or more.
The manganese content in the manganese phosphate coating is more preferably 2.3 g/m ² or more, more preferably 2.5 g/m ² or more, and more preferably 3.0 g/m ² or more. Especially preferred.
^Regarding the content of ^manganese in the manganese phosphate coating, the lower limit ^is important, and the upper limit is not particularly limited. It may be 8.0 g/m ² or less.
In the manganese phosphate coating, the value of the content ratio (weight ratio) of copper/manganese, that is, the ratio of the content of copper and manganese per unit area contained in the manganese phosphate coating is from 0.02 to 0.02. 2.56, preferably 0.05 to 2.20, 0.10 to 2.00 or 0.15 to 1.80, more preferably 0.20 to 1.60, 0.22 to 1 .40 or 0.25 to 1.30.
The content ratio (weight ratio) of copper/manganese is 0.02 or more, preferably 0.05 or more, 0.10 or more, or 0.15 or more, more preferably 0.20 or more, or 0.22 or more. , or greater than or equal to 0.25. In addition, the value of the content ratio of copper/manganese is 2.56 or less, preferably 2.20 or less, 2.00 or less, or 1.80 or less, more preferably 1.60 or less, 1.40 less than or equal to 1.30.
The content ratio (weight ratio) of copper/manganese in the manganese phosphate coating is preferably in the range of 0.04 to 0.62. The content ratio value is preferably in the range of 0.06 to 0.50, more preferably in the range of 0.08 to 0.40, and in the range of 0.10 to 0.30 more preferably within.

Phosphate coatings other than manganese phosphate coatings may be used, and specific examples thereof include zinc phosphate coatings, zinc calcium phosphate coatings, manganese phosphate coatings as well as manganese-containing phosphate coatings. zinc-manganese coating;

As described above, in the phosphate coating containing a metal other than manganese, phosphate and copper co-deposit as in the manganese phosphate coating. The content of the phosphate-derived metal in the phosphate coating and the range of the weight ratio of the phosphate-derived metal to copper are the same as in the manganese phosphate coating described above.
That is, in the phosphate coating containing metals other than manganese, the total content of phosphate-derived metals is preferably 2.1 g/m ² or more, and preferably 2.3 g/m ² or more. is more preferably 2.5 g/m ² or more, and particularly preferably 3.0 g/m ² or more.
Also, regarding the total content of phosphate-derived metals in the phosphate coating containing metals other than manganese, the lower limit is important, and the upper limit is not particularly limited, but for example, 15 g/ ^m2 or less. , 12 g/m ² or less, 10 g/m ² or less, or 8.0 g/m ² or less.
In the phosphate coating containing a metal other than manganese, the content ratio (weight ratio) of the total amount of copper/phosphate-derived metal is, for example, 0.02 to 2.56, preferably 0.05 to 2.20, 0.10 to 2.00 or 0.15 to 1.80, more preferably 0.20 to 1.60, 0.22 to 1.40 or 0.25 to 1 .30.
The value of the content ratio (weight ratio) of the total amount of copper/phosphate-derived metals is, for example, 0.02 or more, preferably 0.05 or more, 0.10 or more, or 0.15 or more, more preferably is greater than or equal to 0.20, greater than or equal to 0.22, or greater than or equal to 0.25. In addition, the value of the content ratio (weight ratio) of the total amount of copper/phosphate-derived metals is, for example, 2.56 or less, preferably 2.20 or less, 2.00 or less, or 1.80 or less. and more preferably 1.60 or less, 1.40 or less, or 1.30 or less.
In addition, the value of the content ratio (weight ratio) of the total amount of copper/phosphate-derived metals in the phosphate coating is preferably in the range of 0.04 to 0.62. The weight ratio range is preferably in the range of 0.06 to 0.50, more preferably in the range of 0.08 to 0.40, and in the range of 0.10 to 0.30. It is even more preferable to have

As is clear from the above, the manganese phosphate coating contains copper co-deposited with the formation of the manganese phosphate coating, and various phosphates are included as other components. It may be For example, the phosphate coating is preferably a manganese phosphate coating, but may be a zinc phosphate coating or a zinc calcium phosphate coating. However, from the viewpoint of improving the adhesion and slidability of the phosphate coating, it is preferable to use a manganese phosphate coating or a zinc manganese phosphate coating.

A copper-containing phosphate coating is formed with various phosphate solutions. For example, manganese phosphate-based treatment agents, zinc phosphate-based treatment agents, zinc calcium phosphate-based treatment agents, and zinc manganese phosphate-based treatment agents (all of which are manufactured by Nihon Parkerizing Co., Ltd. are preferably used (for example, phosphorus A copper-containing phosphate film is formed by a mixed treatment solution in which a compound containing copper ions is added to a treatment solution that has been appropriately adjusted using manganese acid treatment agents such as PF-M1A and PF-M5). is formed.

1-2c. Copper in Manganese Phosphate Coating (Phosphate Coating) The phosphate solution preferably contains the following compound as a copper ion supply source for codepositing copper together with the phosphate.
That is, examples of the copper ion supply source include copper (II) nitrate, aqueous solutions of copper (I) chloride, copper (II) chloride, copper (II) sulfate, metallic copper, and the like. A copper-containing phosphate coating may be formed by adding to the phosphating solution described above and using the added treating solution.
The copper-containing phosphate coating is formed by, for example, immersing the second sliding component, which has been subjected to pretreatments such as cleaning and degreasing, in the mixed treatment liquid described above by a general method.

In the manganese phosphate coating, as described above, the value of the copper/manganese weight ratio is 0.02 to 2.56, preferably 0.04 to 0.62. The value of the weight ratio of the total amount of metals is also preferably adjusted within the range of 0.02 to 2.56, preferably 0.04 to 0.62. Therefore, the content of the copper ion source contained in the phosphate solution is appropriately adjusted so that the weight ratio range can be achieved.

Additives such as sources of metals nobler than iron, such as tin, lead, silver, and gold, are added to the phosphate solution in conjunction with or in place of the copper ion sources described above. good too.
In addition, a resin-based additive may be used together with the metal (metal ion) supply source such as copper, or instead of the metal (metal ion) supply source. That is, fluorine-based resins (such as polytetrafluoroethylene) and polyolefin-based resins (such as polyethylene) that can be dispersed in a solution that is mainly an aqueous solution can also be used.

In the phosphate coating, the weight ratio of the total of the additive-derived components derived from the above-described copper ion source and the like used as an additive to the phosphate-derived metal such as manganese is also preferably 0. It is preferably adjusted within the range of 0.02 to 2.56, more preferably 0.04 to 0.62. Therefore, the total content of the additives contained in the phosphate solution is also appropriately adjusted so that the range of the weight ratio in the phosphate coating can be achieved.

1-3. Properties and Configuration of Copper-Containing Manganese Phosphate Coating (Phosphate Coating) The thickness of the phosphate coating such as the manganese phosphate coating is appropriately adjusted depending on the use of the sliding member, and is, for example, 1 μm to 25 μm. Below is. The thickness of the phosphate coating is preferably 2 μm or more and 20 μm or less, more preferably 3 μm or more and 15 μm or less, and particularly preferably 4 μm or more and 10 μm or less.

In addition, in a phosphate coating such as a manganese phosphate coating, the wear depth is preferably 50 μm or less, preferably 40 μm or less, and 30 μm or less in a sliding performance test described later in detail. is more preferable, and 25 μm or less is particularly preferable.

1-4. Secondary Coating A baked coating containing a solid lubricant may be formed on the phosphate coating such as the manganese phosphate coating. For example, it is a fired film containing an organic binder, a curing agent, a solid lubricant, and the like. However, in order to form a sintered film containing a solid lubricant, a sintering process is required to heat the material such as the sintered film, and depending on the sintering process, carbon dioxide, which is a greenhouse gas, is also emitted. . Therefore, if only a phosphate film containing a predetermined component such as copper is provided by a simple method as described above, it is possible to improve the efficiency of the manufacturing process and reduce the generation of greenhouse gases.

[2. Manufacturing Method of Sliding Member]
Both the first and second sliding parts can be manufactured based on known techniques.
In the first sliding part, the value of the surface roughness Ra of the first sliding surface is measured by a method described in detail below in order to confirm whether the surface roughness Ra of the first sliding surface is adjusted within a predetermined range. is preferred. Then, when the value of the surface roughness Ra is out of the predetermined range, the surface roughness is adjusted by a known method such as lathe turning.
Also, on the second sliding component, a phosphate coating is formed, for example, by the method described above.

[3. Application of Sliding Member]
The combined sliding member described above is used in various applications, and can be widely used particularly in members made of a combination of aluminum and steel materials.
For example, the parts in which the first sliding part containing aluminum or aluminum alloy/second sliding part containing steel material can be used include valves/valve bodies, rocker arms/rocker shafts, pistons/piston rings, pistons/pistons, Pins, pistons/cylinders, housings/bearings (eg, rolling bearings, slide bearings, etc.), electric steering columns (case housings (aluminum)/pipes (eg, steel tubes for mechanical structures (STKM), etc.)).

[4. Application example of sliding member (rolling bearing)]
A preferred combination of the above-described first sliding component/second sliding component, that is, a preferred form of the combined sliding member includes a housing and a bearing, such as a housing and a rolling bearing.
An example of a combined housing and bearing sliding member is shown schematically in the partial cross-sectional view of FIG. In FIG. 3 the combined sliding member comprising the rolling bearing 1 and the housing 5 is installed in a rotating device with a rotating member 7 . The rolling bearing 1 is preferably made of a steel material such as SUJ material such as SUJ2, SCr material, SCM material, or SNCM material, and the housing 5 is preferably made of an aluminum alloy. A rolling bearing 1 includes an outer ring 2 , an inner ring 3 , and a plurality of rolling elements (balls) 4 interposed between the outer ring 2 and the inner ring 3 . The rolling bearing 1 holds a rotating shaft member 7 that rotates around a rotating shaft 7a.

In the rolling bearing 1, one of the outer ring 2 and the inner ring 3 is a rotating ring, and the other is a stationary ring. A manganese phosphate coating 2a containing copper is formed on the surface of the fixed ring, for example, the outer ring 2, which contacts the housing 5. As shown in FIG. As illustrated in FIG. 3, the coating may be provided only on the top surface of the outer diameter surface, which is the surface of the outer ring 2, which is the fixed ring, and which is the surface on the housing side. In addition, of the outer diameter surface of the outer ring 2, the side surface in contact with the housing 5 (in FIG. 3, the surface on the lower left of the top surface where the coating 2a is provided) may be provided with the coating. The coating may be provided, and preferably, the coating is provided on the entire region of the sliding surface of the outer diameter surface of the outer ring 2 that slides against the housing 5 .

Unlike the inner ring rotating type bearing shown in FIG. 3, the outer ring rotating type bearing may be provided with a copper-containing manganese phosphate coating. In a rotating outer ring type bearing, it is preferable that a copper-containing manganese phosphate coating is formed on at least a portion of the inner diameter surface of the inner ring. When the coating is provided on the inner ring side, the manganese phosphate coating may be provided only on a partial region of the sliding surface of the inner diameter surface of the inner ring that slides against the housing. It is preferable that the coating is provided over the entire area of the surface.
In the housing 5 , the surface roughness Ra is adjusted to 2.9 μm or less in the region in contact with the fixed ring such as the outer ring 2 .
The combination sliding member on which the manganese phosphate coating is formed also includes rolling bearings other than the ball bearings, such as roller bearings. Examples of sliding members provided with a manganese phosphate coating include thrust ball bearings, angular contact ball bearings, deep groove ball bearings, self-aligning ball bearings, cylindrical roller bearings, tapered roller bearings, needle roller bearings, and self-aligning roller bearings. , thrust cylindrical roller bearings, thrust tapered roller bearings, thrust needle roller bearings, thrust self-aligning roller bearings, etc., and other bearings may be coated with manganese phosphate.
Also, the rolling bearing as a combined sliding member is suitably used as, for example, vehicle transmissions, bearings for various motors, and the like.

Examples will be described below, but the present invention is not limited to each example.

(Preparation of solution for forming phosphate coating)
A treatment solution for a copper-containing manganese phosphate coating was prepared by the method described below. That is, a manganese phosphate-based treatment agent (PF-M5: manufactured by Nihon Parkerizing Co., Ltd.) and copper (II) nitrate were blended so as to obtain each coating component of Examples 1 to 7 and Comparative Example 3 in Table 1 below. An aqueous solution was obtained by appropriately adjusting the ratio and mixing them. That is, a copper-added manganese phosphate treatment liquid was prepared for forming a manganese phosphate film on the surface of the steel material in the combined sliding member.

(Example 1)
On the outer peripheral surface of a ring-shaped SUJ2 steel material (second sliding part; surface hardness is HRC60; outer diameter φ = 35 mm), pretreatment such as cleaning and degreasing is performed, and the copper-added material prepared as described above is applied. A ring-shaped steel material having a copper-containing manganese phosphate film was obtained by immersing it in the manganese phosphate treatment solution under conditions of a treatment temperature of 90° C. and a treatment time of 10 minutes.

(Examples 2 to 7, Comparative Example 3)
A copper-added manganese phosphate treatment solution having a composition different from that of Example 1 was used so that the film components described in the columns of Examples 2 to 7 and Comparative Example 3 in Table 1 below were obtained. A ring-shaped steel material having a copper-containing manganese phosphate coating was obtained in the same manner as in 1.

(Comparative Examples 1 and 2 and Reference Example)
In Comparative Example 1, only the ring-shaped steel material made of the same SUJ2 as in Example 1 was used for the evaluation test without forming the manganese phosphate coating.
In Comparative Example 2, a manganese phosphate treatment solution containing no copper (II) nitrate was immersed at a treatment temperature of 85 to 90° C. for a treatment time of 10 minutes, and copper was added in the same manner as in Example 1. A ring-shaped steel material having a manganese phosphate coating was obtained.
In Reference Example, a ring-shaped steel material was obtained in which a polymer resin layer containing molybdenum disulfide and graphite as solid lubricants was formed after forming a copper-free manganese phosphate coating.

(Comparative Example 4)
In Comparative Example 4, a ring-shaped steel material was obtained in which a copper plating film was formed by electrolytic copper plating instead of the manganese phosphate treatment film.

As a block material of aluminum alloy ADC12 (first sliding part; Knoop hardness (HK) = 123.9) that slides on the outer peripheral surface of the above-mentioned various ring-shaped steel materials, the block material that contacts the outer peripheral surface of the ring-shaped steel material As shown in Table 1 below, samples having a surface roughness of 0.4 μm, 1.6 μm, 2.0 μm or 3.0 μm were prepared.

(Measurement of film thickness)
The film thicknesses of various coatings of each example, comparative example and reference example were measured as follows. A steel sample having a film formed on its surface was cut perpendicularly to the film, the cut sample was embedded in resin, hardened, and scraped with abrasive paper to expose the cross section of the film. The sample whose cross section was mirror-finished in this way was observed under an enlarged scanning electron microscope to measure the film thickness. Observation conditions of the scanning electron microscope are shown below.
SEM magnification observation measurement conditions Tester: Electron microscope JSM-6510LA manufactured by JEOL Ltd.
Accelerating voltage: 15 kV
Detected electrons: Reflected electrons Observation magnification: 2000 times

　Film thickness was measured by magnified observation of a scanning electron microscope as follows. The distance between two points facing each other on the coating in the enlarged observation image, that is, the two points on the virtual line perpendicular to the coating surface is measured at five points included in one field of view, and the average value of the distance values was calculated and used as the film thickness value of the coating (see FIG. 1). That is, as shown in FIG. 1, a sample in which a copper-containing manganese phosphate coating 12 is formed on the surface of a steel material 10 is embedded in an embedding resin 22, and then the cross section of the exposed sample is observed. The film thickness of the coating 12 was measured.

(Measurement of Ra value)
The values of the surface roughness Ra of the sliding surfaces of the blocks of each example, comparative example and reference example were measured under the following conditions.
Measuring instrument: Surfcom 1400G-12 manufactured by Tokyo Seimitsu Co., Ltd.
Stylus: Conical shape 60°C and tip diameter 2 μm
Standard: JIS B0601:2001
Measurement type: Roughness measurement Evaluation length: 4.000 mm
Standard length: 0.8mm
λs filter: Yes λs cutoff wavelength: 2.5 μm
Cutoff type: Gaussian Cutoff wavelength (λc): 0.8 mm
Shape removal: least-squares straight line

(Measurement of Cu and Mn content in coating (sliding surface))
The amount of Mn and Cu in each coating was measured by fluorescent X-ray measurement for various coatings of each example and comparative example. The conditions for the fluorescent X-ray measurement are as follows.
Testing machine: Fluorescent X-ray analyzer RIX2100 manufactured by Rigaku Corporation
Measurement conditions: voltage value 50 kV
Current value 50mA
Measurement diameter φ10mm

The content of Cu and Mn in the film was measured by fluorescent X-ray under the above conditions as follows. A calibration curve is prepared in advance from the X-ray intensity of each component in the coating of each component and the coating analysis results by ICP-AES by wet peeling, and each example and comparative example that is an unknown sample is based on the created calibration curve. Quantitative analysis of each component in the coating was performed. Table 1 shows the amount of Mn (g/m ² ), the amount of Cu (g/m ² ), and the content ratio of Cu/Mn in the film thus confirmed.
In addition, the method for measuring the content of Cu and Mn in the coating is not limited to the above-described measurement method using fluorescent X-rays, and the content of each component of Cu and Mn may be measured by other methods. . For example, the content of each component in the film may be measured using a technique such as atomic absorption spectrometry (AAS) by wet peeling or ICP emission spectrometry (ICP-AES).

(Sliding performance test (wear resistance: LFW-1 test))
In order to evaluate the wear resistance of each example, comparative example and reference example, LFW-1 test was conducted. In the LFW-1 test, an aluminum block whose surface roughness Ra was previously confirmed was placed on the surface of the steel rings of each example and comparative example on which various coatings were formed except for Comparative Example 1. , the steel ring was rotated while applying a load from above the aluminum block (see Fig. 2).
The conditions for the LFW-1 test are as follows.
Tester Falex block-on-ring friction wear tester (LFW-1)
Rotation speed 100rpm
Load 112-787LBS (Increase by 112.4LBS per step)
Test time 1 step/min x 7 steps Lubrication environment Nissan genuine CVTF NS-3

(Measurement of wear amount (Results of LFW-1 test))
As a result of the LFW-1 test of each example, comparative example and reference example, the wear amount of the aluminum block as a test piece was measured under the following conditions.
Testing machine: SURFCOM 1400G manufactured by Tokyo Seimitsu Co., Ltd.
Calculation standard: JIS-B 0601-2001 standard Measurement conditions: Measurement type Cross-section measurement Measurement speed 0.3 mm/s
Measurement length 10.0mm
Stylus shape φ1.6 ruby Shape removal Least square straight line

The results of the measured wear amount are shown in the aluminum block wear amount column of Table 1 above. In Table 1, the amount of aluminum wear was evaluated as good when 0 to less than 40 μm, somewhat poor when 40 μm or more and less than 100 μm, and poor when 100 μm or more.
Further, as is clear from Table 1 showing the results of Examples 3, 6, 7, Comparative Example 3, etc., in which only the value of the surface roughness Ra on the sliding surface of the aluminum block is different, the sliding It was also confirmed that the amount of wear was remarkably low when the surface roughness Ra of the surface was in the range of 0.4 to 2.0 μm (see Table 1).

From the above results, a copper-containing manganese phosphate coating having a Mn content of 2.1 g/m ² or more and a Cu/Mn ratio of 0.04 to 0.62 was formed on the sliding surface of the steel ring. In each example in which the value of surface roughness Ra on the sliding surface of the aluminum block is in the range of 0.4 to 2.0 μm, the amount of aluminum block wear in the LFW-1 test is suppressed. was confirmed (see Table 1).
In addition, in each example, it can be said that an excellent abrasion resistance effect was recognized only by the film formed by a simple method without a complicated process such as the baking process for forming the baked film in the reference example (Table 1). 1).

(Example 8)
A ring-shaped SCM415 steel material (second sliding part; surface hardness is HRC60; outer diameter φ = 35 mm) was prepared using the copper-containing manganese phosphate coating treatment liquid prepared by the method of Example 1 above. A copper-containing manganese phosphate coating was formed on the outer peripheral surface of the. The method of forming the film is the same as in Example 1, and the ring-shaped SCM415 steel material is subjected to pretreatment such as cleaning and degreasing, and the manganese phosphate treatment solution prepared as described above is applied at a treatment temperature of 90 ° C. It was immersed under the condition that the treatment time was 10 minutes.

(Examples 9 to 12, Comparative Examples 5 and 6)
A copper-added manganese phosphate treatment solution having a composition different from that of Example 8 was used so as to obtain the film components described in the columns of Examples 9 to 12, Comparative Examples 5 and 6 in Table 2 below. Otherwise, in the same manner as in Example 8, a ring-shaped steel material having a copper-containing manganese phosphate coating was obtained.

As a block material (first sliding part; Knoop hardness (HK) = 123.9) of aluminum alloy ADC12 to be slid on the outer peripheral surface of each of the ring-shaped steel materials of Examples 8 to 12 and Comparative Examples 5 and 6, As shown in Table 1 below, block materials having a surface roughness of 0.4 μm, 2.0 μm or 3.0 μm in contact with the outer peripheral surface of the ring-shaped steel material were prepared.

Examples 8 to 12 and Comparative Examples 5 and 6 were evaluated in the same manner as in Examples 1 to 7, Comparative Examples 1 to 4, and Reference Example. That is, for Examples 8 to 12 and Comparative Examples 5 and 6, the film thickness was measured, the Ra value of the aluminum block material was measured, the Cu and Mn contents in the film (sliding surface) were measured, and the sliding surface was measured. A dynamic performance test (wear resistance: LFW-1 test) and an amount of wear of the aluminum block (result of LFW-1 test) were measured. Table 2 shows the results.

From the results in Table 2, the amount of aluminum block wear was suppressed even by the copper-containing manganese phosphate coating, which was adjusted to a range wider than the ranges of the Mn amount and the Cu/Mn ratio in the examples shown in Table 1. (See Table 2). If coatings based on these embodiments are formed on, for example, rolling bearings and other bearings, wear of the housing due to occurrence of creep can be prevented.
In addition, as in the examples shown in Table 1, also in the examples in Table 2, an excellent abrasion resistance effect was observed only by the film formed by a simple method without a complicated process such as a baking process ( See Table 2).

Reference Signs List 1 rolling bearing 2 outer ring 2a coating (copper-containing manganese phosphate coating)
3 inner ring 4 balls (rolling elements)
5 housing 7 rotary shaft member 7a rotary shaft 10 steel material 12 coating (copper-containing manganese phosphate coating)
22 embedded resin 30 steel material ring 40 aluminum block

Claims

A combined sliding member comprising a first sliding component made of aluminum or an aluminum alloy and a second sliding component made of steel,
A surface of the second sliding part that slides against the first sliding part has a copper-containing manganese phosphate coating, and the manganese phosphate coating contains 1.5 g/m 2 of manganese. above, the copper/manganese content ratio is 0.02 to 2.56,
A combination sliding member, wherein a surface roughness Ra of a surface of the first sliding part that slides on the second sliding part is 2.9 μm or less.
Valve/valve body, rocker arm/rocker shaft, piston/piston ring, piston/piston pin, piston/cylinder, housing/bearing and electric steering column/pipe as the first sliding part/second sliding part 2. A combination slide member according to claim 1, which is either
The combined sliding member according to claim 2, wherein said first sliding component is a housing and said second sliding component is a rolling bearing.
the rolling bearing as the second sliding component,
An outer ring, an inner ring, and a plurality of rolling elements arranged to be rollable between the outer ring and the inner ring,
4. The combination slide according to claim 3, wherein at least one of the outer diameter surface of said outer ring and the inner diameter surface of said inner ring, which surface slides on the housing as said first sliding component, has said manganese phosphate coating. moving parts.
A combined sliding member comprising a first sliding component made of aluminum or an aluminum alloy and a second sliding component made of steel,
A surface of the second sliding part that slides on the first sliding part has a copper-containing manganese phosphate coating, and the manganese phosphate coating has a manganese content of 2.1 g/m 2 . above, the copper/manganese content ratio is 0.04 to 0.62,
A combination sliding member, wherein a surface roughness Ra of a surface of the first sliding part that slides on the second sliding part is 2.9 μm or less.
The combined sliding member according to claim 5, wherein the second sliding component is an SUJ material defined by JIS G4805:2008.
The combined sliding member according to claim 1 or 5, wherein the manganese phosphate coating has a thickness of 1 to 25 µm.