JP7082337B2 - Abrasion resistant film and its forming method, and wear resistant member - Google Patents

Description

The present invention relates to a wear-resistant film, a method for forming the film, and a wear-resistant member.

Conventionally, it has been required to impart excellent wear resistance to various mechanical parts, tools, molds and other members, and various techniques have been studied. In particular, in recent years, for example, by forming a film having excellent wear resistance on the surface of a member by a method such as plating, for example, the wear resistance of various members against slipping has been improved.

For example, Patent Document 1 discloses a technique for preventing wear due to slipping by providing unevenness on the surface of a pulley with which a belt comes into contact in a pulley for a stepless transmission and a belt-type unauthorized transmission. Further, Patent Document 1 also discloses that the unevenness is plated, thereby attempting to improve wear resistance against slippage.

Patent Document 2 discloses a technique for forming a microporous or microcracked chrome plating film on a receiving surface of a shaft in a rolling bearing. Such a chrome-plated film can retain the self-lubricating resin by the microporous or microcracks present on its surface, which makes the shaft slippery on the bearing surface and enhances wear resistance to slippage. There is.

Japanese Unexamined Patent Publication No. 2012-117579 Japanese Unexamined Patent Publication No. 2016-180439

However, although the conventional wear-resistant film can certainly improve the wear resistance against slipping of various members, the film may be scraped or deteriorated if the wear is repeated for a long period of time. The problem was that the phenomenon gradually progressed, causing a decrease in wear resistance. For example, as in the technique disclosed in Patent Document 1, only by providing unevenness on the surface of the base material, the wear resistance against slipping gradually decreases, and the plating film formed on the unevenness gradually peels off, so that the wear resistance Is easily damaged over time. Further, even in the method of Patent Document 2, since the self-lubricating resin held in the microcracks or the like is eventually peeled off and disappears, it is difficult to maintain the wear resistance against slipping for a long period of time. Further, in the techniques disclosed in Patent Documents 1 and 2, the adhesion between the plating film and the base material and the adhesion between the self-lubricating resin and the surface of the base material are poor due to repeated slip wear for a long period of time. It was a factor that made it easier for the film to peel off.

In recent years, regarding the wear resistance of various members, there has been a demand for a wear-resistant film that can maintain excellent wear resistance for a long period of time even if wear is repeated. However, the conventional technique has a problem in maintaining wear resistance. There was a need for further improvement.

INDUSTRIAL APPLICABILITY The present invention has been made in view of the above. It is an object of the present invention to provide a wear resistant member.

As a result of diligent research to achieve the above object, the present inventor has found that the above object can be achieved by forming the film into a specific layer structure, and has completed the present invention.

That is, the present invention includes, for example, the inventions described in the following sections.
Item 1. It has a plating layer and a lubricating layer laminated on the plating layer.
The lubricating layer is a wear-resistant film containing a solid lubricant.
Item 2. Item 2. The wear-resistant film according to Item 1, wherein a plurality of holes are formed in the plating layer.
Item 3. Item 2. The wear-resistant film according to Item 2, wherein a part or all of the solid lubricant has entered the inside of the hole.
Item 4. Item 2. The wear resistance according to any one of Items 1 to 3, wherein the solid lubricant is at least one selected from the group consisting of graphite, molybdenum disulfide, boron nitride, tungsten disulfide, lead oxide and fluororesin. Sex film.
Item 5. The wear-resistant film according to any one of Items 1 to 4 and the base material are provided.
The base material is coated with the wear-resistant film, and the base material is coated with the wear-resistant film.
A wear-resistant member in which the surface of the wear-resistant film on the plating layer side is fixed to the base material.
Item 6. Item 5. The wear-resistant member according to Item 5, wherein the surface of the base material covered with the wear-resistant film has irregularities.
Item 7. With a wear-resistant film and a base material,
The base material is coated with the wear-resistant film, and the base material is coated with the wear-resistant film.
The wear resistant film comprises a plating layer containing molybdenum disulfide and has a plating layer.
A wear-resistant member having irregularities formed on the surface of the base material covered with the wear-resistant film.
Item 8. The first step of forming a plating layer by plating the surface of the base material, and
The second step of forming a lubricating layer containing a solid lubricant on the surface of the plating layer, and
A method for forming a wear-resistant film including.
Item 9. The plating process of the first step further includes a step of forming a plating layer containing resin particles by using a plating solution containing resin particles and burning the resin particles by heat-treating the plating layer. Item 8. The forming method according to Item 8.
Item 10. Item 8. The forming method according to Item 8 or 9, further comprising a step of forming irregularities on the surface of the base material before performing the plating treatment.

The wear-resistant film according to the present invention can maintain excellent wear resistance for a long period of time even if wear against slipping is repeated, and also has excellent adhesion to a substrate, so that wear resistance can be maintained. Excellent.

The wear-resistant member according to the present invention has excellent wear resistance for a long period of time by providing the wear-resistant film, and also has high adhesion between the base material and the wear-resistant film. Excellent wear resistance.

According to the method for forming a wear-resistant film according to the present invention, it is a method suitable as a method for manufacturing the wear-resistant film and the wear-resistant member. In particular, the wear-resistant film produced by the method for forming the wear-resistant film according to the present invention can maintain excellent wear resistance for a long period of time because the solid lubricant is easily held by the plating layer. can.

It is an example of an embodiment of the wear-resistant film of the present invention, and is a schematic cross-sectional view showing a state of being coated on a base material. It is an example of another embodiment of the wear-resistant film of the present invention, and is a schematic cross-sectional view showing a state of being coated on a base material. It is a schematic cross-sectional view which shows the method of forming the wear-resistant film of this invention on a base material. It is a schematic cross-sectional view which shows the other method of forming the wear-resistant film of this invention on a substrate. It is a graph which shows the wear test result of an Example and a comparative example.

Hereinafter, embodiments of the present invention will be described in detail.

1. 1. Abrasion resistant film FIG. 1 is a schematic cross-sectional view showing a state in which the wear resistant film of the present invention is coated on a base material.

The wear-resistant film 10 of the present invention has a plating layer 11 and a lubricating layer 12 laminated on the plating layer 11, and the lubricating layer 12 contains a solid lubricant 2.

In the embodiment of FIG. 1, the wear-resistant film 10 is coated on the surface of the base material 20. The surface of the wear-resistant film 10 on the plating layer 11 side (the surface opposite to the lubricating layer 12) is fixed to the surface of the base material 20. That is, in the embodiment of FIG. 1, the base material 20, the plating layer 11, and the lubricating layer 12 are laminated in this order. As a result, the wear resistant member 30 is formed.

The plating layer 11 is a layer formed by the plating treatment. The plating layer 11 is a layer formed by, for example, electrolytic plating, electroless plating, or the like.

The plating layer 11 is a layer capable of holding the solid lubricant 2 contained in the lubricating layer 12 in the wear-resistant film 10. When the surface of the plating layer 11 has irregularities as described later, it becomes easy to hold the solid lubricant 2. Further, by coating the plating layer 11 having a friction coefficient lower than that of the base material 20 (for example, iron (S45C)), the holding power of the solid lubricant 2 can be enhanced.

Examples of the plating layer 11 include plating layers of various metals. The metal forming the plating layer 11 is not particularly limited. Specific examples of the metal include nickel, copper, chromium, zinc, tin, palladium, lead, silver, gold and the like.

The metal forming the plating layer 11 may be only one type or two or more types. Further, the metal forming the plating layer 11 may be an alloy. Alternatively, the metal forming the plating layer 11 may be an oxide, a nitride, a sulfide, or the like. Further, the plating layer 11 may have other elements (for example, non-metal elements such as phosphorus and boron) as constituent elements in addition to or in place of the metal.

The plating layer 11 is based on other metal plating such as Ni, for example, fluororesin (PTFE), mica, alumina (Al ₂ O ₃ ), boron nitride (BN), silicon carbide (SiC), molybdenum disulfide (SiC), and molybdenum disulfide (PTFE). It may be a composite plating in which MoS ₂ ), tungsten disulfide (WS ₂ ), silicon dioxide (SiO ₂ ) and the like are combined.

Examples of the plating layer 11 include an electroless nickel plating layer (electroless nickel plating layer) formed by an electroless plating treatment and an electroless Ni-P composite plating layer. When the plating layer 11 is an electroless Ni-P composite plating layer, the hardness and corrosion resistance of the plating layer 11 can be improved by the effect of the eutectoided P. Further, when the plating layer 11 is an electroless Ni-P composite plating layer, there is an advantage that the plating layer 11 having a shape conforming to the shape of the base material can be easily obtained.

The method for forming the plating layer 11 is not particularly limited, and for example, the plating layer 11 can be formed by various known plating treatment methods. Hereinafter, the process for forming the plating layer 11 is referred to as “first plating process”.

As the first plating treatment, for example, electroplating, electroless plating, hot-dip plating, vapor phase plating and the like can be performed. The plating process can be adopted by either a continuous method or a batch method. A known plating solution can be used as the plating solution used in the first plating treatment, and for example, a plating solution containing various metals containing a metal forming the plating layer 11 can be used.

In electrolytic plating, nickel (Ni), copper (Cu), chromium (Cr), zinc (Zn), tin (Sn), palladium (Pd), lead (Pb), silver (Ag), gold (Au), etc. A plating solution containing one or more kinds of metals can be used.

In electroless plating, a plating solution containing Ni-P, Ni-B, Ni-Co, Cu, Ag and the like can be used. In composite plating, fluororesin (PTFE), mica, alumina (Al ₂ O ₃ ), boron nitride (BN), silicon carbide (SiC), molybdenum disulfide (MoS ₂ ), and tungsten disulfide (WS 2) are based on Ni plating. ₂ ) A plating solution containing one or more of silicon dioxide (SiO ₂ ) and the like can be used.

The thickness of the plating layer 11 is not particularly limited. For example, the thickness of the plating layer 11 can be appropriately set, and is preferably 5 μm or more, more preferably 5 to 20 μm, for example.

The surface of the plating layer 11 can be formed flat. Alternatively, the surface of the plating layer 11 is not flat and can be formed so as to have irregularities, for example. When the surface of the plating layer 11 has irregularities, the degree of irregularities is not particularly limited as long as the lubricating layer 12 can be laminated on the surface. For example, the unevenness can be formed so that the maximum roughness Rz of the surface of the plating layer 11 is larger than the primary average particle diameter of the lubricating particles described later. In this case, the plating layer 11 can easily hold the lubricating particles contained in the lubricating layer 12, the wear-resistant film 10 has excellent wear resistance, and the effect is easily maintained. The maximum roughness Rz (μm) referred to in the present specification is defined by JIS B 0601: 2001.

More specifically, the maximum roughness (Rz) of the unevenness on the surface of the plating layer 11 can be about 2 to 5 times the average primary particle diameter of the lubricating particles, for example, 0.01 to 100 μm, 0.1. It can be ~ 300 μm, more preferably 0.25 to 4 μm, and particularly preferably 0.5 to 2 μm. The unevenness is preferably formed on at least the entire surface of the plating layer 11 covered with the lubricating layer 12, and is also preferably formed on the entire surface of the plating layer 11.

The lubricating layer 12 is a layer formed so as to cover the surface of the plating layer 11 in the wear-resistant film 10. The lubricating layer 12 is located on the outermost surface of the wear-resistant film 10, and is a layer capable of imparting wear resistance to the base material 20 and the like.

The lubricating layer 12 is a layer containing the solid lubricant 2 as an essential component. The lubricating layer 12 may be a layer formed only of the solid lubricant 2. Alternatively, the lubricating layer 12 may contain a material other than the solid lubricant 2. The lubricating layer 12 preferably contains 50% by mass or more of the solid lubricant 2 with respect to the total mass thereof.

The solid lubricant 2 can be formed of a material capable of exhibiting wear resistance, and for example, known wear resistant materials and lubricating materials can be used.

Examples of the solid lubricant 2 include graphite (C), molybdenum disulfide (MoS ₂ ), boron nitride (BN), tungsten disulfide (WS ₂ ), lead oxide (PbO), and a resin.

Examples of the resin include a fluororesin. Examples of the fluororesin include polytetrafluoroethylene (PTFE), tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer, tetrafluoroethylene-hexafluoropropylene copolymer, polychlorotrifluoroethylene and tetrafluoroethylene-ethylene copolymer weight. Coalescence etc. can be mentioned.

The solid lubricant 2 is preferably formed in the form of particles. In the present specification, the solid lubricant 2 formed in the form of particles is particularly referred to as “lubricating particles”. When the solid lubricant 2 is a lubricating particle, the adhesive force of the solid lubricant 2 on the plating layer 11 is increased, so that the adhesion of the lubricating layer 12 is improved. Further, when the hole described later is formed in the plating layer 11, the lubricating particles are likely to enter into the hole.

The average primary particle size of the lubricating particles is not particularly limited. It is preferable that the diameter is smaller than the diameter of the holes described later, and the particles are formed on the surface of the plating layer 11 from the viewpoint that they can easily enter the holes described later and that a plurality of lubricating particles can easily enter one hole. It is preferable that the unevenness to be formed is smaller than the Rz. Further, the lubricating particles are preferably smaller than the average primary particle diameter of the resin particles described later. For example, the average primary particle size of the lubricating particles can be 0.5 to 2 μm. The average primary particle diameter of the lubricating particles is a value measured by a particle size distribution measuring instrument by a dynamic light scattering method.

The lubricating particles can have various shapes such as spherical, elliptical, and flat.

It is particularly preferable that the lubricating particles are molybdenum disulfide particles. Since molybdenum disulfide has a layered crystal structure with good slipperiness and is a particle having excellent load resistance, the wear resistant film 10 to be formed has excellent wear resistance and the wear resistant member has. It is easy to improve the sustainability of the wear resistance effect, and it is easy to adhere to the surface of the plating layer 11 and also to easily enter the holes. From this point of view, the lubricating layer 12 is preferably formed only of molybdenum disulfide particles.

The lubricating layer 12 can cover the entire surface or a part of the plating layer 11. For example, the lubricating layer 12 preferably covers 50% or more of the surface of the plating layer 11, and preferably covers 100% (that is, the entire surface).

The thickness of the lubricating layer 12 is not particularly limited. For example, the thickness of the lubricating layer 12 can be 1 to 30 μm.

The method for forming the lubricating layer 12 is not particularly limited. The method of forming the lubricating layer 12 will be referred to as "lubricating layer forming means" below.

Examples of the lubricating layer forming means include known means such as shot blasting, barreling, painting, coating, and imprinting using a raw material containing the solid lubricant 2. The raw material containing the solid lubricant 2 used in the lubricating layer forming means may be composed of only the solid lubricant 2. Note that shot blasting here means accelerating particles to collide with an object, and does not necessarily mean using a shot blasting device or the like.

The lubricating layer 12 may be formed so that its surface has irregularities. Alternatively, the lubricating layer 12 can be formed so that its surface is flat. Even if the surface of the lubricating layer 12 has irregularities, it can be gradually flattened by the addition of wear. That is, as the wear-resistant film 10 continues to be used, the surface of the lubricating layer 12 is eventually flattened. When flattened, the compatibility of the lubricating layer 12 can be improved.

FIG. 2 is a schematic cross-sectional view showing a state in which a wear-resistant film of another embodiment of the present invention is coated on a base material.

The wear-resistant film 10 in the form of FIG. 2 has a plating layer 11 and a lubricating layer 12 laminated on the plating layer 11, and the lubricating layer 12 contains a solid lubricant 2. It is the same as the embodiment of.

In the wear-resistant film 10 of the form shown in FIG. 2, a plurality of holes 15 are formed in the plating layer 11. In other words, the plating layer 11 has a porous shape. This point is different from the wear-resistant film 10 of the embodiment of FIG. In the embodiment of FIG. 2, the same configuration as that of the embodiment of FIG. 1 can be adopted except that a plurality of holes 15 are formed in the plating layer 11.

When a plurality of holes 15 are formed in the plating layer 11 as in the embodiment of FIG. 2, the solid lubricant 2 contained in the lubricating layer 12 can enter the holes 15 and is plated with the lubricating layer 12. The adhesion of the layer 11 is improved. Further, even if the lubricating layer 12 existing on the surface is peeled off due to the solid lubricant 2 contained in the lubricating layer 12 entering the holes 15, the solid lubricant 2 entering the holes 15 will be removed from the plating layer 11. Is hard to fall off. As a result, the wear resistance of the wear resistant film 10 can be maintained for a longer period of time. When the solid lubricant 2 is a lubricating particle, it is easily held in the hole 15, so that the wear-resistant effect of the wear-resistant film 10 is particularly likely to be maintained.

It is preferable that the plurality of holes 15 formed in the plating layer 11 are distributed and exist over the entire region of the plating layer 11. That is, it is preferable that the plurality of holes 15 are formed not only on the surface layer of the plating layer 11 but also on the inside of the plating layer 11. In this case, even if the surface of the plating layer 11 is scraped by wear, an internal hole 15 appears from the scraped portion, and the solid lubricant 2 remaining on the surface can enter the hole 15. As a result, the solid lubricant 2 can continue to maintain the wear resistance, and the effect of the wear resistance can be maintained for a longer period of time.

The content ratio of the pores in the plating layer 11 is not particularly limited. For example, the pores are preferably present in the plating layer 11 in a proportion of 30 to 70% by volume. The volume ratio of the pores existing in the plating layer 11 can be obtained by measuring the volume ratio of the resin particles contained in the plating layer 11 in the second forming method described later. In the second forming method, the volume ratio of the resin particles contained in the plating layer 11 is calculated, for example, by dissolving the plating layer 11 in a solvent and taking out only the resin particles, and calculating the volume from the weight of the obtained resin particles. It can be measured with.

The size of the hole 15 is preferably formed to a size that allows the solid lubricant 2 to enter. In particular, when the solid lubricant 2 is the lubricating particles, it is preferable that the pores 15 have a diameter of twice or more the average primary particle diameter of the lubricating particles. The diameter of the holes 15 here means that the surface or cross section of the plating layer 11 is observed by direct observation with a transmission electron microscope, 50 holes 15 are randomly selected, and the diameters corresponding to these circles are measured. Arithmetic mean value.

In the embodiment of FIG. 2, it is preferable that a part or all of the solid lubricant 2 contained in the lubricating layer 12 penetrates into the hole 15 formed in the plating layer 11. In this case, the solid lubricant 2 is less likely to fall off due to wear, and the effect of wear resistance can be maintained for a long period of time. The solid lubricant 2 can enter the hole 15 from the initial state, and may gradually enter the hole 15 due to repeated wear after use.

In particular, it is preferable that a plurality of lubricating particles are contained in one hole 15. In this case, it is easy to prevent the lubricating particles from falling off, and it is also easy to prevent the plating layer 11 from peeling off. However, it is preferable that a space remains inside the hole 15. In this case, even if the wear-resistant film 10 is in a reduced pressure state, there is an advantage that the wear-resistant film 10 is less likely to be peeled off.

The holes 15 may be colored. The colored holes 15 make it possible to visually identify the holes 15.

The holes 15 are preferably formed so as not to penetrate the plating layer 11 in the thickness direction. If the holes 15 are formed without penetrating the plating layer 11 in the thickness direction, the through holes do not reach the base material 20, so that the corrosion resistance of the wear-resistant film due to so-called plating defects (cracks, pinholes) The decrease can be suppressed.

The method for forming the plating layer 1 having the holes 15 is not particularly limited. Hereinafter, the method of forming the plating layer 1 having the pores 15 will be referred to as a “pore forming method”.

Examples of the pore forming method include a method in which resin particles are contained in a plating solution used in the first plating process for forming the plating layer 11, and the plating layer 11 is formed using the resin particles.

The type of the plating solution containing the resin particles is the same as that of the plating solution used in the first forming method, except that the plating solution contains the resin particles.

The plating layer 11 formed from the plating solution containing the resin particles contains the resin particles. By heat-treating the plating layer 11 to burn out the resin particles, holes 15 can be formed in the plating layer 11. The holes 15 can be formed in the portion where the resin particles were present before the heat treatment.

The type of resin particles is not particularly limited. For example, at least one resin particle selected from the group consisting of acrylic resin particles and polyester resin that evaporate at 350 ° C. or higher can be exemplified.

The average primary particle size of the resin particles is not particularly limited. For example, if the solid lubricant 2 is a lubricating particle, it preferably has an average primary particle size of 2 to 5 times the average primary particle size of the lubricating particle.

From another point of view, the average primary particle diameter of the resin particles can be made larger than the maximum roughness Rz of the surface of the plating layer 11. In this case, the lubricating particles are likely to enter the pores 15 formed after the resin particles are burnt down, and the lubricating particles are easily held in the pores 15, so that the wear resistance is likely to be improved.

From yet another viewpoint, the average primary particle diameter of the resin particles can be made equal to or less than the maximum roughness Rz of the surface of the plating layer 11. In this case, unevenness is likely to be present on the surface of the plating layer 11, and particularly when the surface is worn, the unevenness is likely to appear, and the wear resistance is improved. For example, the average primary particle diameter of the resin particles can be 1 μm or more and 10 μm or less.

The plating solution containing the resin particles preferably contains a surfactant. In this case, the dispersibility of the resin particles in the plating solution is improved, and the resin particles are easily dispersed uniformly in the formed plating layer 11. As a result, the holes 15 formed in the plating layer 11 are likely to be uniformly distributed.

The type of surfactant is not particularly limited. For example, known anionic, cationic or nonionic surfactants can be used.

As for the amount of the surfactant used, for example, 0.5 to 2.0% by weight of the surfactant can be used with respect to the resin particles.

The conditions for heat treatment of the plating layer 11 containing the resin particles are not particularly limited. For example, the heating temperature can be 300 to 350 ° C. The heating time can be appropriately changed according to the heating temperature, and can be, for example, 120 to 300 minutes. The heating conditions are not limited, and heating can be performed in various atmospheres such as an atmosphere of an inert gas such as nitrogen and an air atmosphere. The heat treatment can be performed by a commercially available heating furnace or the like.

As another example of the hole forming method, an electrolytic plating method such as a porous nickel plating method can be mentioned. In addition, the holes 15 can also be formed by roughening the surface of the plating layer 11 formed by the first plating treatment by an appropriate method such as shot blasting or etching.

In the embodiment of FIG. 2, other configurations can be the same as those of the embodiment of FIG. 1 except that the holes 15 are formed in the plating layer 11 and the lubricating particles can enter the holes 15.

The wear-resistant film 10 of the present invention can have, for example, the forms shown in FIGS. 1 and 2, and can be suitably used for various members as a film for imparting wear resistance. The wear-resistant member 30 described later can be formed. When various members are covered with the wear-resistant film 10 of the present invention, as shown in FIGS. 1 and 2, the wear-resistant film 10 is coated so that the lubricating layer 12 is located on the surface side.

The wear-resistant film 10 of the present invention is provided with the lubricating layer 12 having excellent wear resistance, so that high wear resistance can be imparted, and the adhesion between the lubricating layer 12 and the plating layer 11 is also good. Even if the wear is repeated, the effect of wear resistance is not easily lost.

In particular, when the holes 15 are formed in the plating layer 11 as in the embodiment of FIG. 2, the solid lubricant 2 contained in the lubricating layer 12 is easily held by the plating layer 11, so that the effect of wear resistance can be improved. Can last for a long time. When the solid lubricant 2 is a lubricating particle, the effect is particularly remarkable.

Since the conventional wear-resistant film peels off as it continues to be worn, the wear-resistant film may gradually lose its wear resistance. However, the wear-resistant film 10 of the present invention is provided with the above-mentioned configuration. The effect of wear resistance can be maintained for a longer period than before.

2. 2. Abrasion-resistant member As shown in FIGS. 1 and 2, the wear-resistant member 30 of the present invention includes a wear-resistant film 10 and a base material 20, and the base material 20 is the wear-resistant film 10. The wear-resistant film 10 is coated, and the surface of the plating layer side 11 is fixed to the base material 20.

The wear-resistant film 10 has the same configuration as described in the section “1. Wear-resistant member” of the present specification.

Various solid materials can be applied to the base material 20, and the type thereof is not particularly limited. For example, various materials such as metal, alloy, resin, ceramics, paper, wood, and cloth can be used as the base material 20.

The shape of the base material 20 is not particularly limited. For example, the shape of the base material 20 may be a substrate shape, a film shape, a rod shape, a block shape, a spherical shape, an elliptical spherical shape, a distorted shape, or the like. Further, the base material 20 may be various sliding parts, machine parts, tools, molds and the like.

It is preferable that the surface of the base material 20 covered with the wear-resistant film 10 has irregularities. In this case, the adhesion between the wear-resistant film 10 and the base material 20 can be particularly improved. As a result, even if the wear is repeated, the wear resistance effect is not easily lost, and the wear resistance effect can be maintained for a longer period of time.

The maximum roughness (Rz) of the unevenness formed on the base material 20 is not particularly limited. For example, the maximum roughness (Rz) of the unevenness formed on the base material 20 can be about 2 to 5 times the average primary particle diameter of the lubricating particles. Specifically, the maximum roughness of the unevenness formed on the base material 20 is preferably 0.25 to 4 μm, more preferably 0.5 to 2 μm. The unevenness is preferably formed on the entire surface of the base material 20 covered with at least the wear-resistant film 10, and is also preferably formed on the entire surface of the base material 20.

The surface of the wear-resistant film 10 on the plating layer side 11 can be directly fixed to the base material 20. Alternatively, another layer may be interposed between the surface of the wear-resistant film 10 on the plating layer side 11 and the base material 20, and the wear-resistant film 10 may be fixed to the base material 20.

By providing the wear-resistant film 10 in the wear-resistant member 30 of the present invention, excellent wear resistance can be maintained for a long period of time even if wear is repeated.

In the wear-resistant member 30, a part or all of the solid lubricant contained in the lubricating layer 12 may enter the inside of the hole 15 formed in the plating layer 11.

As another form of the wear-resistant member according to the present invention, the wear-resistant film and the base material are provided, the base material is coated with the wear-resistant film, and the wear-resistant film contains molybdenum disulfide. It is also possible to mention a form (hereinafter, may be referred to as “third form”) in which an unevenness is formed on a surface provided with a plating layer and covered with a wear-resistant film of a base material.

In the third form, the wear-resistant film does not have a lubricating layer, but is formed only of, for example, a plating layer containing molybdenum disulfide. The solid lubricant is the same as in the embodiment of FIG.

The plating layer of the third form can be formed, for example, by using a plating solution containing molybdenum disulfide in the plating solution used in the first plating treatment. The type of plating solution can be the same as that of the plating solution used in the first plating process, except that the plating solution contains molybdenum disulfide.

Also in the third form, the holes 15 may be formed in the plating layer 11. The holes 15 can be formed by the same method as the above-mentioned hole forming method.

Even in the wear-resistant member 30 of the third form, since the adhesion between the wear-resistant film 10 and the base material 20 is high, the effect of wear resistance is not easily lost even if the wear is repeated, and the wear-resistant effect is not easily lost for a longer period of time. The wear resistance effect can be sustained throughout.

3. 3. Method for Forming Abrasion-Resistant Film The method for forming the wear-resistant film 10 is not particularly limited, and the wear-resistant film 10 can be produced by various methods as long as the above-mentioned configuration is provided. Hereinafter, as an example, a method of forming the wear-resistant film 10 of the form of FIG. 1 on the base material 20 (hereinafter referred to as “first forming method”) and the wear-resistant film 10 of the form of FIG. 2 Will be described on the substrate 20 (hereinafter referred to as “second forming method”).

(First forming method)
The method for forming the wear-resistant film 10 is a first step of forming a plating layer 11 by plating the surface of the base material 20, and forming a lubricating layer 12 containing a solid lubricant 2 on the surface of the plating layer 11. The second step may be included.

FIG. 3 is a schematic explanatory view of the first forming method.

The structure of the base material 20 shown in FIG. 3A is the same as that of the base material 20 described in “2. Abrasion resistant member”.

As shown in FIG. 3B, it is also possible to further include a step of forming irregularities on the surface of the base material 20 before performing the plating treatment in the first step. In this case, the wear-resistant film 10 is formed on the uneven surface formed on the surface of the base material 20, and the wear-resistant member 30 including the base material 20 having the uneven surface can be obtained.

The method for forming irregularities on the surface of the base material 20 is not particularly limited. For example, unevenness can be formed on the surface of the base material 20 by a known means. Specifically, the surface of the base material 20 can be treated with shot blasting, shot peening, etching, or the like to form irregularities on the surface of the base material 20.

As a method for forming irregularities on the surface of the base material 20, it is particularly preferable to use shot blasting. By adopting shot blasting, it is easy to adjust the maximum roughness (Rz) of the surface of the base material 20 to a desired range, and the surface after treatment tends to have a satin finish in which continuous unevenness is deeply formed. The unevenness is preferably formed on the entire surface of the base material 20 covered with at least the wear-resistant film 10, and is also preferably formed on the entire surface of the base material 20.

The plating process in the first step is the same as the first plating process.

When the surface of the base material 20 is uneven in the first step, the surface of the plating layer 11 formed by the first plating treatment may also be uneven. The unevenness formed on the base material 20 can be, for example, the same as the unevenness described in the embodiment of FIG.

By the first step, as shown in FIG. 3C, the plating layer 11 is laminated on the base material 20.

In the second step, the lubricating layer 12 containing the solid lubricant 2 is laminated on the surface of the plating layer 11 formed in the first step.

In the second step, the lubricating layer 12 can be formed by the above-mentioned lubricating layer forming means. As a result, as shown in FIG. 3D, the lubricating layer 12 containing the solid lubricant 2 is laminated on the plating layer 11. When the surface of the plating layer 11 is uneven, the surface of the lubricating layer 12 immediately after formation may also be uneven.

When the lubricating layer 12 is formed of the lubricating particles, the lubricating layer forming means is suitable, and in particular, by adopting a means such as shot blasting, the lubricating particles tend to adhere to the surface of the plating layer 11 by physical action. As a result, the lubricating layer 12 having a large adhesive force can be formed on the plating layer 11. Further, when unevenness is formed on the surface of the base material 20 by using shot blasting in the first step, it is preferable to use shot blasting as a method of laminating the lubricating layer 12.

The wear-resistant film in the form shown in FIG. 1 can be formed on the base material 20 by the forming method including the first step and the second step. According to such a forming method, a wear-resistant film can be easily formed.

(Second forming method)
FIG. 4 is a schematic explanatory view of the second forming method.

The second forming method is that in the first forming method, in the plating treatment of the first step, a plating solution containing resin particles is used to form a plating layer containing resin particles, and the plating layer is heat-treated. Further, a step of burning off the resin particles is provided. In the second forming method in which the resin particles are burnt down by heat treatment and a plurality of pores are formed in the plating layer, the method for forming a plurality of pores in the plating layer is the above-mentioned "pore forming method". It is the same method as.

In FIG. 4, as an example, the resin particles 5 are formed by performing a first plating treatment using a plating solution containing the resin particles to form a plating layer 11 (FIG. 4B), and then heat-treating the plating layer 11 (FIG. 4B). Is shown in a form (FIG. 4 (c)) in which the holes 15 are formed by burning. In FIG. 4, the resin particles 5 correspond to the resin particles.

In the second forming method, the heat treatment can be performed between the first step and the second step as shown in FIG. Alternatively, the heat treatment can be performed after the second step. However, in that the solid lubricant 2 easily enters the pores 15, the heat treatment is performed between the first step and the second step, that is, the resin particles are formed in the first step as shown in FIG. 4 (b). It is preferable to perform heat treatment after forming the plating layer 11 to be contained and before forming the lubricating layer 12.

When the heat treatment is performed before the lubricating layer 12 is formed, the holes 15 may be colored after the heat treatment is performed to form the holes 15. As the coloring method, for example, a known coloring method can be adopted, and a method of applying a known coloring agent such as ink or paint can be exemplified.

In the second forming method, the method of providing unevenness on the base material 20 and the method of forming the lubricating layer 12 are the same as those of the first forming method.

In the second forming method, it is preferable to adopt shot blasting as the method for forming the lubricating layer 12, and in this case, the solid lubricant 2 easily enters the holes 15. Further, according to shot blasting, the lubricating particles are fixed to the plating layer 11 by the action of a physical external force. Therefore, it is easy to insert the lubricating particles into the surface and the holes 15 of the plating layer 11.

In particular, when the diameter of the hole 15 becomes larger toward the inside of the plating layer 11 (when the opening cross section of the hole 15 is larger inside than the surface of the plating layer 11), it is possible to insert the hole 15 by shot blasting. Lubricating particles easily enter the holes 15. As a result, the lubricating particles are less likely to fall off from the plating layer 11, and the effect of wear resistance can be maintained for a longer period of time.

By the above-mentioned second forming method, the wear-resistant film in the form of FIG. 2, that is, the wear-resistant film 10 having the plating layer 11 on which the plurality of holes 15 are formed is formed on the base material 20.

In the method of forming the pores 15 in the plating layer 11 using 5 resin particles, the pores 15 having a large aspect ratio are likely to be formed, and steep irregularities are also likely to be formed. As a result, the solid lubricant 2 such as lubricating particles is easily held by the plating layer 11, and the wear-resistant film 10 having excellent wear resistance sustainability is easily formed.

According to the method for forming a wear-resistant film according to the present invention, it is a method suitable as a method for manufacturing the wear-resistant film and the wear-resistant member. In particular, the wear-resistant film produced by the method for forming the wear-resistant film according to the present invention can maintain excellent wear resistance for a long period of time because the solid lubricant is easily held by the plating layer. can.

The method of the present invention, the wear-resistant film 10 and the wear-resistant member 30 can be suitably used for various members. Applicable members include various mechanical parts, power system parts such as sliding bearings and piston rings of various engine parts, continuously operating power transmission parts such as chains, tools, dies, etc. Various sliding parts such as those used for household goods, industrial machines, transport machines, leisure goods, etc. are also exemplified.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to the embodiments of these Examples.

(Example 1)
Iron (S45C) was prepared as a base material, and unevenness was formed on the base material by shot blasting. Ceramic projection material (alumina, garnet) is used for shot blasting, the sand grid has a mesh size of # 100 to 150, the pressure is 10 kgf / cm ² , and the maximum roughness Rz of the unevenness of the substrate surface is 2 to. It was set to 4 μm.

Next, an electroless Ni-P plating treatment was performed on the base material on which the unevenness was formed. As the electroless Ni plating solution, "Nimden KTB (registered trademark)" (Uyemura & Co., Ltd.) was used, and the other working environment conformed to the standard conditions of the above plating solution. The thickness of the formed plating layer was 10 μm.

Next, molybdenum disulfide particles (average primary particle diameter of 1 μm) were retained on the plating layer by shot blasting to form a lubricating layer having a thickness of about 3 μm. In this way, the base material coated with the wear-resistant film was obtained as the wear-resistant member.

(Example 2)
Iron (S45C) was prepared as a base material, and unevenness was formed on this base material by shot blasting. Ceramic projection materials (alumina, garnet) are used for shot blasting, the sand grid is # 100 to 150, the pressure is 10 kgf / cm ² , and the maximum roughness Rz of the unevenness of the substrate surface is 2 to 4 μm. did.

Next, an electroless Ni-P plating treatment was performed on the base material on which the unevenness was formed. As the electroless Ni plating solution, "Nimden KTB (registered trademark)" (Uyemura & Co., Ltd.) is used, and the amount of acrylic resin particles having an average primary particle diameter of 2.5 μm is further added to this plating solution in an amount of 5 g / L. In addition, a trace amount of cationic surfactant was added. Other working environments conformed to the standard conditions of the above plating solution. The thickness of the formed plating layer was 10 μm, and acrylic resin particles were contained inside.

The substrate on which the plating layer was formed was heat-treated at 350 ° C. for 120 minutes. As a result, the acrylic resin particles were burnt down and pores were formed in the plating layer.

Next, molybdenum disulfide particles (average primary particle diameter of 1 μm) were held on the plated layer having pores formed by shot blasting to form a lubricating layer having a thickness of about 3 μm. In this way, the base material coated with the wear-resistant film was obtained as the wear-resistant member.

(Example 3)
Iron (S45C) was prepared as a base material, and unevenness was formed on this base material by shot blasting. Ceramic projection materials (alumina, garnet) are used for shot blasting, the sand grid is # 100 to 150, the pressure is 10 kgf / cm ² , and the maximum roughness Rz of the unevenness of the substrate surface is 2 to 4 μm. did.

Next, an electroless Ni-P plating treatment was performed on the base material on which the unevenness was formed. For the electroless Ni plating solution, "Nimuden KTB (registered trademark)" (Uyemura & Co., Ltd.) is used, and molybdenum disulfide particles (average primary particle diameter 1 μm) are further added to this plating solution in an amount of 5 g / L. Added. Other working environments conformed to the standard conditions of the above plating solution. The thickness of the formed plating layer was 10 μm, and molybdenum disulfide particles were contained therein. In this way, the base material coated with the wear-resistant film was obtained as the wear-resistant member.

(Example 4)
A wear-resistant member was obtained by the same method as in Example 2 except that no unevenness was formed on the base material.

(Comparative Example 1)
In Example 1, a base material having irregularities formed without forming a plating layer and a lubricating layer was obtained as a comparative sample.

(Comparative Example 2)
In Example 1, a lubricating layer (molybdenum disulfide particles) having a thickness of about 3 μm was directly formed on the substrate without forming a plating layer, and this was obtained as a wear-resistant member.

(Comparative Example 3)
A wear-resistant member was obtained by the same method as in Example 1 except that the lubricating layer was not formed.

(Comparative Example 4)
A wear-resistant member was obtained by the same method as in Example 3 except that biotite (average primary particle diameter of 1 μm or less) was used instead of molybdenum disulfide particles and a cationic surfactant was added to the plating solution. rice field.

(Comparative Example 5)
A wear-resistant member was obtained by the same method as in Example 3 except that PTFE particles (average primary particle diameter of 1 μm or less) were used instead of molybdenum disulfide particles.

(Abrasion resistance test)
The wear resistance test of the wear resistant member was performed under the following conditions.
・ Load: 10N
-Mating material: Stainless steel-Rotation speed: The wear-resistant member was set to 100 rpm, and the mating material was set to 100 rpm.
・ Wear time: Performed until the film disappears. ・ Measure the amount of wear of the film every 15 minutes after the start of measurement. The wear resistance test can be performed using a pin-on-disk type wear tester.

FIG. 5 shows the results of the wear resistance test of the wear resistant members obtained in each Example and Comparative Example. From this figure, it can be seen that the wear-resistant member obtained in the example is unlikely to increase in the amount of wear even when the wear-resistant test is performed for a long time, whereas the wear-resistant member of the comparative example has. It can be seen that the amount of wear increases remarkably immediately after the start of measurement or after a certain period of time has elapsed. As a result, it can be said that the wear-resistant member obtained in the examples can maintain excellent wear resistance for a long period of time even if the wear is repeated.

It was found that Comparative Examples 1 and 2 did not have the plating layer 12, and peeling due to wear occurred immediately. Comparative Example 2 did not wear during the presence of the initial molybdenum disulfide, but at the same time as the molybdenum disulfide disappeared from the surface, wear of the material was immediately confirmed.

In Comparative Example 3, since there is a plating layer, it is difficult to wear at the initial stage, but it is considered that the plating layer 12 gradually disappears and the wear progresses.

The composite plating of Comparative Examples 4 and 5 is good because the amount of wear is small at the initial stage due to the effect of the composite particles, but the progress of wear is fast in the latter half, and the entire coating is worn in about 60 to 90 minutes. It has reached the material.

On the other hand, Examples 1 to 4 gave good results. In particular, Example 2 resulted in the smallest amount of wear due to wear time. It is considered that the second embodiment is because the plating layer is formed in a porous shape and has holes.

In Example 1, since molybdenum disulfide is inserted into the uneven portion of the plating layer and fixed, the wear resistance can be maintained for a long period of time.

In the second embodiment, since the molybdenum disulfide is inserted into the hole 15, the lubricating layer is firmly fixed, and as a result, the wear resistance is excellent.

Unlike Examples 1 and 2, Molybdenum disulfide is held in the plating layer in Example 3, so that it has slidability and is firmly fixed to the plating layer. As a result, Example 3 showed better wear resistance than Comparative Examples 4 and 5 as the composite plating layer.

In Example 4, since the substrate 15 was not unevenly treated, the adhesion between the base material 15 and the plating layer was not as high as in other examples, but the substrate 15 had better wear resistance than the comparative examples.

2: Solid lubricant 5: Resin particles 10: Abrasion resistant film 11: Plating layer 12: Lubricating layer 13: Coat layer 15: Hole 20: Base material 30: Abrasion resistant member

Claims (6)

A wear-resistant member including a wear-resistant film and a base material.
The wear-resistant film has a plating layer and a lubricating layer laminated on the plating layer.
The plating layer is an electroless Ni-P composite plating layer.
The lubricating layer contains a solid lubricant and
The base material is coated with the wear-resistant film, and the base material is coated with the wear-resistant film.
The surface of the wear-resistant film on the plating layer side adheres to the substrate,
Unevenness is formed on the surface of the base material covered with the wear-resistant film.
A wear-resistant member having a plurality of holes formed on the surface layer and the inside of the plating layer. The wear-resistant member according to claim 1, wherein a part or all of the solid lubricant has entered the inside of the hole. The wear-resistant member according to claim 1 or 2, wherein the solid lubricant is at least one selected from the group consisting of graphite, molybdenum disulfide, boron nitride, tungsten disulfide, lead oxide and fluororesin. The method for manufacturing a wear-resistant member according to any one of claims 1 to 3 .
The first step of forming a plating layer by plating the surface of the base material, and
The second step of forming a lubricating layer containing a solid lubricant on the surface of the plating layer, and
A method for manufacturing a wear-resistant member including. The plating process of the first step further includes a step of forming a plating layer containing resin particles by using a plating solution containing resin particles and burning the resin particles by heat-treating the plating layer. The manufacturing method according to claim 4 . The manufacturing method according to claim 4 or 5 , further comprising a step of forming irregularities on the surface of the base material before performing the plating treatment.

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