JPH09209189A - Sliding member and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To improve the seizing resistance and wear resistance of the sliding face of an Al allay layer or a reinforcing material-contg. Al alloy layer of a sliding member. SOLUTION: On the sliding face 2 of an Al alloy or a reinforcing material- contg. Al alloy of a sliding member, an inorganic compound film layer 3 with 0.1 to 20μm film thickness composed of one or more kinds among the compounds of Mo, W and Cr by 20 to 70wt.% (expressed in terms of metal), and the balance oxygen or composed of one or more kinds among the compounds of Mo, W and Cr by 2 to 48wt.%. (expressed in terms of metal), Al compounds by 1 to 25wt.% (expressed in terms of Al), phosphorus compounds by 1 to 25wt.% (expressed in terms of P), and the balance oxygen is formed by a chemical conversion treating method or an electrolytic treating method (with the sliding member as the cathode).

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a sliding member used in transportation machines such as automobiles and ships, general industrial machinery, etc., and a method for manufacturing the sliding member. More specifically, it is suitable as an engine part. The present invention relates to a sliding member and a manufacturing method thereof.

[0002]

2. Description of the Related Art A non-ferrous metal sliding member such as an aluminum alloy used in an engine or the like is generally a non-ferrous metal base or a base material formed by joining a non-ferrous metal alloy for a sliding member to a backing material. Is manufactured into a desired shape, for example, in the case of a slide bearing, processed into a cylindrical bush or a half-split shape.

Copper-lead alloys or aluminum alloys are mainly used as alloys for sliding members. In recent years, however, aluminum alloys or aluminum alloys have been used in order to cope with high engine rotation and output and reduce production costs. The use of aluminum alloys containing reinforcement tends to increase.

As the aluminum alloy for the sliding member, when an aluminum-tin alloy or an aluminum-silicon alloy is used, and when the Sn content is high, it can be used without an overlay layer. Generally, the Sn content is lowered to about 5 to 7% to improve its fatigue resistance and corrosion resistance.

In this case, the initial familiarity (rapid b)
In order to improve the reak-in, it was necessary to apply soft Sn-based or Pb-based overlay plating on the aluminum alloy layer.

As an alloy for a sliding member which requires such an overlay plating layer, for example, JIS H5402
AJ-1 (10% Sn-0.75Cu-0.5Ni-
AlBal), JIS H5402 AJ-2 (6% S
n-2.5Cu-1.0Ni-Al Bal), and JIS AC8A (12% Si-1.0Cu-1.5N).
i-Al Bal) and the like are known.

However, even in a sliding member obtained by overlaying a soft metal overlay on these sliding member alloys,
Since the melting temperature of overlay plating is low, phenomena such as fatigue, seizure, and wear occur under high load conditions due to the temperature rise of the lubricating oil and the temperature of the lubricating surface rises, and there are cases in which it cannot be used.

Further, a metal material for a sliding member is machined,
There is also known a method of performing electroplating for overlay formation after that, but this method requires a large number of processing steps,
Therefore, there are problems that productivity is low and cost is high.

On the other hand, on the surface of the aluminum alloy layer,
As an example of a sliding member provided with a chemical conversion treatment film having excellent heat resistance, European Patent EP-PS 0059273 and Japanese Patent Laid-Open No. Sho 64-64 are cited.
There is a chemical slide bearing described in 49713.

The former is one in which a zinc phosphate coating is formed on an aluminum bearing alloy layer, and a uniform load is applied to the bearing surface to remove the localized concentrated load and improve the conformability. The latter is an improvement of this to prevent the formation of a zinc phosphate film on the outer peripheral surface of the bearing layer.

However, even in the above-mentioned aluminum alloy bearing having a zinc phosphate coating, zinc phosphate has a drawback that it is not crystalline because it is not sufficiently smooth and is easily worn. The obtained sliding member was insufficient in seizure resistance and wear resistance under high load.

Further, as disclosed in JP-A-64-49713, coarse zinc phosphate crystals attached to the back surface of the bearing are
When the bearing is fixed to the bearing housing, it causes looseness in this fixing. In order to prevent the loosening of the fixing, there is a problem that it is necessary to previously perform a treatment for preventing the formation of a phosphate film on the back surface of the bearing.

That is, up to now, no surface treatment film or surface treatment method has been found which imparts excellent seizure resistance and wear resistance to a sliding surface formed of an aluminum alloy or a reinforcing material-containing aluminum alloy. Of.

[0014]

SUMMARY OF THE INVENTION In order to solve the above problems of the prior art, the present invention provides overlay plating on the sliding surface of a sliding member formed of an aluminum alloy or an aluminum alloy containing a reinforcing material. Instead, by providing a special inorganic chemical conversion coating layer that is smooth, and has excellent lubricity and wear resistance, a sliding member having better seizure resistance and wear resistance than before, and a method for manufacturing the same are provided. It is the one we are trying to provide.

[0015]

DISCLOSURE OF THE INVENTION The present inventors have improved seizure resistance and wear resistance of an aluminum alloy sliding member which has conventionally been required to be overplated without the above plating. In order to do so, various chemical conversion treatment films were formed on the surface of the aluminum alloy layer or the reinforcing material-containing aluminum alloy layer, and the sliding performances thereof were studied thoroughly.

As a result, the sliding surface of the base body made of the aluminum alloy or the aluminum alloy containing the reinforcing material is formed from a conventionally known crystalline compound such as zinc phosphate, sodium aluminum fluoride or manganese phosphate. When a film is formed, this sliding surface has a crystal diameter of 3-4 μm
It was found that it is covered with the above coarse chemical crystals, which reduces the smoothness of the sliding surface and raises the friction coefficient (μ) of the sliding surface, so that seizure easily occurs under high load. It was

Based on these findings, the present inventors have found that the sliding surface is amorphous or low in crystallinity, smooth and hard,
Moreover, further research was conducted to form a chemical conversion film having excellent wear resistance and heat resistance.

As a result, an inorganic compound film layer containing a compound of at least one metal of molybdenum, tungsten, or chromium as a main component, and the balance substantially consisting of oxygen is used as an aluminum alloy or a strengthening material for the sliding member substrate. By forming it on the sliding surface made of aluminum alloy containing aluminum, it is possible to obtain a sliding member that has better seizure resistance and wear resistance than the conventional zinc phosphate conversion coating, or is highly compatible. I found that Further, the inorganic compound film layer exhibiting such performance contains a compound of at least one metal selected from molybdenum, tungsten, and chromium in a total amount of 2 to 70% by weight in terms of metal,
It has been found that the balance consists essentially of oxygen.

Further, the inventors have continued to research, and at least one metal selected from molybdenum, tungsten, and chromium was formed on the sliding surface of the sliding member substrate formed of the aluminum alloy or the reinforcing alloy containing aluminum. By forming an inorganic compound film containing a compound, an aluminum compound, and a phosphorus compound, and the balance substantially consisting of oxygen, it has further excellent seizure resistance and abrasion resistance, or is excellent in familiarity. A sliding member is obtained, and the inorganic compound film has a total of 2 to 48% by weight of a compound of at least one metal selected from molybdenum, tungsten, and chromium in terms of metal.
Converting aluminum compound to aluminum metal
It has been found that it contains 25% by weight and 1 to 25% by weight of phosphorus compound in terms of phosphorus, and the balance substantially consists of oxygen.

The present inventors have also diligently studied the method for producing the sliding member of the present invention, and have investigated molybdate ion,
Formed by an aluminum alloy or an aluminum alloy containing a reinforcing material on a sliding member base in an aqueous solution containing tungstate ion and / or chromate ion and containing fluorine ion and optionally inorganic phosphorus compound ion such as phosphoric acid It is possible to produce the sliding member of the present invention by the chemical conversion treatment method of bringing the sliding surfaces into contact with each other, or even when a treatment liquid containing no fluorine ion is used, sliding is performed in this treatment liquid. The present invention has been completed by finding that the sliding member of the present invention can be manufactured by a method in which an aluminum alloy layer is subjected to electrolytic treatment using the sliding surface of the member as a cathode.

The sliding member of the present invention comprises a substrate having a sliding surface formed of an aluminum alloy or a reinforcing material-containing aluminum alloy, and a molybdenum compound, a tungsten compound and a chromium compound formed on the substrate sliding surface. An inorganic compound film layer containing at least one metal compound selected from the above, a total of 20 to 70% by weight in terms of metal, and the balance substantially consisting of oxygen, and having a film thickness of 0.1 to 20 μm. It is characterized by having. This sliding member is hereinafter referred to as the sliding member of the first invention.

Another sliding member of the present invention is a substrate having a sliding surface formed of an aluminum alloy or a reinforcing material-containing aluminum alloy, and a molybdenum compound, a tungsten compound and a molybdenum compound formed on the sliding surface of the substrate. At least one metal compound selected from chromium compounds,
2 to 48% by weight in terms of metal, 1 to 25% by weight of aluminum compound in terms of aluminum metal, 1 to 25% by weight of phosphorus compound in terms of phosphorus, and
0.1 to 20 μm, including the balance consisting essentially of oxygen
and an inorganic chemical conversion coating layer having a thickness of m. Hereinafter, this sliding member will be referred to as the sliding member of the second invention.

The method for producing the sliding member according to the first aspect of the present invention comprises:
The sliding surface of the base having a sliding surface formed of an aluminum alloy or a reinforcing material-containing aluminum alloy,
It is characterized in that it is brought into contact with an aqueous solution containing at least one selected from molybdate ion, tungstate ion and chromate ion, and fluorine ion.

Another method for producing the sliding member of the first invention is a substrate having a sliding surface formed of an aluminum alloy or a reinforcing material-containing aluminum alloy, wherein the sliding surface has molybdate ions or tungsten. The method is characterized in that electrolytic treatment is performed in an aqueous solution containing at least one selected from acid ions and chromate ions, with the sliding surface of the substrate as a cathode.

The method for producing the sliding member according to the second aspect of the invention is
At least one selected from molybdate ion, tungstate ion, and chromate ion is used as the base material having a sliding surface formed of an aluminum alloy or a reinforcing material-containing aluminum alloy, and phosphoric acid. It is characterized in that it is brought into contact with an aqueous solution containing ions of at least one phosphorus compound selected from, phosphorous acid, and condensed phosphoric acid, and fluorine ions.

Another method for producing the sliding member according to the second aspect of the present invention is that a molybdate ion, tungsten is formed on the sliding surface of a substrate having a sliding surface formed of an aluminum alloy or a reinforcing material-containing aluminum alloy. The substrate sliding surface in an aqueous solution containing at least one selected from acid ions and chromate ions and at least one phosphorus-containing ion selected from phosphoric acid, phosphorous acid, and condensed phosphoric acid. Is used as a cathode for electrolytic treatment.

In addition to the chemical conversion treatment method and the electrolytic treatment method described above, the sliding member of the present invention has a CVD method (chemical vapor deposition method), a PVD method (physical vapor deposition method), an atmospheric pressure CVD method (pyrosol method). ), Or a thermal spraying method.

[0028]

BEST MODE FOR CARRYING OUT THE INVENTION A slide bearing material can be cited as an embodiment of the sliding member of the present invention. As shown in FIG. 1, this plain bearing material has a metal back surface 1, for example, a steel back metal 1, on which a layer 2 of an aluminum alloy or a reinforcing material-containing aluminum gold layer is formed, and further, an inorganic compound film thereon. The layer 3 is formed. In such a sliding member of the present invention, a compound of at least one metal selected from molybdenum, tungsten, and chromium is provided on the sliding surface formed of the aluminum alloy layer or the reinforcing material-containing aluminum alloy. In the above, it is characterized by having an inorganic compound film layer containing a total amount of 2 to 70% by weight (metal conversion) and the balance substantially consisting of oxygen. In the case of the second invention, the inorganic compound coating layer may further contain an aluminum compound and a phosphorus compound. In this case, the inorganic compound coating layer has a total content of molybdenum, tungsten, and / or chromium compounds. 2 to 48% by weight (metal conversion), aluminum compound content is 1 to 25% by weight (aluminum metal conversion), phosphorus compound content is 1 to 25% by weight (phosphorus conversion), and the balance is substantially oxygen. It will be. In other sliding members except the plain bearing, the sliding surface can be formed of a reinforcing material-containing aluminum alloy.

The base of the sliding member to which the present invention is applicable has a sliding surface made of an aluminum alloy or an aluminum alloy containing a reinforcing material, and the sliding alloy layer is a metal backing, for example, a steel backing. It may be formed in. The type of aluminum alloy is JIS H5402 A
J-1 (10% Sn-0.75Cu-0.5Ni-Al
Bal), and JIS H5402 AJ-2 (6
% Sn-2.5Cu-1.0Ni-AlBal) and other Al-Sn-Cu based alloys, as well as Al-Si alloys, A
1-Sn-Si-Pb-Cu alloy, Al-Pb alloy, Al-Zn-Si-Cu-Pb alloy, etc. are included. Further, the reinforcing material-containing aluminum alloy includes the above aluminum alloy reinforced by an inorganic material such as alumina fiber, silica fiber, alumina particles and / or silica particles. In this case, the reinforcing material has a thickness of 0.1 to 200 μm.
m, a length of 1 to 100 mm, or an alumina or silica fiber, or an alumina particle or a silica particle having a particle diameter of 0.1 to 500 μm, and the content thereof is 1 to 40% by volume.

Such a sliding member is arranged such that its aluminum alloy layer or aluminum alloy layer containing a reinforcing material forms an inner surface (sliding surface), is machined and surface-finished, and thereafter, The inorganic compound film layer according to the present invention is formed on the top surface.

The thickness of the inorganic compound film layer formed on the sliding surface is 0.1 to 20 μm, preferably 0.2 to
It is 4 μm. If this thickness is less than 0.1 μm, the abrasion resistance of the sliding surface of the resulting sliding member will be insufficient, and if it exceeds 20 μm, the aluminum alloy layer of the inorganic compound film layer or the reinforcing material-containing aluminum alloy layer will be described. Adhesion to is insufficient.

The inorganic compound film formed on the sliding surface contains at least one metal compound selected from oxides, hydrated oxides, complex oxides, etc. of molybdenum, tungsten, and chromium, and is required. In addition to this, it is an inorganic composite film containing an aluminum compound such as aluminum phosphate and aluminum phosphite and a phosphorus compound. This film layer contains a compound such as a heteropolyacid salt such as molybdophosphate in addition to the above components. May be included. The appearance of this inorganic compound film layer exhibits a color tone such as gray, golden to brown, or black, and may exhibit an interference color.

In addition to these, small amounts of Sn, Ni, Pb, Si contained in the sliding alloy, or Na, F contained in the treatment bath as eutectoids in the inorganic compound film layer. However, a small amount of these does not adversely affect the sliding performance.

In the sliding member of the present invention, the inorganic compound film layer formed on the aluminum alloy layer or the reinforcing material-containing aluminum alloy layer of the substrate is at least one selected from molybdenum compounds, tungsten compounds and chromium compounds. 2 to 70% by weight, preferably 3 to 60% by weight (in terms of metal), of the total amount of the seed metal compound, and the balance substantially consisting of oxygen, and if necessary, further contains an aluminum compound and a phosphorus compound. Maybe,
In this case, the inorganic compound film layer contains at least one metal compound selected from the group consisting of molybdenum compounds, tungsten compounds and chromium compounds in a total amount of 2 to 48% by weight, preferably 10 to 40% by weight.
42% by weight (metal conversion) and 1 to aluminum compound
25% by weight, preferably 5 to 20% by weight (converted to aluminum metal), 1 to 25% by weight, preferably 5 to 23% by weight (converted to phosphorus) of a phosphorus compound, and the balance substantially consisting of oxygen. is there. The most preferable composition of the inorganic compound film is such that the total content of at least one of a molybdenum compound, a tungsten compound, and a chromium compound is 2 or less.
5 to 42% by weight (metal conversion), and the content rate of the aluminum compound is 5 to 15% by weight (aluminum metal conversion)
The content of the phosphorus compound is 7 to 17% by weight (converted to phosphorus), and the balance is substantially oxygen.

Immediately after the inorganic compound coating layer forming treatment, the obtained coating contains a large amount of hydrogen atoms constituting hydrated water such as hydrated oxide and adsorbed water. Much of the water is lost by dehydration, and the film hardens and stabilizes accordingly, so the content of hydrogen atoms derived from the above-mentioned water among the constituent atoms of the film is practically negligible. Becomes

Of the molybdenum compound, tungsten compound and chromium compound in the inorganic compound film component,
Compounds of molybdenum and tungsten are more preferable from the viewpoint of improving the adhesion and heat resistance of the film.

In the sliding member according to the first aspect of the present invention, molybdenum compound, tungsten compound in the inorganic compound film component,
And the total content of chromium compounds is 2% (metal conversion)
If it is less than 1, the abrasion resistance of the coating is insufficient. In addition,
If it exceeds 70% by weight (metal conversion), the chemical stability of the film becomes insufficient, which is a disadvantage. In the sliding bearing material of the second aspect of the present invention, the total content of molybdenum compound, tungsten compound and chromium compound is 2% by weight.
When the content is less than (metal equivalent), the content of the aluminum compound exceeds 25% by weight (metal conversion), or the content of the phosphorus compound exceeds 25% by weight (phosphorus conversion), the obtained coating layer is obtained. Has an excessively large surface roughness, resulting in insufficient seizure resistance.

In the sliding member of the second invention, when the total content of the metal compounds is less than 2% by weight (metal conversion) or when the content of the aluminum compounds exceeds 25% by weight (metal conversion), When the phosphorus compound content exceeds 25% by weight (converted to phosphorus), the surface roughness of the obtained coating layer becomes excessive and the seizure resistance becomes insufficient. Furthermore, in the second invention sliding member, when the total content of compounds of molybdenum, tungsten, and chromium in the inorganic compound coating layer exceeds 48% by weight (metal conversion),
When the content of the aluminum compound is less than 1% by weight (metal conversion) and when the content of the phosphorus compound is less than 1% (phosphorus conversion), the surface roughness of the obtained coating layer becomes excessive.

Further, when the inorganic compound film layer is formed on the sliding surface of the sliding member by the method of the present invention, the interference color to the opposite side (rear surface) of the metal backing, especially the steel backing, can be simultaneously improved.
Although a thin film containing black oxide of molybdenum, tungsten, or chromium or iron phosphate as a component is formed, this thin film has an effect of imparting corrosion resistance to a steel backing and preventing rusting. More preferably, the method is collectively applied to the entire sliding member including the back surface.

Next, the method for manufacturing the sliding member of the present invention will be described in detail.

Since the oil content such as cutting oil adheres to the surface of the base member of the surface-finished sliding member, it is preliminarily subjected to degreasing cleaning with an aqueous cleaning solution containing an organic solvent or a surfactant. Need to be kept.

In order to manufacture the sliding member of the first invention, the surface of the aluminum alloy layer or the reinforcing material-containing aluminum alloy layer of the substrate is provided with at least one kind selected from molybdate ion, tungstate ion and chromate ion. In an aqueous solution containing at least one selected from a molybdate ion, a tungstate ion, and a chromate ion, by contacting an aqueous solution containing an ion and a fluorine ion with a method such as a dipping method or a spray method. It is possible to use a method of subjecting the sliding surface of the base body to a cathode and subjecting the aluminum alloy layer or the reinforcing material-containing aluminum alloy layer of the base body to electrolytic treatment.

In order to manufacture the sliding member of the second invention,
On the surface of the aluminum alloy layer or the reinforcing material-containing aluminum alloy layer of the substrate, at least one selected from molybdate ion, tungstate ion, and chromate ion, and phosphoric acid, phosphorous acid, and condensed phosphoric acid are used. A chemical conversion treatment method in which an aqueous solution containing at least one selected phosphorus compound ion and a fluorine ion is contacted in the same manner as described above, and at least one selected from molybdate ion, tungstate ion, and chromate ion.
And an electrolytic treatment on the sliding surface of the base in an aqueous solution containing a seed and at least one phosphorus compound ion selected from phosphoric acid, phosphorous acid, and condensed phosphoric acid. A method of applying can be used.

The molybdate ion, tungstate ion, and chromate ion used in the method of the present invention are produced by dissolving these ortho acids or polyacids in water. Therefore, the existence form of these metal-containing ions in the treatment bath is Mo ₇ O ₂₄ B ⁻ , W ₈
It includes polymolybdic acid such as O ₂₆ ⁴⁻ , polytungstic acid and dichromate ions such as Cr ₂ O ₇ ²⁻ .

The molybdate ion, tungstate ion, and chromate ion are formed by dissolving an alkali metal salt or ammonium salt of ammonium molybdate, sodium molybdate, potassium tungstate, sodium dichromate, etc. in water. Preferably.

The molybdate ion, tungstate ion and chromate ion in the treatment bath used in the method of the present invention have a total concentration of 0.1 to 0.1 in each case.
It is preferably in the range of 400 g / liter. If the metal-containing ion concentration is less than 0.1 g / liter, a coating layer having a sufficient thickness cannot be obtained, and if it exceeds 400 g / liter, the maximum solubility is exceeded and precipitation occurs, which makes practical use difficult. More preferable concentration range is 1 to 100 g
/ Liter.

In the chemical conversion treatment method for producing the sliding member of the second invention, the ion of the inorganic phosphorus compound selected from phosphoric acid, phosphorous acid or condensed phosphoric acid in the treatment bath is
Although it may be produced from these acids, sodium phosphate, ammonium phosphate, potassium phosphite,
It is preferably produced from a soluble salt such as sodium pyrophosphate, and most preferably an acidic phosphate such as monosodium phosphate or monoammonium phosphate is used.

In this case, the preferable concentration range of the ions of phosphoric acid, phosphorous acid, or condensed phosphoric acid is 0.1 to 300.
g / liter, more preferably 0.5 to 10
It is 0 g / liter.

Further, in the method of the present invention, when the treatment liquid contains fluorine ions, the fluorine ions are sodium fluoride, sodium acid fluoride, potassium fluoride, ammonium fluoride, sodium borofluoride, silica fluoride. It may be supplied by a compound such as sodium fluoride, hydrofluoric acid, borohydrofluoric acid, hydrosilicofluoric acid, zircon hydrofluoric acid, titanium hydrofluoric acid, and these compounds are appropriately selected. Can be used.

In this case, the concentration of fluorine ions measured by a fluorine ion meter or the like is preferably 0.02 to 100 g / liter, and the most preferable range is 0.
It is 1 to 5 g / liter.

When the fluorine ion concentration is less than 0.02 g / liter, the inorganic compound film layer is not formed because the etching effect on the aluminum alloy layer or the reinforcing material-containing aluminum alloy layer is insufficient, and it is 100 g / l.
If it exceeds liter, the surface roughness of the sliding surface of the obtained sliding member becomes excessive and the sliding performance deteriorates, which is not preferable.

It is also possible to improve the rate of film formation and the stability of the bath by adding an oxidizing agent such as nitrate ions and hydrogen peroxide to the treatment bath for the aqueous solution contact method.

In order to obtain a smooth and sufficient coating amount,
The pH value of the treatment bath is preferably in the range of 2 to 7, and most preferably 3 to 6. Generally, when an acidic phosphate such as monosodium phosphate or monoammonium phosphate is used as the source of phosphorus compounds, an appropriate pH value can be obtained without adjusting the pH value.

The treatment temperature of the treatment solution for the aqueous solution contacting method is preferably 20 to 80 ° C., and the treatment time is usually 5 seconds or more, though it depends on the fluorine ion concentration and the treatment temperature.
600 seconds is sufficient.

In the method of the present invention, when the inorganic compound film is formed by the cathodic electrolysis method, the cathodic current density in this electrolytic treatment is preferably 0.2 to 20 A / dm ² , and at this time, platinum-coated titanium and DSE are used. It is preferable to use an insoluble electrode such as carbon, stainless steel or the like as the anode.

Further, the adhesion of the coating can be further improved by immersing it in the electrolytic solution for several seconds to several tens of seconds before the start of energization.

In addition to the above components, an oxidizing agent such as nitrate ion or hydrogen peroxide may be added to the electrolytic bath to improve the film forming rate and the stability of the bath. Further, the inclusion of fluorine ions in the electrolytic bath is not generally preferable because it adversely affects the life of the anode, but it is practically acceptable if the concentration is low.

The electrolytic treatment temperature is preferably 20 to 70 ° C., and the treatment time varies depending on the current density, but usually 10
The range of 180 seconds is preferable.

When the formation of the inorganic compound film layer is completed by the above method of the present invention, it is immediately washed with water and dried to complete the treatment. In this drying, in order to accelerate the dehydration of the hydrated oxide and stabilize the sliding performance, 80 to 15
It is more preferable to heat-dry at a temperature of about 0 ° C for several seconds to several minutes.

The sliding member of the present invention has an inorganic compound film containing a large amount of molybdenum, tungsten, chromium, and oxygen on the surface of the aluminum alloy layer or the reinforcing material-containing aluminum alloy layer. These compounds are extremely fine crystalline materials. Since it is amorphous, the surface roughness of the sliding surface is not increased, and at the same time, it is a hard coating having a small friction resistance and excellent adhesion.

Therefore, when the inorganic compound film is formed on the relatively soft aluminum alloy layer or the reinforcing material-containing aluminum alloy layer, not only the wear resistance of the sliding surface is improved but also the sliding member is improved. Even when a large load is partially applied, elastic deformation of the aluminum alloy layer or the reinforcing material-containing aluminum alloy layer, the inorganic compound film layer can easily follow the plastic deformation, without peeling, Dispersion of the load improves seizure resistance and does not impair familiarity.

Most of the water of hydration of the inorganic compound is lost in the formed inorganic compound film by drying or heat drying. At this time, a slight amount of volume shrinkage accompanies some fine cracks in the coating, but even if a load is applied to the sliding surface, the adhesiveness is not lost and the abrasion resistance is good, so excellent sliding is achieved. Show performance.

The above sliding member of the present invention is made of one kind selected from aluminum alloy, aluminum alloy containing reinforcing material, steel of HV400 or more, cast iron, and steel subjected to nitriding treatment or metal plating treatment, A sliding member-abutting member composite is constructed by combining with the abutting member that abuts on the sliding surface of the sliding member and slides relative to each other.

In the composite, for example, the sliding member is selected from the groove and skirt of the engine piston, the cylinder bore, the valve lifter, the A / T hydraulic control valve spool, the brake master cylinder piston, and the slide bearing. The contact member can be selected from a piston ring, a cylinder bore, a cylinder head, a valve body, a shaft and the like corresponding to the sliding member.

[0065]

EXAMPLES The present invention will be specifically described with reference to the following examples.

Examples 1 to 15 and Comparative Examples 1 to 3 As a test bearing base material, an aluminum alloy for bearing (Al-6Sn-1Cu-Ni) thin plate was roll-bonded by a roll rolling method to a steel backing, and this was joined to this. A bimetal was manufactured by annealing at a temperature of 350 ° C. for 4 hours.

Next, the obtained bimetal was cut and machined to prepare a bearing test piece, which was degreased for aluminum (Fine Cleaner 315: manufactured by Nippon Parkerizing Co., Ltd.) in a concentration of 20 g / liter and 70 After degreasing at 0 ° C. for 2 minutes and washing with water, the inorganic compound film layer forming treatment described in each of the Examples and Comparative Examples was applied, and further washed with water, and then 12
It was dried with hot air at 0 ° C. for 5 minutes.

Tables 1 and 2 show the surface treatment conditions of Examples 1 to 15 and Comparative Examples 1 to 3, the coating amount and the coating composition.

In Examples 12, 13, 14 and 15, the bearing test piece was used as a cathode and platinum-plated titanium was used as an anode to subject the bearing test piece to electrolytic treatment to form an inorganic compound film layer. The cathode current density at this time was 0.5 A / dm ² in Example 12, and 10 A in Example 13.
/ Dm ² , and in Examples 14 and 15 2A /
It was dm ² .

In the other examples and comparative examples, the bearing test piece was brought into contact with the treatment liquid by the spray method or the dipping method to form the inorganic compound film layer on the bearing test piece.

Molybdate ions in the treatment liquid are formed by adding ammonium molybdate, and tungstate ions are formed by adding sodium tungstate.
Chromate ions are formed by adding ammonium dichromate, and fluorine ions are formed by adding sodium fluoride or ammonium fluoride.
It adjusted so that it might become the numerical value shown in 2 and 2.

Phosphate ions are produced by adding monosodium phosphate, phosphite ions are produced by adding monosodium phosphite, and pyrophosphate ions and tripolyphosphate ions are It was produced by adding the potassium salt of.

In the formation of the zinc phosphate film in Comparative Example 3, 3.8 g of zinc oxide was dissolved in 30 g of phosphoric acid, and water was added to make the total amount 1 liter. Sodium hydroxide was added to this to adjust the pH. The treatment liquid was prepared as 3 to 3.5, and the bearing test piece was treated with this treatment liquid.

The contents (%) of molybdenum, tungsten, chromium, and phosphorus in the inorganic compound film were measured by an X-ray photoelectron spectroscopy analyzer (XPS: Shimadzu ESCA-850).
Quantitative analysis was performed using M), and it was confirmed that oxygen was mainly contained in the rest of the film components of the examples and comparative examples except molybdenum, tungsten, chromium and phosphorus.

The adhered amount of the entire coating was calculated from the difference in weight before and after dissolution after masking the back metal portion and dissolving only the coating with 36% nitric acid.

[0076]

[Table 1]

[0077]

[Table 2]

The bearing test pieces obtained in the respective examples and comparative examples were subjected to a seizure test and a wear test using a rotary load tester. The seizure test and wear test conditions are shown below, and the test results are shown in FIGS. 2 and 3.

[Seizure test condition] Test device: Static load bearing tester Rotation speed: 5000 rpm, Lubrication amount: 0.1 liter / division speed: 12.5 m / sec, Lubricating oil: SAE 10W-30 Lubrication temperature: 100 ± 2 ° C, Shaft material: S50C (quenched, surface roughness Rz: 0.8 μm) Judgment method: When the bearing back surface temperature rises sharply or when the motor overloads.

[Abrasion test condition] Test apparatus: Static load bearing tester Rotation speed: 5000 rpm, Lubrication amount: 0.1 liter / division speed: 12.5 m / sec, Lubricating oil: SAE 10W-30 Surface pressure: 50 MPa , Shaft material: S50C (quenched, surface roughness Rz: 0.8 μm) Test time: 10 hr

As is clear from the results of the examples and comparative examples shown in Table 1, Table 2, FIG. 2 and FIG. 3, the inorganic compound film layer according to the present invention was formed on the aluminum alloy layer of the bearing material. By providing it, excellent seizure resistance and wear resistance are exhibited. Further, it is apparent that the inorganic compound film layer of the present invention exhibits a sliding performance superior to that in the case of forming the conventional zinc phosphate film as shown in Comparative Example 3.

[0082] In each of Examples 16-23 and Comparative Examples 4-6 Examples 16 to 23 and Comparative Examples 4 to 6,
Simultaneously with Example 1, a sliding member was manufactured. However, the composition of the surface treatment liquid used, the treatment time, and the treatment liquid temperature were as shown in Table 3.

[0083]

[Table 3]

As a base member for the sliding member under test, a flat plate (30 mm × 30 mm) of (A) aluminum alloy (JIS AC8A) was used.
(2 mm) or (B) Alumina-silica fiber reinforced aluminum alloy (MMC) flat plate (30 mm x 3)
0 mm × 2 mm) was used. This was degreased with a degreasing agent for aluminum (Fine Cleaner 315: manufactured by Nihon Parkerizing Co., Ltd.) at a concentration of 20 g / liter for 2 minutes at 70 ° C., washed with water, and then subjected to an inorganic compound film layer forming treatment on the test substrate, After further washing with water, it was dried with hot air at 120 ° C. for 5 minutes.

Table 4 shows Examples 16 to 23 and Comparative Example 4
6 to 6 show the test materials used, the surface treatment conditions, and the materials and surface treatment methods of the abutting members combined therewith. As the contact member, a cylindrical test piece (diameter: 25
mm) was used. This cylindrical test piece is made of steel (SUS4
40C) sliding surface (2 mm ² ) with gas soft nitriding treatment, chromium plating, SiC dispersed Ni-
It was P alloy plated or untreated.

[0086]

[Table 4]

Examples 24-27 and Comparative Examples 7 and 8 In each of Examples 24-27 and Comparative Examples 7-8,
The test material A (aluminum alloy plate) was subjected to the same pretreatment as in Example 16 and then subjected to the inorganic compound film layer forming treatment using the surface treatment liquid shown in Table 5. However, in Comparative Example 7, an electrotin plating film was formed, and in Comparative Example 8, an electroless iron plating film was formed. As the cylindrical test piece (φ: 25 mm) of the contact member, as shown in Table 5, cast iron (FC23), alumina-silica reinforcing material-containing aluminum alloy, or an inorganic compound film forming treatment thereon. The applied one was used.

[0088]

[Table 5]

Examples 28-32 and Comparative Examples 9 and 1
0 In each of Examples 28 to 32 and Comparative Examples 9 to 10, the test material A (aluminum alloy plate) was used and Example 1 was used.
The same inorganic compound film formation treatment as in No. 6 was performed. However, the treatment liquid used was that shown in Table 6. In Comparative Examples 9 to 10, the film forming treatment was not performed. Further, the cylindrical test piece (φ: 25 mm) used as the contact member is an untreated aluminum alloy (AC2C or ADC10), or an aluminum alloy material of which alumite treatment is applied, Fe—C-based spraying Treated, electroless Ni
-P alloy plating was used.

[0090]

[Table 6]

Examples 15 to 32 and Comparative Examples 4-1
The sliding material-contact member combination obtained according to No. 0 was subjected to the following test. [Seizure test conditions] Test apparatus: Suzuki type thrust tester (ring-on-plate tester) Rotation speed: 1500 rpm (2.0 m / s) Load: Step-up gradual increase method (10 kgf / step) Lubricating oil: 5W-30 base oil (Temperature change) Lubricant amount: 200cc oil bath

[Abrasion test conditions] Test apparatus: Suzuki type thrust tester (ring-on-plate tester) Rotation speed: 1500 rpm (2.0 m / s) Load: 150 kgf Test time: 2 Hr Lubricating oil: 5W-30 Base oil (temperature Nariyuki) Lubricant amount: 200cc oil bath

In the seizure test, for various combinations of the test pieces (sliding member and contact member) shown in Tables 4 to 6, an average test piece (sliding member) and a cylindrical test piece (contact member) were used. Lubricant was applied to the contact part, and the cylindrical test piece was rotated at 1500 rp.
While rotating at m, gradually increase the pressing load of the cylindrical test piece against the flat plate test piece from 10 kgf,
Thereby, the seizure limit load was determined. Further, in the wear test, the flat plate test piece and the cylindrical test piece were slid in a lubricating oil similarly to the seizure test, and the wear depth of the flat plate test piece after the test of 150 kgf × 2 Hr was completed was measured. The test results are shown in FIGS. 4 and 5.

FIG. 4 shows that in Examples 16 to 23, the seizure resistance was significantly improved by providing the inorganic compound film layer, as compared with Comparative Examples 4 to 6. Among them, seizure resistance is higher in MMC reinforced with ceramic fibers than in the case where the base material of the flat plate test piece is an aluminum alloy. In addition, the seizure load varies depending on the difference in the mating material, and the characteristics were best when combined with the steel + nitriding product. In Examples 24 to 27, the base material of the flat plate test piece is the same as that of Example 16, but the mating material is different, and the result is the case of using cast iron or MMC as the mating material (piston skirt * cylinder bore combination). . Similar to the case of Example 16, when the inorganic compound coating layer of the present invention was provided, seizure resistance superior to that of Sn plating or Fe plating of Comparative Example was obtained. Also in the case of Examples 28 to 32, the material and surface treatment of the cylindrical test piece of the contact member are different from those of Examples 16 to 23 and 24 to 27, but Comparative Example 9,
As shown in 10, the case where the inorganic compound film layer of the present invention was formed on the surface of the flat plate test piece showed better seizure characteristics than the case where the contact member surface was subjected to alumite treatment (anodizing treatment). It was

Next, FIG. 5 shows that in Examples 16 to 23 in which the inorganic compound film layer of the present invention was provided on the surface of the flat plate test piece, the abrasion resistance was improved as compared with Comparative Examples 5 to 6. It indicates that (Note that in Comparative Example 4 and Comparative Example 9, seizure occurred during the abrasion test, so no abrasion strength data was obtained.) In Examples 24 to 27 and Examples 28 to 32 as well,
It was confirmed that the amount of wear was significantly smaller than that of Comparative Example, and that the wear resistance of the plate test piece was improved by forming the inorganic compound film layer of the present invention on the surface of the test piece.

[Brief description of drawings]

FIG. 1 is an explanatory sectional view of a sliding bearing shown as an embodiment of a sliding member of the present invention.

FIG. 2 is a graph showing the seizure test results of sliding members of Examples 1 to 15 and Comparative Examples 1 to 3.

FIG. 3 is a graph showing wear test results of sliding members of Examples 1 to 15 and Comparative Examples 1 to 3.

4 is a graph showing seizure test results of sliding member-contact member composites of Examples 16 to 32 and Comparative Examples 4 to 10. FIG.

FIG. 5 is a graph showing wear test results of sliding member-contact member composites of Examples 16 to 32 and Comparative Examples 4 to 10.

[Explanation of symbols]

 1 ... Steel back metal 2 ... Aluminum alloy layer 3 ... Inorganic compound film layer

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location F16C 33/14 7123-3J F16C 33/14 Z (72) Inventor Takashi Koyama 1 Nihonbashi, Chuo-ku, Tokyo Chome 15-1 Japan Parkerizing Co., Ltd. (72) Inventor Yoshio Fuwa 1 Toyota Town, Toyota City, Aichi Prefecture Toyota Automobile Co., Ltd. (72) Inventor Hirofumi Michioka 1 Toyota Town, Toyota City, Aichi Prefecture Toyota Automobile Within the corporation

Claims (8)

[Claims] 1. A base having a sliding surface formed of an aluminum alloy or an aluminum alloy containing a reinforcing material, and a molybdenum compound formed on the sliding surface of the base.
At least one metal compound selected from a tungsten compound and a chromium compound is converted into a metal and a total of 2 to
70% by weight, and the balance consisting essentially of oxygen,
And a slide member having an inorganic compound film layer having a film thickness of 0.1 to 20 μm. 2. A base having a sliding surface formed of an aluminum alloy or a reinforcing material-containing aluminum alloy, and a molybdenum compound formed on the sliding surface of the base.
At least one metal compound selected from a tungsten compound and a chromium compound is converted into a metal and a total of 2 to
48% by weight, 1 to 25% by weight of aluminum compound in terms of aluminum metal, 1 to 25% by weight of phosphorus compound in terms of phosphorus, and the balance consisting essentially of oxygen, and 0. A sliding member having an inorganic chemical conversion coating layer having a film thickness of 1 to 20 μm. 3. A substrate having a sliding surface formed of an aluminum alloy or a reinforcing material-containing aluminum alloy, wherein the sliding surface is at least one selected from molybdate ions, tungstate ions and chromate ions.
The method for producing the sliding member according to claim 1, wherein the sliding member is brought into contact with an aqueous solution containing fluorine ions. 4. At least one selected from molybdate ions, tungstate ions, and chromate ions is formed on the sliding surface of a substrate having a sliding surface formed of an aluminum alloy or a reinforcing material-containing aluminum alloy.
The method for producing a sliding member according to claim 1, wherein the sliding member is subjected to electrolytic treatment in an aqueous solution containing a seed, using the sliding surface as a cathode. 5. The at least one sliding surface of a substrate having a sliding surface formed of an aluminum alloy or a reinforcing material-containing aluminum alloy is selected from molybdate ion, tungstate ion and chromate ion.
The slide according to claim 2, which is brought into contact with an aqueous solution containing a fluorine ion and a seed and an ion of at least one phosphorus compound selected from phosphoric acid, phosphorous acid, and condensed phosphoric acid. A method of manufacturing a member. 6. At least one selected from molybdate ions, tungstate ions, and chromate ions is formed on the sliding surface of a substrate having a sliding surface formed of an aluminum alloy or a reinforcing material-containing aluminum alloy.
The electrolytic treatment is performed in an aqueous solution containing seeds and at least one phosphorus compound ion selected from phosphoric acid, phosphorous acid, and condensed phosphoric acid, with the sliding surface as a cathode. 2. A method for producing the sliding member according to 2. 7. A sliding member according to claim 1 or 2, an aluminum alloy, a reinforcing material-containing aluminum alloy,
It is made of one selected from HV400 or more steel, cast iron, and steel subjected to nitriding treatment or metal plating treatment, and is in contact with the sliding surface of the sliding member and slides relative to each other. A sliding member-contact member composite comprising a contact member. 8. The sliding member of the composite is selected from a groove portion and a skirt portion of an engine piston, a cylinder bore, a valve lifter, an A / T hydraulic control valve spool, a brake master cylinder piston, and a slide bearing. The sliding member-contact member composite according to claim 7, wherein the contact member is selected from a piston ring, a cylinder bore, a cylinder head, a valve body, and a shaft corresponding to the sliding member.