JP2001020054A - Copper-aluminum composite thermal spraying layer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a copper-aluminum composite layer by thermal spraying by allowing it to contain copper or a 1st copper alloy and aluminum or a 1st aluminum alloy, allowing the copper or 1st copper alloy to contain at least an undissolved phase and allowing the aluminum or 2nd aluminum alloy to contain at least a dissolved phase. SOLUTION: The ratio of a copper alloy and an aluminum alloy is desirably controlled to, by weight, 80 to 30% copper alloy, and the balance aluminum alloy. The preferable combination of the composite components is composed of the copper alloy contg., by weight, <=40% Pb and 12 to 60% Si-Al alloy. The desirable Si content is 15 to 50 wt.%, and the dimensions of the Si particles are desirably controlled to 1 to 40 μm. The compsn. of the whole of the copper- aluminum composite thermal spraying layer is preferably composed of, by weight, 8 to 82% Cu, 5 to 50% Al, <=40% Pb and 5 to 50% Si. In the undissolved copper alloy, fine Pb in the copper alloy powder remains in the thermal spraying layer and contributes to the improvement of its sliding characteristics, and, in the dissolved Al alloy, shapeless Si disperses into the thermal spraying layer to improve its wear resistance.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a sprayed copper-aluminum composite material. The technical fields to which the present invention relates are composite materials, thermal spraying techniques, aluminum alloy sliding materials and copper alloy sliding materials.

[0002]

2. Description of the Related Art As a metal-based composite material, a composite material of a metal and a ceramic has been mainly studied, and a method for producing the composite material is a method of sintering a mixed powder of copper powder and Al ₂ O ₃ powder after press molding ( Japanese Patent No. 2854916), a method of impregnating a ceramic carbon with a molten Al alloy (Japanese Patent No. 2846635)
No.). As a sliding layer having a composite structure of metal and metal, there is a clad material. Regarding the thermal spraying technology, see the Metallurgy Society of Japan, Vol. 33 (1994) No.
3. P268-275 "Recent Advances in Thermal Spraying Technology"
And a method for producing a metal-ceramic composite material. Similarly, Tribologist Vo
l41 (1996), no. There is a commentary on thermal spraying technology on pages 11, 19-24.

As a material belonging to the copper-aluminum composite material, there is Japanese Patent Application Laid-Open No. 9-129555 which discloses a plain bearing in which a soft layer having a hardness similar to that of white metal is dispersed in an aluminum alloy base material. This composite material manufacturing method includes a first step of testing a flat plate made of an aluminum alloy material with a back metal, and a second step of closely adhering a soft material of Sn, Pb or white metal to a front surface of the flat plate with a thickness of 50 to 100 μm. A third step of forming a soft alloy layer by dissolving the soft material into the aluminum alloy by locally irradiating a laser beam to the flat plate on which the soft material is adhered; It comprises a fourth step of bending and a fifth step of grinding the soft material after each of the laser-sprayed surfaces has been machined and finished and exposing a composite layer of an aluminum alloy and a soft alloy layer inside the soft material.

Among copper alloys, particularly, as a sliding alloy, Cu-Pb, in which Pb is added to improve adhesion and seizure resistance by adding Pb, is frequently used. Copper alloys have poor abrasion resistance, and for example, the present applicant's US Pat. No. 5,326,384
It is known that sintering is performed by adding a hard material such as Fe ₂ P as proposed in the above-mentioned publication, but it is unavoidable that the addition of the hard material deteriorates the adaptability and the like.

A technique for spraying a copper alloy sliding material is known from the applicant's International Publication WO95 / 25224.
This publication also discloses a copper-hard composite material.

[0006]

Problems to be Solved by the Invention WO 95/252, supra.
From 24, a part of the structure of the Cu-Pb alloy by thermal spraying technology,
In particular, although it has been proposed that the Pb phase is not coarsened by not spraying the Pb structure to improve the sliding characteristics, it is difficult to improve the wear resistance by hardening the copper sprayed alloy. It is. In other words, the hardening method of copper alloys is widely performed mainly by using precipitation hardening for working alloys such as rolling and drawing, but it is basically impossible to harden a sprayed alloy that is a cast alloy by devising the composition. There is a limit.

[0007]

That is, the present invention comprises copper or a first copper alloy and aluminum or a first aluminum alloy, wherein the copper or the first copper alloy has at least an undissolved phase. In addition, the aluminum or the first aluminum alloy provides a sprayed copper-aluminum composite material having at least a molten phase.
Copper or copper alloy (hereinafter collectively referred to as “copper alloy”) and aluminum or aluminum alloy (hereinafter “aluminum alloy”)
In order to obtain a composite material of (hereinafter collectively referred to as), it is necessary that a part of these alloys is dissolved to serve as a binder. From another viewpoint, for example, P in a Cu-Pb alloy
b, It is necessary to avoid complete dissolution of the copper and aluminum alloys, since even small amounts of Si in the Al-Si alloy will interfere with the properties of the other alloy's matrix and will not be a useful composite. In the present invention, if at least the aluminum alloy is dissolved, a binder effect for forming a composite structure is realized. That is, copper and aluminum are originally compatible substances and are suitable for bonding.

The above-mentioned composite material can be obtained by a thermal spraying method. As a general tendency of thermal spraying, (a) when the average particle size of the copper alloy powder and the aluminum alloy powder are equal, the aluminum alloy powder dissolves, and (b) when the average particle size of the aluminum alloy powder is much larger than the copper alloy powder. Also dissolves the latter. By utilizing such a tendency, it is possible to produce a copper-aluminum composite material in which at least a part of the aluminum alloy powder is dissolved and the remainder substantially maintains the properties of the solid powder. Pure aluminum wear resistance is superior to copper (alloy), and many aluminum alloys have excellent wear resistance in the cast state,
By compounding this with the copper alloy without entirely alloying it, the wear resistance of the entire composite material can be improved as compared with copper (alloy). In consideration of these, the ratio of the copper alloy and the aluminum alloy is 80 to 3 by weight.
It is preferred that the content is 0% and the balance is the latter. In the present invention, the “dissolved phase” is a structure dissolved during thermal spraying of the copper-aluminum composite material. That is, according to most of the manufacturing processes, the metal material has been melted, but is in a state of being melted and solidified particularly during thermal spraying.

In the present invention, copper and aluminum alloys include all alloys that can be sprayed. When the tempered state of metal is roughly classified into cast state and rolling, drawing and other processing states, thermal spray alloys belong to the former tempered state,
Cast copper alloys, such as bronze, lead bronze, phosphor bronze, are the subject of the present invention. On the other hand, since the copper-brought product used in the electronic equipment is an alloy in a processed and tempered state, it can be sprayed, but cannot exhibit its original performance. Similarly, wrought aluminum alloy is excluded from the present invention, and Al-S having excellent wear resistance is used.
A cast aluminum alloy such as an i-type cast alloy is an object of the present invention. Further, the first copper alloy and the first aluminum alloy according to the first aspect of the present invention also include a second copper alloy and a second aluminum alloy, respectively, which are partially fused by thermal spraying. That is, the composite material of the present invention excludes a state in which the copper alloy and the aluminum alloy are completely fused, but may partially fuse. Thus, the composite material of such an embodiment comprises a thermally sprayed copper alloy, a thermally sprayed aluminum alloy, and a thermally sprayed copper-aluminum alloy. In the following description, unless otherwise specified, the copper alloy and the aluminum alloy are the first copper alloy and the second aluminum alloy, respectively.

In the present invention, a preferred combination of composite components is a copper alloy containing a Pb-containing alloy having excellent seizure resistance, and an aluminum alloy containing a Si-containing alloy having excellent wear resistance. More specifically, 40% or less by weight of Pb
And a combination of a 12-60% Si-Al alloy. When the Si content of the aluminum alloy is less than 12%, the effect of improving the wear resistance and seizure resistance is small, and it is 60%.
If it exceeds 300, the strength is remarkably reduced, and the wear resistance is lowered.
The preferred Si content is 15-50%. If the size of the Si particles exceeds 50 μm, the Si particles will easily fall off. Preferred dimensions are between 1 and 40 μm. The composition of the entire copper-aluminum composite material according to this combination is Cu:
8 to 82% by weight, Al: 5 to 50% by weight,: 40% by weight
Hereinafter, the content of Si is preferably 5 to 50% by weight.

In the present invention, the copper alloy is expressed as a percentage by weight,
Up to 40% Pb, up to 30% Sn, up to 0.5% P, up to 15% Al, up to 15% Ag, up to 5% Mn, up to 5% Cr, up to 20% Ni and One or more selected from the group consisting of 30% or less of Zn is 0.5% or more, preferably 1% or more and 50% or more in total.
The following can be contained. Lead is the most preferred element for improving the sliding characteristics under dry conditions. However, if the lead content exceeds 40%, the strength of the copper alloy is reduced, so it is necessary to set the upper limit to 40%. The preferred lead content is 1 to 30%, more preferably 2 to 15%. The additional elements other than lead mainly form a solid solution in copper to enhance its wear resistance and seizure resistance. Among them, Ag significantly enhances the sliding characteristics under the condition that the lubricating oil is small. Regarding the addition amount, Sn precipitates at 10% or more and Mn at 1% or more, and the precipitates enhance the wear resistance. Sn exceeds 30%,
P exceeds 0.5%, Al exceeds 15%, Mn is 5%
, Cr exceeds 5%, Ni exceeds 20%, Zn
Exceeds 30%, the thermal conductivity inherent in copper, good sliding properties with iron or aluminum-based mating materials, wear resistance,
Seizure resistance is lost. Therefore, it is necessary that these elements do not exceed the above upper limits. Preferred contents are Sn: 0.1 to 20%, P: 0.2 to 0.5% or less,
Ag: 0.1-8%, Mn: 0.5-4%, Cr: 0.
5 to 3%, Ni: 0.5 to 15%, Zn: 5 to 25%, more preferably Sn: 0.1 to 15%, Ag:
0.2-5%, Mn: 0.5-3%, Cr: 1-2%,
Ni: 1 to 10%, Zn: 10 to 20%. For the above reasons, the total amount of the added elements should be in the range of 0.5 to 50%. The first copper alloy containing these additional elements (excluding the second copper alloy) is made of a Cu crystal (that is, a Cu solid solution) in which these elements are dissolved, or a Cu crystal (including a Cu solid solution) And other phases. Other phases are a crystallization phase, a precipitation phase, a decomposition phase, and the like. These phases are composed of metals, intermetallic compounds, Cu ₃
And other compounds such as P. That is, if the first copper alloy (excluding the second copper alloy) is made only of these compounds, etc., the sliding characteristics inherent to copper are not exhibited, so that the Cu crystal is an essential component as described above. Is preferred. However, the second copper alloy may be composed of only a compound.

The composition of the entire composite material obtained by compounding these copper alloys is, by weight percentage, Cu: 8 to 82%, Al: 5 to 5%.
50%, Pb: 40% or less, Si: 5 to 50%, Sn:
30% or less, P: 0.5% or less, Ag: 10% or less, M
n: 5% or less, Cr: 5% or less, Ni: 20% or less, Z
n: preferably 30% or less.

An Al-Si-Sn alloy is a material having excellent wear resistance and seizure resistance as a wear-resistant and seizure-resistant part. Sn is a component that imparts lubricity and conformability, and is uniformly dispersed in the aluminum matrix. or,
Sn adheres preferentially to the partner shaft and adheres to the partner shaft.
1 and Al of the bearing are prevented from sliding with each other by the same material, and seizure resistance is enhanced. If the Sn content is less than 0.1%, the effect of improving lubricity is small, and if it exceeds 30%, the strength of the alloy is reduced. Preferred Sn content is 5 to 25%
It is. It is thought that it exists very close to the Sn particles and prevents the Sn particles from coarsening, thereby improving the fatigue resistance.

The aluminum alloy can contain the following optional elements. Cu: Cu is supersaturated in the aluminum matrix to form a solid solution to increase the strength, thereby suppressing the adhesive wear of aluminum and the wear caused by the Si particles falling off. Further, Cu forms a part of Sn and an Sn-Cu intermetallic compound to enhance wear resistance. However, if the Cu content exceeds 7.0%, the alloy is excessively hardened, and thus becomes unsuitable as a sliding member. The preferred Cu content is 0.1.
5 to 5%. Mg: Mg combines with a part of Si to form an Mg-Si intermetallic compound and enhances wear resistance. However, if the Mg content exceeds 5.0%, a coarse Mg phase is generated, and the sliding characteristics deteriorate. Mn: Mn has a similar effect to Cu by forming a super-saturated solid solution in an aluminum matrix to increase its strength. However, when the content of Mn exceeds 1.5%, the alloy is excessively hardened and thus becomes unsuitable as a sliding member. The preferred Mn content is 0.1-1%. Ni: Ni has a similar effect to Cu by forming a solid solution in an aluminum matrix in a supersaturated manner to increase its strength. However, if the Ni content exceeds 8%, the alloy is excessively hardened, and thus becomes unsuitable as a sliding member. The preferred Ni content is 0.1-5%. A first aluminum alloy containing these additional elements (however,
The aluminum alloy (excluding the aluminum alloy) is composed of an Al crystal (that is, an Al solid solution) in which these elements are dissolved, or is composed of an Al crystal (including an Al solid solution) and another phase. Other phases are a crystallization phase, a precipitation phase, a decomposition phase, and the like, and these phases are metals, intermetallic compounds, other compounds, and the like. That is, if the first aluminum alloy (excluding the second aluminum alloy) is made only of these compounds, etc., the binder function of the aluminum alloy is not exerted, so that the Cu crystal is an essential component as described above. Is preferred. However, the second aluminum alloy may be composed of only a compound.

The overall composition of the copper-aluminum composite material is, by weight percentage, Cu: 8 to 82%, Al: 5 to 5%.
0%, Pb: 40% or less, Si: 12 to 60%, Sn:
30% or less, Mg: 5% or less, Mn: 5% or less, Fe:
Preferably, it is 1.5% or less, Cr: 5% or less, and Ni: 20% or less.

Before explaining the features of the structure of the copper-aluminum composite material of the present invention, general features of the metal structure of the sprayed layer will be described. This is a structure obtained by melting and solidifying powder such as atomized powder. In one embodiment, the droplets generated by melting in the thermal spraying frame are deformed by colliding with the substrate surface, and when viewed in a layer cross section, a layered, flaky or flat portion is viewed as a small disk in a layer plane, Scales are piled up. In yet another form, when the powder such as atomized powder is pumped into the frame by gas, it retains the form of isolated particles in which each is dispersed, and a part of the particles is united, but in the form as it is. It is thought to melt. The molten droplet collides with the base material and solidifies, but if the thickness of the sprayed layer is reduced and the cooling is accelerated, one or several droplets do not coalesce with many other droplets due to fusion etc. Solidifies as independent particles. In this way, relatively small droplets are crushed, and a large number of fine layered pieces are stacked as a whole to form a sprayed layer.
In other forms, the droplets coalesce into a large layer and solidify.

In the present invention, the copper alloy powder is contained at least in the sprayed layer without being melted during the spraying, and a mixed structure of a dissolved phase of the aluminum alloy and an undissolved phase of the copper alloy powder is formed. The undissolved phase of the copper alloy powder constituting this structure is a structure in which the structure of the copper alloy powder does not disappear even during the spraying flame and remains in the sprayed layer. Therefore, the dissolved phase is a normal spray-dissolved tissue having the form described in the previous paragraph,
That is, the tissue dissolved during thermal spraying, and the undissolved phase is a tissue that does not dissolve during thermal spraying. The undissolved phase can be distinguished from the dissolved phase by light microscopy because some of the morphology described in the preceding paragraph is missing or less pronounced, as exemplified below. The dissolved phase coalesces and melts, the undissolved phase does not coalesce. The dissolved phase has a large deformation due to collision, and the undissolved phase has a small deformation due to collision. In the case of an alloy such as Cu-Pb, P constituting the secondary phase
Focusing on b, the dissolved phase and the undissolved phase can sometimes be distinguished. Since the Al alloy phase of the thermal sprayed layer is composed of a pattern having a similar form, it may be difficult to determine the above by (1). In this case, it is impossible to determine the crystal grain boundary, and when it looks like a continuous phase at a glance and the secondary phase also has a uniform morphology, it can be determined to be a dissolved structure. When the Al alloy phase of the thermal spray layer is composed of particles of the same form, it is compared with known powder forms such as atomized powder, pulverized powder, and electrolytic powder. A part of the copper (alloy) powder and the aluminum alloy powder fuse, and then the Cu-based secondary phase is dispersed from the aluminum matrix. This is the molten phase of the second aluminum alloy referred to in the present invention. Note that this secondary phase is easily distinguished from other tissues. When a part of the copper (alloy) powder melts and takes in aluminum, and then an Al-based secondary phase precipitates and disperses from the copper matrix, such a structure is a dissolved phase of the second copper alloy. or,
Even when the taken-in aluminum remains in a solid solution state, it is also a dissolved phase of the second copper alloy. Since copper (alloy) always has an undissolved structure, it is easy to distinguish the dissolved structure of copper (alloy) from the undissolved structure.

The properties of each of the constituent alloy phases of the copper-aluminum composite material having these structures are described as Cu-Pb alloy and Al-
An example of Si will be described. In the undissolved Cu alloy, the fine Pb phase in the copper alloy powder such as atomized remains in the sprayed layer and contributes to the improvement of the sliding characteristics, and further (dissolves or does not dissolve) the components of the Al alloy, that is, Al, Si When dissolved in a Cu alloy, it may weaken the inherent hard-to-adhere property of copper, but this can be prevented. In the molten Cu-Pb alloy, the Pb phase coarsens when Cu and Pb are melted and solidified, and the Al-Si alloy powder is bonded by a reaction occurring between the molten Cu, Pb and the Al-Si alloy powder. At this time, the surface of the powder is often melted. The molten Al alloy does not have a particle shape that has a clearly long one-way direction in the thermal sprayed layer, such as the primary crystal Si of a conventional ingot alloy or the Si particles of a rolled alloy. However, granular Si particles having almost the same dimensions and being spherical, massive, polygonal, and other irregular shapes not classified into these are dispersed. Further, in the case of the present invention, it is difficult to distinguish between primary crystal eutectic Si and eutectic Si, which is obvious in the conventional ingot alloy. The improvement in wear resistance is large due to such a Si structure. Also, molten Al-Si alloy powder and Cu-Pb
The reaction that takes place with the alloy powder binds the latter powder.

Subsequently, a method of forming the composite sliding layer by thermal spraying will be specifically described. In the present invention, various thermal spraying methods described in the above-mentioned tribologist, page 20, FIG. 2 can be employed. Among them, high-speed gas flame thermal spraying (HVOF, High velocity oxyfuel) is preferably employed. it can. This method is described on page 20, right column, Nos. 4-13.
Since it has the features described in the row,
And Sn particle morphology is believed to be obtained. Since the sprayed Al is hardened by rapid solidification, it has a feature of high retention of Si particles. Therefore, as a thermal spray powder capable of suppressing abrasion due to Si particles falling off, Cu-Pb
An atomized powder such as an alloy, an Al-Si alloy, or an Al-Si-Sn alloy can be used. Thermal spraying conditions include an oxygen pressure of 0.45 to 0.76 MPa and a fuel pressure of 0.
It is preferably 45 to 0.76 MPa and a spraying distance of 50 to 250 mm. The thickness of the sprayed layer is preferably from 10 to 500 μm.

Subsequently, an average powder particle size adjusting method will be described as a method for producing a composite material having the structure of the present invention. Table 1 shows an example in which an aluminum alloy powder similar to a copper alloy powder having a particle size showing a normal distribution around one average value is mixed.

[0021]

[Table 1]

In the following table, fine powder Cu-Pb and coarse powder Al-Si
By selecting the combination, the amount of copper alloy dissolved can be increased. In general, the hardness of a composite material of a hard material and a soft material is in between these, but in the composite material of the present invention,
Since a reaction phase of the copper alloy and the aluminum alloy may be generated, the average value of the hardness is higher than both.

[0023]

[Table 2]

As the substrate on which the thermal spray layer is formed, iron, copper,
Various metal substrates such as aluminum can be used. The shape of the substrate is arbitrary, such as a plate, a disk, and a tube. If the surface of the substrate is roughened to a surface roughness of preferably Rz 10 to 60 μm by shot blasting or the like, the adhesion strength of the film increases. The hardness can be adjusted by subjecting the sprayed layer to heat treatment. At this time, some tissues may be dissolved.

The above-mentioned copper-aluminum composite material, 30% or less, preferably 1 to 10% by weight of Al ₂
O ₃ , SiO ₂ , SiC, ZrO ₂ , Si ₃ N ₄ , BN, A
1N, TiN, TiV, B, C, iron-phosphorus compound, iron-
One or more compounds selected from the group consisting of phosphorus compounds, iron-boron compounds, and iron-nitrogen compounds can be added as a wear resistance improving component. If the added amount of these components exceeds 30%, lubricity and conformability become poor, and as a result, seizure tends to occur.

Furthermore, in the present invention, graphite can be contained in an amount of 30% or less by weight percentage. Graphite is an additive that improves lubricity and prevents cracking of the sliding layer. If the graphite content exceeds 30%, the strength of the sprayed layer is undesirably reduced. The preferred graphite content is 1.
5 to 15%.

In the present invention, copper, nickel, aluminum, a copper-nickel-based alloy, a nickel-aluminum-based alloy, a copper-aluminum-based alloy, a copper-tin-based alloy are provided between the sprayed layer and the substrate in order to enhance the adhesion of the sprayed layer. System alloy, nickel self-fluxing alloy and cobalt self-fluxing alloy, an intermediate layer made of one or more materials selected from the group consisting of plating, sputtering,
It is preferably formed by a method such as thermal spraying. All of these materials require their surfaces to be rough, but since they are easily alloyed with bronze, they are firmly bonded to the (un) dissolved layer during thermal spraying and are bonded to the thermal spray layer and back metal. Increase strength. The preferred thickness of the intermediate layer is 5 to 100 μm. As the copper-tin alloy, a Cu-Sn-P-based alloy can be used. Since this alloy has a good molten metal flow and is hard to be oxidized, excellent performance can be obtained when the intermediate layer is formed by thermal spraying.

The above thermal sprayed surface layer is made of Pb, Pb alloy,
When coated with a soft metal layer such as Sn or Sn alloy plating, they wear rapidly and create a good conforming surface, so that subsequent abrasion is difficult to occur. The soft metal layer is
For example, it is a plating layer mainly composed of Pb and Sn. Further, the above-mentioned thermal sprayed surface layer may be covered with a film containing MoS ₂ or graphite or a mixture of MoS ₂ and graphite, which is bonded with a resin binder. The thickness of these coating layers is preferably 1 to 50 μm. Less than,
The examples illustrate the method of the present invention in more detail.

[0029]

EXAMPLE 1 60 wt% Cu-10 wt% Pb-10 wt% Sn alloy atomized powder (average particle size 30 μm) and 40 wt% aluminum alloy atomized powder (however, 40 wt% Si was added to A2024 aluminum alloy) Atomized powder of the alloy thus obtained, and an average particle size of 100 μm) were mixed, and a commercially available pure aluminum rolled plate was coated with a steel grid (size 0.7 m).
m) by shot blasting to make the surface Rz45
A 250 μm-thick spray was applied to the substrate roughened to μm. For the thermal spraying, an HVOF type thermal spraying machine (DJ manufactured by Sulzer Metco) was used to perform thermal spraying under the following conditions. Oxygen pressure: 150 psi Fuel pressure: 100 psi Spray distance: 180 mm Spray thickness: 250 μm The hardness of this sprayed layer was Hv 260-300. or,
The overall composition was 36% Cu, 31% Al,
They were 3% Pb, 22% Si, 4% Sn, and the remaining impurities.

The sprayed alloys of Example 1 and Comparative Example 1 were subjected to a wear resistance test by the following method. Abrasion resistance test method A steel ball (SUJ2) having a diameter of 8 mm was pressed against the sprayed layer of a test piece with a load of 1 kgf, and slid at a speed of 0.5 mm / sec under dry conditions. The test results are shown in Table 3.

Example 2 In place of the copper alloy atomized powder of Example 1, Cu-24w
Thermal spraying was carried out in the same manner as in Example 1 except that atomized powder of t% Pb-4wt% Sn alloy was used. Example 1
Table 3 shows the results of the same abrasion resistance test. The hardness of this sprayed layer was Hv220-280. The total composition is 36% Cu, 32% Al, 7% Pb,
It was 23% Si, 2% Sn, and residual impurities.

Example 3 75 wt% Cu-10 wt% Pb-4 wt% Sn alloy atomized powder (average particle diameter 60 μm) and 25 wt% aluminum alloy atomized powder (however, 40 wt% Si was added to A2024 aluminum alloy) Atomized powder of the alloy and an average particle diameter of 100 μm) were mixed, and commercially available pure aluminum was sprayed under the same conditions as in Example 1. Fig. 1 shows the microstructure observed without etching the surface of the sprayed layer.
FIG. 2 shows a surface structure etched with a Grade solution (5 g of ferric chloride, 100 cc of hydrochloric acid, 100 cc of water) for 5 seconds, and FIG. 3 shows a microstructure observed without etching the cross section. Fig. 4
Shown in That is, the copper alloy powder has a lump portion that remains in the form of an atomized powder, judging from the form, and a portion that disappears and crystallizes together with the aluminum alloy melted during thermal spraying. Aluminum alloy, on the other hand, leaves little powder form. Since the aluminum alloy phase is a base for crystallizing the copper alloy phase into a net or flake, the aluminum alloy is almost completely melted, reacts with the dissolved copper, and is judged to have crystallized as a Cu-Al compound Is done. The hardness of this sprayed layer was Hv200-260.
The overall composition is 45% Cu, 27% A by weight.
1, 6% Pb, 16% Si, 6% Sn, and the remaining impurities.

Example 4 Instead of the copper powder of Example 3, Cu-24 wt% Pb-4% S
Thermal spraying was performed under the same conditions as in Example 3 except that an n-alloy atomized powder (average particle size: 60 μm) was used. Table 3 shows the results of the same abrasion resistance test as in Example 1. The average hardness of this sprayed layer was Hv90-260. The total composition is 42% Cu, 26% Al, 13% by weight.
% Pb, 17% Si, 2% Sn, and the remaining impurities.

Example 5 In place of the copper alloy atomized powder having an average particle diameter of 60 μm in Example 3, a copper alloy atomized powder having an average particle diameter of 30 μm, and A
Thermal spraying was performed under the same conditions as in Example 3 except that atomized powder of an alloy obtained by adding 20 wt% Si to a 2024 aluminum alloy was used. Table 3 shows the results of the same abrasion resistance test as in Example 1. The average hardness of this sprayed layer is Hv2
20-260. The total composition is 57% Cu, 26% Al, 5% Pb, 5% Si, 6% by weight percentage.
Sn and the remainder were impurities.

Example 6 The copper powder of Example 5 (that is, Cu-10 wt% Pb-1)
0 wt% Sn alloy atomized powder) instead of Cu-24
Thermal spraying was performed under the same conditions as in Example 3 except that atomized Pb-10% Sn alloy atomized powder (average particle size: 30 μm) was used. Table 3 shows the results of the same abrasion resistance test as in Example 1. The hardness of this sprayed layer is Hv190-240.
Met. The total composition is 50% C by weight percentage.
u, 32% Al, 9% Pb, 7% Si, 2% Sn, and the remaining impurities.

Comparative Example 1 Only the copper alloy powder of Example 1 was sprayed in the same manner as in Example 1. Table 3 shows the results of the same abrasion resistance test as in Example 1. The hardness of this sprayed layer was Hv180-210.

Comparative Example 2 Only the aluminum alloy of Example 1 was sprayed in the same manner as in Example 1. Table 3 shows the same wear resistance test effects as in Example 1. The hardness of this sprayed layer is Hv210-230.
Met.

[0038]

[Table 3]

Example 7 A 90% Pb-1 layer having a thickness of 5 μm was formed on the sprayed layer of Example 1.
A 0% Sn plating layer was formed. This sprayed layer and Example 1
Was subjected to an abrasion test by the following method. The test results are shown in FIG. By comparing the results of these examples, it can be seen that the Pb-Sn plating layer reduces the rate of increase in the amount of wear.

[0040]

As described above, the copper (alloy) -aluminum (alloy) composite material by thermal spraying according to the present invention is significantly enhanced as compared with the aluminum (alloy) or copper (alloy) thermal sprayed layer.

[Brief description of the drawings]

FIG. 1 is a photomicrograph of the surface structure of a thermal sprayed composite material of Example 3 of the present invention observed without etching.

FIG. 2 is a micrograph obtained by etching and observing a surface structure of a thermal sprayed composite material in Example 3 of the present invention.

FIG. 3 is a photomicrograph of the cross-sectional structure of the thermal sprayed composite material of Example 3 of the present invention observed without etching.

FIG. 4 is a micrograph obtained by etching and observing a cross-sectional structure of a thermal sprayed composite material according to Example 3 of the present invention.

FIG. 5 is a graph showing the results of a friction test of Example 7 of the present invention.

[Procedure amendment]

[Submission Date] August 7, 2000 (2000.8.7)

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] Name of invention

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[Title of the Invention] Copper-aluminum composite sprayed layer

[Procedure amendment 2]

[Document name to be amended] Statement

[Correction target item name] Claims

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[Claims]

[Procedure amendment 3]

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[Correction target item name] 0001

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[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention
The present invention relates to a composite sprayed layer . The technical fields to which the present invention relates are composite materials, thermal spraying techniques, aluminum alloy sliding materials and copper alloy sliding materials.

[Procedure amendment 4]

[Document name to be amended] Statement

[Correction target item name] 0007

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[0007]

That is, the present invention comprises copper or a first copper alloy and aluminum or a first aluminum alloy, wherein the copper or the first copper alloy has at least an undissolved phase. In addition, the aluminum or the first aluminum alloy provides a copper-aluminum composite sprayed layer having at least a molten phase. In order to form a composite sprayed layer of copper or copper alloy (hereinafter collectively referred to as "copper alloy") and aluminum or aluminum alloy (hereinafter collectively referred to as "aluminum alloy"), a part of these alloys is melted to form a binder. It is necessary to play a role. From another viewpoint, for example, P in a Cu-Pb alloy
b, It is necessary to avoid complete dissolution of the copper and aluminum alloys, since even small amounts of Si in the Al-Si alloy will interfere with the properties of the other alloy's matrix and will not be a useful composite. In the present invention, if at least the aluminum alloy is dissolved, a binder effect for forming a composite structure is realized. That is, copper and aluminum are originally compatible substances and are suitable for bonding.

[Procedure amendment 5]

[Document name to be amended] Statement

[Correction target item name] 0008

[Correction method] Change

[Correction contents]

As a general tendency of thermal spraying , (a) when the average particle size of the copper alloy powder and the aluminum alloy powder are equal, the aluminum alloy powder is dissolved, and (b) the average particle size of the aluminum alloy powder is much higher than that of the copper alloy powder. If larger, the latter also dissolves. By taking advantage of these trends,
A copper-aluminum composite sprayed layer can be produced in which at least a part of the aluminum alloy powder is dissolved and the remainder substantially maintains the properties of the solid powder. Pure aluminum has higher wear resistance than copper (alloy), and many aluminum alloys have excellent wear resistance in the cast state. By doing so, the wear resistance of the entire composite sprayed layer can be improved over copper (alloy). Considering these,
As for the ratio between the copper alloy and the aluminum alloy, the former is preferably 80 to 30% by weight, and the balance is preferably the latter. In the present invention, the “dissolved phase” refers to the copper-aluminum composite thermal spray.
Tissue dissolved during spraying of the layer . In other words, the metal material has undergone melting according to most manufacturing processes,
In particular, it is in a state of being melted and solidified during thermal spraying.

[Procedure amendment 6]

[Document name to be amended] Statement

[Correction target item name] 0009

[Correction method] Change

[Correction contents]

In the present invention, copper and aluminum alloys include all alloys that can be sprayed. When the tempered state of metal is roughly classified into cast state and rolling, drawing and other processing states, thermal spray alloys belong to the former tempered state,
Cast copper alloys, such as bronze, lead bronze, phosphor bronze, are the subject of the present invention. On the other hand, since the copper-brought product used in the electronic equipment is an alloy in a processed and tempered state, it can be sprayed, but cannot exhibit its original performance. Similarly, wrought aluminum alloy is excluded from the present invention, and Al-S having excellent wear resistance is used.
A cast aluminum alloy such as an i-type cast alloy is an object of the present invention. Further, the first copper alloy and the first aluminum alloy according to the first aspect of the present invention also include a second copper alloy and a second aluminum alloy, respectively, which are partially fused by thermal spraying. That is, the composite sprayed layer of the present invention excludes the state where the copper alloy and the aluminum alloy are completely fused,
It may be partially fused. Accordingly, the composite sprayed layer of such an embodiment comprises a sprayed copper alloy, a sprayed aluminum alloy, and a copper-aluminum alloy formed by spraying. In the following description, unless otherwise specified, copper alloy and aluminum alloy are the first copper alloy and aluminum alloy, respectively .
1 is an aluminum alloy.

[Procedure amendment 7]

[Document name to be amended] Statement

[Correction target item name] 0010

[Correction method] Change

[Correction contents]

In the present invention, a preferred combination of composite components is a copper alloy containing a Pb-containing alloy having excellent seizure resistance, and an aluminum alloy containing a Si-containing alloy having excellent wear resistance. More specifically, 40% or less by weight of Pb
And a combination of a 12-60% Si-Al alloy. When the Si content of the aluminum alloy is less than 12%, the effect of improving the wear resistance and seizure resistance is small, and it is 60%.
If it exceeds 300, the strength is remarkably reduced, and the wear resistance is lowered.
The preferred Si content is 15-50%. If the size of the Si particles exceeds 50 μm, the Si particles will easily fall off. Preferred dimensions are between 1 and 40 μm. The composition of the entire copper-aluminum composite sprayed layer according to this combination is C
u: 8 to 82% by weight, Al: 5 to 50% by weight, Pb: 40
% By weight or less, preferably 5 to 50% by weight of Si.

[Procedure amendment 8]

[Document name to be amended] Statement

[Correction target item name] 0012

[Correction method] Change

[Correction contents]

The composition of the entire composite sprayed layer obtained by compounding these copper alloys is, as a percentage by weight, Cu: 8 to 82%, Al: 5%.
-50%, Pb: 40% or less, Si: 5-50%, S
It is preferable that n: 30% or less, P: 0.5% or less, Ag: 10% or less, Mn: 5% or less, Cr: 5% or less, Ni: 20% or less, and Zn: 30% or less.

[Procedure amendment 9]

[Document name to be amended] Statement

[Correction target item name] 0015

[Correction method] Change

[Correction contents]

The total composition of the copper-aluminum composite sprayed layer is, as a percentage by weight, Cu: 8 to 82%, Al: 5 to 5%.
50%, Pb: 40% or less, Si: 12 to 60%, S
n: 30% or less, Mg: 5% or less, Mn: 5% or less, F
e: 1.5% or less, Cr: 5% or less, and Ni: 20%
The following is preferred.

[Procedure amendment 10]

[Document name to be amended] Statement

[Correction target item name] 0016

[Correction method] Change

[Correction contents]

Before describing the features of the structure of the copper-aluminum composite sprayed layer of the present invention, general features of the metalized structure of the sprayed layer will be described. This is a structure obtained by melting and solidifying powder such as atomized powder. In one embodiment, the droplets generated by melting in the thermal spraying frame are deformed by colliding with the substrate surface, and when viewed in a layer cross section, a layered, flaky or flat portion is viewed as a small disk in a layer plane, Scales are piled up. In yet another form, when the powder such as atomized powder is pumped into the frame by gas, it retains the form of isolated particles in which each is dispersed, and a part of the particles is united, but in the form as it is. It is thought to melt. The molten droplet collides with the base material and solidifies, but if the thickness of the sprayed layer is reduced and the cooling is accelerated, one or several droplets do not coalesce with many other droplets due to fusion etc. Solidifies as independent particles. In this way, relatively small droplets are crushed, and a large number of fine layered pieces are stacked as a whole to form a sprayed layer.
In other forms, the droplets coalesce into a large layer and solidify.

[Procedure amendment 11]

[Document name to be amended] Statement

[Correction target item name] 0018

[Correction method] Change

[Correction contents]

A copper-aluminum composite having these structures
The characteristics of each alloy phase of the sprayed layer are represented by Cu-Pb alloy and Al
An example of -Si will be described. In the undissolved Cu alloy, the fine Pb phase in the copper alloy powder such as atomized remains in the sprayed layer and contributes to the improvement of the sliding characteristics, and further (dissolves or does not dissolve) the components of the Al alloy, that is, Al, Si When dissolved in a Cu alloy, it may weaken the inherent hard-to-adhere property of copper, but this can be prevented. In the molten Cu-Pb alloy, the Pb phase coarsens when Cu and Pb are melted and solidified, and the Al-Si alloy powder is bonded by a reaction occurring between the molten Cu, Pb and the Al-Si alloy powder. At this time, the surface of the powder is often melted. The molten Al alloy does not have a particle shape that has a clearly long one-way direction in the thermal sprayed layer, such as the primary crystal Si of a conventional ingot alloy or the Si particles of a rolled alloy. However, granular Si particles having almost the same dimensions and being spherical, massive, polygonal, and other irregular shapes not classified into these are dispersed. Further, in the case of the present invention, it is difficult to distinguish between primary crystal eutectic Si and eutectic Si, which is obvious in the conventional ingot alloy. The improvement in wear resistance is large due to such a Si structure. Also, molten Al-Si alloy powder and Cu-Pb
The reaction that takes place with the alloy powder binds the latter powder.

[Procedure amendment 12]

[Document name to be amended] Statement

[Correction target item name] 0020

[Correction method] Change

[Correction contents]

Next, an average powder particle size adjusting method will be described as a method for producing a composite sprayed layer having a structure according to the present invention. Table 1 shows an example in which an aluminum alloy powder similar to a copper alloy powder having a particle size showing a normal distribution around one average value is mixed.

[Procedure amendment 13]

[Document name to be amended] Statement

[Correction target item name] 0022

[Correction method] Change

[Correction contents]

In the following table, fine powder Cu-Pb and coarse powder Al-Si
By selecting the combination, the amount of copper alloy dissolved can be increased. In general, the hardness of a material obtained by combining a hard material and a soft material is in between these values.However, in the composite sprayed layer of the present invention, a reaction phase of a copper alloy and an aluminum alloy may be generated. , The average value of the hardness becomes higher than both.

[Procedure amendment 14]

[Document name to be amended] Statement

[Correction target item name] 0025

[Correction method] Change

[Correction contents]

The above-mentioned copper-aluminum composite thermal spray layer , which is 30% or less, preferably 1 to 10% of Al
₂ O ₃ , SiO ₂ , SiC, ZrO ₂ , Si ₃ N ₄ , BN, A
1N, TiN, TiV, B, C, iron-phosphorus compound, iron-
One or more compounds selected from the group consisting of phosphorus compounds, iron-boron compounds, and iron-nitrogen compounds can be added as a wear resistance improving component. If the added amount of these components exceeds 30%, lubricity and conformability become poor, and as a result, seizure tends to occur.

[Procedure amendment 15]

[Document name to be amended] Statement

[Correction target item name] 0032

[Correction method] Change

[Correction contents]

Example 3 75 wt% Cu-10 wt% Pb-4 wt% Sn alloy atomized powder (average particle diameter 60 μm) and 25 wt% aluminum alloy atomized powder (however, 40 wt% Si was added to A2024 aluminum alloy) Atomized powder of the alloy and an average particle diameter of 100 μm) were mixed, and commercially available pure aluminum was sprayed under the same conditions as in Example 1. Fig. 1 shows the microstructure observed without etching the surface of the sprayed layer.
FIG. 2 shows a surface structure etched with a Grade solution (5 g of ferric chloride, 100 cc of hydrochloric acid, 100 cc of water) for 5 seconds, and FIG. 3 shows a microstructure observed without etching the cross section. Fig. 4
Shown in In other words, the copper alloy powder is in the form of a lump that remains in the form of an atomized powder as judged from the form.
(Undissolved phase) and a portion (second copper alloy) that disappeared and crystallized together with the aluminum alloy melted during thermal spraying. Aluminum alloy, on the other hand, leaves little powder form. The aluminum alloy phase is a matrix ( first aluminum alloy melting
Phase) , the aluminum alloy is almost completely melted and reacts with the dissolved copper to form a Cu-Al compound (second
Is determined to be crystallized as a copper alloy) . The hardness of this sprayed layer was Hv200-260. The total composition is 45% Cu, 27% Al, 6% P by weight percentage.
b, 16% Si, 6% Sn, and residual impurities.

[Procedure amendment 16]

[Document name to be amended] Statement

[Correction target item name] 0040

[Correction method] Change

[Correction contents]

[0040]

As described above, the sprayed copper (alloy) -aluminum (alloy) composite sprayed layer according to the present invention has significantly improved wear resistance as compared with the aluminum (alloy) or copper (alloy) sprayed layer. .

[Procedure amendment 17]

[Document name to be amended] Statement

[Correction target item name] Brief description of drawings

[Correction method] Change

[Correction contents]

[Brief description of the drawings]

FIG. 1 is a photomicrograph of the surface structure of a composite sprayed layer in Example 3 of the present invention observed without etching.

FIG. 2 is a micrograph obtained by etching and observing a surface structure of a composite sprayed layer in Example 3 of the present invention.

FIG. 3 is a micrograph of a cross-sectional structure of a composite sprayed layer in Example 3 of the present invention, which was observed without etching.

FIG. 4 is a micrograph obtained by etching and observing a sectional structure of a composite sprayed layer in Example 3 of the present invention.

FIG. 5 is a graph showing the results of a friction test of Example 7 of the present invention. ────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] October 26, 2000 (2000.10.
26)

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0032

[Correction method] Change

[Correction contents]

Example 3 75 wt% Cu-10 wt% Pb-4 wt% Sn alloy atomized powder (average particle diameter 60 μm) and 25 wt% aluminum alloy atomized powder (however, 40 wt% Si was added to A2024 aluminum alloy) Atomized powder of the alloy and an average particle diameter of 100 μm) were mixed and sprayed under the same conditions as in Example 1. FIG. 1 shows the microstructure observed without etching the surface of the sprayed layer, and FIG. 2 shows the surface structure etched for 5 seconds with a graded liquid (5 g of ferric chloride, 100 cc of hydrochloric acid, 100 cc of water). FIG. 3 shows the microscopic structure observed in the above, and FIG. 4 shows the cross-sectional structure obtained by etching with the graded liquid. That is, the copper alloy powder is a lump portion that remains in the form of an atomized powder, judging from the form, and the first copper alloy (undissolved phase) and the part that disappears and crystallizes together with the aluminum alloy melted during thermal spraying. (A second copper alloy). Aluminum alloy, on the other hand, leaves little powder form. Since the aluminum alloy phase is a matrix (first aluminum alloy dissolved phase) for crystallizing the copper alloy phase into a net or flake,
It is determined that the aluminum alloy was almost completely melted, reacted with the dissolved copper, and crystallized as a Cu-Al compound (second copper alloy). The hardness of this sprayed layer is Hv200-
260. The overall composition is 45% by weight.
% Cu, 27% Al, 6% Pb, 16% Si, 6% S
n, the remaining impurities.

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4K031 AB03 AB08 CB01 CB09 CB21 CB25 CB28 CB35 CB37 CB39 CB42 CB43 CB44 CB45 CB46 CB50

Claims (19)

[Claims] 2. The method according to claim 1, wherein the copper or the first copper alloy comprises at least an undissolved phase, and the aluminum or the second copper alloy comprises at least an undissolved phase. A sprayed copper-aluminum composite material, wherein the aluminum alloy comprises at least a molten phase. 2. The thermal sprayed copper-aluminum composite material according to claim 1, wherein the first copper alloy contains the aluminum or a component of the first aluminum alloy and includes a second copper alloy formed by thermal spraying. 3. The thermal sprayed copper-aluminum composite material according to claim 1, wherein said first aluminum alloy includes said copper or a second aluminum alloy containing a component of said first copper alloy. 4. The sprayed copper-aluminum composite material according to claim 1, wherein the main structure comprises a copper or first copper alloy undissolved phase and an aluminum or second aluminum alloy dissolved phase. 5. The method according to claim 1, wherein the thermal sprayed surface layer is made of copper or a first material.
5. The method according to claim 4, further comprising at least one of a copper alloy dissolved phase and aluminum or the first aluminum alloy undissolved phase.
A sprayed copper-aluminum composite material as described. 6. The method according to claim 1, wherein the first copper alloy contains Pb, and the first aluminum alloy contains Si.
6. The thermal sprayed copper-aluminum composite material according to any one of items 1 to 5. 7. The sprayed copper according to claim 6, wherein said first copper alloy contains 40% by weight or less of Pb, and said first aluminum alloy contains 12 to 60% by weight of Si. -Aluminum composite material. 8. The total composition is as follows: Cu: 8 to 82% by weight;
Al: 5 to 50% by weight, Pb: 40% by weight or less, Si:
The sprayed copper-aluminum composite material according to claim 7, wherein the amount is 5 to 50% by weight. 9. The method according to claim 1, wherein the first aluminum alloy comprises 30% by weight or less of Sn, 7.0% by weight or less of Cu, 5.0% by weight or less of Mg, 1.5% by weight or less of Mn, 1.5% by weight or less. weight%
8. The thermal sprayed copper-aluminum composite material according to claim 7, further comprising at least one element of the group consisting of the following Fe, 8% by weight or less of Cr, and 8.0% by weight or less of Ni. 10. The total composition is as follows: Cu: 8 to 82% by weight, Al: 5 to 50% by weight, Pb: 40% by weight or less,
Si: 5 to 50% by weight, Sn: 30% by weight or less, Mg:
5% by weight or less, Mn: 5% by weight or less, Fe: 1.5% by weight or less, Cr: 5% by weight or less, Ni: 20% by weight or less,
And Zn: not more than 30% by weight. 11. The first copper alloy comprises at most 30% by weight of Sn, at most 0.5% by weight of P and at most 15% by weight of A.
1, 10% by weight or less of Ag, 5% by weight or less of Mn, 5% by weight or less of Cr, 20% by weight or less of Ni and 30% by weight
The sprayed copper-aluminum composite material according to claim 7, further comprising one or more selected from the group consisting of the following Zn in the range of 0.5 to 50% by weight. 12. The total composition is as follows: Al: 15 to 50% by weight, Cu: 8 to 50% by weight, Pb: 40% by weight or less, S:
i: 5 to 50% by weight, Sn: 30% by weight or less, P: 0.
5% by weight or less, Ag: 10% by weight or less, Mn: 5% by weight
Below, Cr: 5% by weight or less, Ni: 20% by weight or less, Z
n: not more than 30% by weight.
A sprayed copper-aluminum composite material as described. 13. A method according to claim 1, wherein at least a part of the first copper alloy (excluding the second copper alloy) is made of Cu crystals, and at least a part of the first aluminum alloy (excluding the second aluminum alloy). The thermal sprayed copper-aluminum composite material according to claim 11 or 12, wherein a part of the composite material is made of Al crystal. 14. The method according to claim 6, further comprising 30% by weight or less of graphite particles.
A spray-coated copper-aluminum composite material as described in the above item. 15. Al ₂ O ₃ , S in an amount of not more than 30% by weight.
iO ₂ , SiC, ZrO ₂ , Si ₃ N ₄ , BN, AlN, T
iN, TiC, B ₄ C, and 1 selected from the group consisting of iron-phosphorus, iron-boron, and iron-nitrogen iron-based compounds.
2. The method according to claim 1, wherein the composition contains at least one species.
5. The thermal sprayed copper-aluminum composite material according to any one of 4 to 4. 16. The semiconductor device according to claim 1, wherein the semiconductor device is laminated on a substrate.
The sprayed copper-aluminum composite material according to any one of claims 1 to 15, wherein the sprayed copper-aluminum composite material according to any one of (1) to (5) is coated with a soft metal layer. 17. The soft metal layer is made of Pb, a Pb alloy, Sb.
17. The sprayed copper-aluminum composite material according to claim 16, which is an n or Sn alloy plating. 18. The soft metal layer is mainly composed of Pb and Sn.
17. The thermal sprayed copper-aluminum composite material according to claim 16, which is a plating layer comprising: 19. The sprayed copper-aluminum composite according to claim 1, wherein the sprayed surface layer is coated with a film containing MoS ₂ or graphite or a mixture of MoS ₂ and graphite. material.