WO2011132703A1 - 摺動材用銅合金 - Google Patents

摺動材用銅合金 Download PDF

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Publication number
WO2011132703A1
WO2011132703A1 PCT/JP2011/059713 JP2011059713W WO2011132703A1 WO 2011132703 A1 WO2011132703 A1 WO 2011132703A1 JP 2011059713 W JP2011059713 W JP 2011059713W WO 2011132703 A1 WO2011132703 A1 WO 2011132703A1
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Prior art keywords
copper alloy
sliding
fes
sintering
powder
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PCT/JP2011/059713
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English (en)
French (fr)
Inventor
知広 佐藤
良政 平井
丸山　徹
小林　武
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株式会社栗本鐵工所
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Application filed by 株式会社栗本鐵工所 filed Critical 株式会社栗本鐵工所
Priority to CN2011800184160A priority Critical patent/CN102844451A/zh
Priority to JP2012511684A priority patent/JP5902615B2/ja
Priority to KR1020127026345A priority patent/KR101777717B1/ko
Priority to EP11772036.7A priority patent/EP2562279B1/en
Priority to US13/641,880 priority patent/US8906129B2/en
Publication of WO2011132703A1 publication Critical patent/WO2011132703A1/ja
Priority to US14/338,795 priority patent/US20140331819A1/en

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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/04—Making non-ferrous alloys by powder metallurgy
    • C22C1/0425—Copper-based alloys
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F7/00—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression
    • B22F7/02—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression of composite layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F7/00—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression
    • B22F7/02—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression of composite layers
    • B22F7/04—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression of composite layers with one or more layers not made from powder, e.g. made from solid metal
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F7/00—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression
    • B22F7/06—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression of composite workpieces or articles from parts, e.g. to form tipped tools
    • B22F7/08—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression of composite workpieces or articles from parts, e.g. to form tipped tools with one or more parts not made from powder
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/02—Making metallic powder or suspensions thereof using physical processes
    • B22F9/06—Making metallic powder or suspensions thereof using physical processes starting from liquid material
    • B22F9/08—Making metallic powder or suspensions thereof using physical processes starting from liquid material by casting, e.g. through sieves or in water, by atomising or spraying
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/02—Making metallic powder or suspensions thereof using physical processes
    • B22F9/06—Making metallic powder or suspensions thereof using physical processes starting from liquid material
    • B22F9/08—Making metallic powder or suspensions thereof using physical processes starting from liquid material by casting, e.g. through sieves or in water, by atomising or spraying
    • B22F9/082—Making metallic powder or suspensions thereof using physical processes starting from liquid material by casting, e.g. through sieves or in water, by atomising or spraying atomising using a fluid
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C32/00—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ
    • C22C32/0089—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ with other, not previously mentioned inorganic compounds as the main non-metallic constituent, e.g. sulfides, glass
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C9/00—Alloys based on copper
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C9/00—Alloys based on copper
    • C22C9/02—Alloys based on copper with tin as the next major constituent
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
    • F16C—SHAFTS; FLEXIBLE SHAFTS; ELEMENTS OR CRANKSHAFT MECHANISMS; ROTARY BODIES OTHER THAN GEARING ELEMENTS; BEARINGS
    • F16C2204/00—Metallic materials; Alloys
    • F16C2204/10—Alloys based on copper
    • F16C2204/12—Alloys based on copper with tin as the next major constituent
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
    • F16C—SHAFTS; FLEXIBLE SHAFTS; ELEMENTS OR CRANKSHAFT MECHANISMS; ROTARY BODIES OTHER THAN GEARING ELEMENTS; BEARINGS
    • F16C2220/00—Shaping
    • F16C2220/20—Shaping by sintering pulverised material, e.g. powder metallurgy

Definitions

  • This invention relates to a copper alloy used for a sliding member such as a bearing material, which contains a component contributing to slidability other than lead as a component contributing to slidability.
  • a copper alloy containing lead typified by CAC603 (Cu—Sn—Pb-based copper alloy) is used, and lead contributes to the sliding property.
  • CAC603 Cu—Sn—Pb-based copper alloy
  • lead contributes to the sliding property.
  • various copper alloys for sliding materials that suppress the use of lead have been studied.
  • Patent Document 1 Cu that may be partially replaced with Sn or Zn is used as a matrix material, and one of Fe, Ni, Co, and an alloy of Mo and S is used as a low friction alloy. A sliding member obtained by sintering is described. The fact that the MoS 2 phase contributes to the reduction of the friction coefficient and the generation of MoS 2 by iron sulfide is prevented by replacing part of Fe with Mi and Co.
  • an object of the present invention is to obtain a copper alloy that exhibits effective sliding characteristics without relying on MoS 2 that may be oxidized.
  • the present invention solves the above-mentioned problems with a copper alloy for a sliding material containing Cu 5 FeS 4 .
  • a copper alloy containing Cu 5 FeS 4 exhibits high sliding performance.
  • a method for obtaining a copper alloy containing Cu 5 FeS 4 for example, when a raw material powder containing Cu, S and Fe is formed by an atomizing method, a copper alloy containing Cu 5 FeS 4 is generated. This is considered to be due to the rapid cooling of the atomizing method, and the production method is not particularly limited as long as similar conditions can be achieved.
  • this copper alloy can contain Cu 5 FeS 4 even after it is made into a sintered body, the particle powder generated by the gas atomization method is sprayed on the back metal of the metal fitting used for the bearing, and sintered and rolled to slide the surface. It can be used as a laminated sintered member in which a layer exhibiting dynamic performance is formed.
  • X-ray diffraction graph of raw material powder before sintering of Example 1 X-ray diffraction graph of raw material powder before sintering of Example 2
  • X-ray diffraction graph of raw material powder after sintering of Example 1 X-ray diffraction graph of raw material powder after sintering of Example 2
  • the present invention is a copper alloy for a sliding material containing Cu 5 FeS 4 .
  • Cu 5 FeS 4 is produced in a copper alloy by melting and mixing a raw material containing Cu, Fe, and S and then rapidly cooling it by a method such as a gas atomizing method or a water atomizing method.
  • the copper alloy refers to an alloy containing 50% by mass or more of copper.
  • This copper alloy may contain elements other than Cu, Fe and S.
  • a bronze-based copper alloy containing 1 mass% or more and 15 mass% or less of Sn may be used. Firing with such a component that becomes a bronze-based copper alloy is preferable because of high strength.
  • P may be included in a molten stage before performing rapid cooling.
  • the molten metal is rapidly cooled to produce a copper alloy material or copper alloy containing Cu 5 FeS 4 .
  • the rapid cooling method it is preferable to use an atomizing method because it can be quickly cooled and uniform particles can be easily obtained.
  • the gas atomizing method particles that are a uniform and good raw material for a copper alloy material can be obtained.
  • the molten metal is flowed from a nozzle hole provided at the bottom of a container containing the molten metal, and an inert gas is blown toward the flow with a jet.
  • the inert gas is used to prevent the raw material from being oxidized. Specifically, nitrogen, argon, or the like can be used.
  • the temperature of the inert gas is not specified, rapid cooling is required due to a sufficient temperature difference from the molten metal.
  • the cooling rate may be about 10 3 K / sec or higher.
  • the molten metal stream is refined by an inert gas blown by a jet and rapidly cooled to a fine powder. Since droplet formation and cooling are performed simultaneously, the particles are nearly spherical and uniform. During this rapid cooling, a compound of Cu 5 FeS 4 is once formed in the alloy.
  • the particle diameter of the raw material powder produced by this gas atomization method is preferably 150 ⁇ m or less. If the particle size is too large, the sliding material may not be efficiently produced.
  • the raw material powder thus obtained is sintered to obtain a copper alloy suitable as a sliding material.
  • This sintering may be performed, for example, by a method in which powder is dispersed on the material on which the sliding layer is to be formed and then heated to a temperature to be sintered.
  • a sliding layer integrated with the base material is obtained more firmly than in the case of only temporary sintering. be able to.
  • after mixing other alloy powder such as copper alloy with the powder before sintering it can be used for sintering.
  • the temperature at which the raw material powder is sintered is preferably 800 ° C. or higher and 900 ° C. or lower, and particularly preferably sintered at 830 ° C. or higher and 860 ° C. or lower for 5 minutes to 60 minutes. If the temperature is too low, the time is too short, or if the temperature is too high or the time is too long, there is a risk that mechanical properties suitable as a sliding material cannot be obtained. Further, the sintering is preferably performed in a reducing atmosphere. This is because the powder may be oxidized.
  • the sintering furnace may be a batch furnace or a continuous furnace.
  • the copper alloy for a sliding material according to the present invention can exhibit necessary slidability when Cu 5 FeS 4 is contained in an amount of 1% by mass or more, and sufficient slidability is ensured when the content is 2% by mass or more. It is more preferable because it is possible. On the other hand, even if it is made to contain more than 20 mass%, it is difficult because other phases are generated, and if it is 15 mass% or less, it is practical and preferable as a copper alloy for a sliding material.
  • Example 1 Single Cu, simple Sn, iron sulfide, Cu—Fe, and CuP are mixed, put in a crucible, heated and melted in a nitrogen atmosphere to obtain a molten metal.
  • the molten metal was poured out, normal temperature nitrogen gas was sprayed from the nozzle on the flow path, and the molten metal was rapidly cooled at about 10 3 K / s and particles were obtained.
  • a powder having a particle size of 150 ⁇ m or less was used in the test described later.
  • the target elemental ratio of the material obtained in the example obtained by the atomization method is 9.0 to 11.0% by mass of Sn, 1.5 to 2.5% by mass of Fe, and 0.5 to 2.5% of S in Example 1. 0.7% by mass, P is 0.01 to 0.03% by mass, and the balance is Cu and inevitable impurities.
  • Sn is 9.0 to 11.0% by mass
  • Fe is 1.5 to 2.5% by mass
  • S is 1.8 to 2.2% by mass
  • P is 0.01 to 0%. 0.03 mass% balance is Cu and inevitable impurities.
  • Example 1 The powder of the particles thus obtained was analyzed by a powder X-ray diffraction method.
  • the apparatus used was an X-ray diffractometer (XRD, Rigaku RINT-2500H / PC).
  • the X-ray source is CoK ⁇ (30 kV-100 mA), and the method is the ⁇ -2 ⁇ method.
  • the sample was rotated at 60 rpm so that the scanning resolution was 0.02 ° and the scanning speed was 2 ° / min.
  • the result of Example 1 is shown in FIG. 1, and the result of Example 2 is shown in FIG. (A) is a total intensity graph, and (b) is an enlarged graph.
  • a mixture of this particle powder and Cu (80) -Sn (20) alloy powder is dispersed on a 3.2 mm thick back metal (SPC steel plate 100 mm ⁇ 28 mm) to a thickness of 2.5 mm,
  • SPC steel plate 100 mm ⁇ 28 mm back metal
  • primary sintering was performed by heating for 10 minutes in the range of 830 to 860 ° C.
  • primary rolling is performed with a roller, and then secondary sintering is performed under the same conditions as the primary sintering, and a sintered sample having a total thickness of about 90% (a thickness of the copper alloy layer of about 2 mm) is obtained. Obtained.
  • This sintered sample was analyzed by the powder X-ray diffraction method in the same manner as described above.
  • Example 1 The result of Example 1 is shown in FIG. 3, and the result of Example 2 is shown in FIG.
  • a clear peak was observed at a position corresponding to the diffraction peak (peak at the bottom of each figure) of PDF25-1424 which is one form of Cu 5 FeS 4 .
  • other sulfides and simple sulfur were not detected. For this reason, although the structure of Cu 5 FeS 4 is changed after sintering, it is considered that almost all of the sulfur remains forming Cu 5 FeS 4 .
  • Component analysis was performed on the sintered test pieces of Examples 1 and 2.
  • the content of each component is analyzed by ICP emission spectroscopy for Sn and Fe, the content of S is analyzed by high frequency combustion infrared absorption, and the content of P is determined by molybdovanadophosphate absorptiometry.
  • Pb was measured by ICP emission spectroscopic analysis.
  • a thermoelectron IRIS Advantage RP CID detector was used as an ICP analyzer. The remainder was calculated as copper. The results are shown in Table 1.
  • Example 1 As described above, it is considered that the total amount of S forms Cu 5 FeS 4 , and therefore, from the component ratio, 2.03 mass% in Example 1 and 6.34 mass% in Example 2 are Cu 5 FeS 4. Is considered to be included.
  • the target values of the alloys are shown in Table 1.
  • Comparative Example 1 is a conventional lead-containing sliding material alloy CAC603
  • Comparative Example 2 is a Cu—Sn alloy composed of Cu: 88 wt% -Sn: 12 wt%. A piece was prepared and subjected to a frictional wear test, and the PV value was measured.
  • test piece preparation of the test piece will be described.
  • Examples 1 and 2 X-ray diffraction test using particles obtained by gas atomization and Cu (80) -Sn (20) alloy powder mixed, and in Comparative Example 2 using powders having the component ratios shown in Table 1 below. Specimens were produced in the same manner as
  • the sintered products of Examples 1 and 2 and Comparative Example 2 were processed into bimetal chips 11 having a shape shown in FIG. 5 and a sliding surface of Ra 3.2 with ⁇ 5 ⁇ 4t.
  • the left side 12 is a copper alloy layer
  • the right side 13 is a back metal. This was fixed to a chip holder 15 having an inner circumference of ⁇ 5.0 in the shape shown in FIG.
  • the pin 17 having the shape shown in FIG. 7 (the stepped portion 19 is ⁇ 8 ⁇ 25t and the stepped portion 18 is ⁇ 5 ⁇ 6t is stepped on the sliding side.
  • the test piece was processed with a sliding surface of Ra 3.2).
  • an S45C steel sample disk 21 having a diameter of 55 ⁇ 5t and a test surface of Ra3.2 as shown in FIG. 8 was used.
  • the test machine used was a friction and wear tester RI-S-500NP manufactured by Takachiho Seiki Co., Ltd.
  • the disk 21 and the chip test piece 22 of the test machine were immersed in oil (Rimla D20W-20 manufactured by Showa Shell Co., Ltd.) flowing at a flow rate of 200 ml / min, and the temperature of the test environment was maintained at 80 ⁇ 5 ° C.
  • the test was a step operation in which the peripheral speed of the disk was 6.2 m / s and the load (average surface pressure) was increased by 25 MPa after a 3 minute conforming operation, and each load was held for 2 minutes. The test was terminated on the assumption that oil smoke was generated during the test.
  • Table 1 shows the maximum PV value that is the product of the average friction coefficient at each load and the average surface pressure and peripheral speed in addition during seizure.
  • Examples 1 and 2 showed an average friction coefficient and PV value equal to or higher than those of the conventional sliding material CAC603 having lead, and it was confirmed that effective sliding characteristics were exhibited. Further, comparing Examples 1 and 2, it can be seen that Example 2 containing more Cu 5 FeS 4 shows a better average friction coefficient and PV value. On the other hand, Comparative Example 2 not having Cu 5 FeS 4 caused seizure immediately after the first step of pressure increase and did not exhibit sliding characteristics.
  • an X-ray diffraction test was performed on a test piece manufactured in the same manner as described above using a particle powder manufactured by the water atomization method and the powder before sintering. A peak was clearly observed at a position corresponding to the diffraction peak of 5FeS 4 (PDF25-1424), and no other sulfide or sulfur peak was observed.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Composite Materials (AREA)
  • Manufacturing & Machinery (AREA)
  • Inorganic Chemistry (AREA)
  • Powder Metallurgy (AREA)
  • Manufacture Of Metal Powder And Suspensions Thereof (AREA)
  • Sliding-Contact Bearings (AREA)

Abstract

　鉛やモリブデンに頼ることなく、摺動性に優れた銅合金を得る。ガスアトマイズ法により形成させたＣｕとＦｅとＳを含有する原料粉末を焼結して得られるＣｕ５ＦｅＳ４の焼結体を含む銅合金とする。

Description

摺動材用銅合金
　この発明は、軸受材料などの摺動部材に用いる銅合金であって、摺動性に寄与する成分として鉛以外の摺動性に寄与する成分を含有するものに関する。
　軸受材料などの摺動部材には、ＣＡＣ６０３（Ｃｕ－Ｓｎ－Ｐｂ系銅合金）に代表される鉛を含む銅合金が使用されており、いずれも鉛が摺動性に寄与している。しかし、鉛の使用を抑制する社会的要請に応えるため、鉛の使用量を抑制した摺動材用銅合金が様々に検討されている。
　例えば、特許文献１には、一部をＳｎかＺｎで置き換えても良いＣｕをマトリクス材料とし、低摩擦合金としてＦｅ、Ｎｉ、Ｃｏのいずれかと、ＭｏとＳとからなる合金を用いてこれらを焼結して得られる摺動部材が記載されている。ＭｏＳ２相が摩擦係数の低減に寄与し、硫化鉄によりＭｏＳ２の生成が妨げられることを、Ｆｅの一部をＭｉ、Ｃｏに置き換えることで抑制する。
特開２００３－７３７５８号公報
　しかしながら、ＭｏＳ２を主な摺動材とする銅合金（特許文献１）では、ＭｏＳ２を得る焼結工程だけでなく、使用中でもＭｏＳ２が酸化して劣化することがあるため、焼結工程での酸化を防ぐだけでは潤滑性能の低下を防ぐことができないという問題がある。
　そこでこの発明は、酸化の恐れがあるＭｏＳ２に頼ることなく、有効な摺動特性を発揮する銅合金を得ることを目的とする。
　この発明は、Ｃｕ５ＦｅＳ４を含む摺動材用銅合金により上記の課題を解決したのである。Ｃｕ５ＦｅＳ４を含む銅合金は、高い摺動性能を発揮する。
　Ｃｕ５ＦｅＳ４を含む銅合金を得る方法としては、例えば、アトマイズ法によりＣｕとＳとＦｅとを含有する原料粉末を形成させると、Ｃｕ５ＦｅＳ４を含む銅合金が生じる。これはアトマイズ法の急冷によるものと考えられ、同様の条件を達成できるのであれば製造方法は特に限定されない。
　この発明にかかる銅合金は、含有するＣｕ５ＦｅＳ４が摺動性を発揮するため、従来の摺動材用銅合金が有していた問題を解決したものとなる。
　この銅合金は焼結体とした後もＣｕ５ＦｅＳ４が存在できるため、軸受に用いる金具の裏金上にガスアトマイズ法により生成した粒子粉を散布し、焼結、圧延することで、表面に摺動性能を発揮する層を形成した積層焼結部材として用いることができる。
実施例１の焼結前の原料粉末のＸ線回折グラフ 実施例２の焼結前の原料粉末のＸ線回折グラフ 実施例１の焼結後の原料粉末のＸ線回折グラフ 実施例２の焼結後の原料粉末のＸ線回折グラフ 摩擦摩耗試験に用いるチップの形状を示す図 摩擦摩耗試験に用いるチップホルダーの形状を示す図 摩擦摩耗試験に用いるピンの形状を示す図 摩擦摩耗試験に用いるディスクの形状を示す図
　以下、この発明について詳細に説明する。この発明は、Ｃｕ５ＦｅＳ４を含む摺動材用銅合金である。Ｃｕ５ＦｅＳ４はＣｕとＦｅとＳを有する原料を溶融混合した後ガスアトマイズ法や水アトマイズ法などの方法で急冷することで銅合金中に生成する。ここで、銅合金とは５０質量％以上が銅からなる合金をいう。
　この銅合金はＣｕとＦｅとＳ以外の元素を含んでいてもよい。例えば、Ｓｎを１質量％以上１５質量％以下含む青銅系銅合金でもよい。このような青銅系銅合金となる成分で焼成すると、高強度となるため好ましい。
　また、脱酸効果を発揮させるため、急冷を実行する前の溶融した段階でＰを含めてもよい。
　焼結後の上記銅合金中が有するＰｂの量は、少ないほど好ましい。Ｐｂが多いと環境負荷の点から好ましくない。
　これらの元素を含む、急冷を行う溶湯を作製する際に用いる原料としては、Ｃｕの単体、Ｓｎの単体、硫化鉄、Ｃｕ－Ｆｅ、ＣｕＰなどを用いることができる。
　これらの材料を混合して溶解した後、溶湯を急冷してＣｕ５ＦｅＳ４を含有する銅合金材料または銅合金を生成させる。急冷方法としては、アトマイズ法を用いると、速やかに冷却できるとともに均一な粒子が得られやすいので好ましく、ガスアトマイズ法によると均一で良好な銅合金材料の原料となる粒子が得られる。ガスアトマイズ法により銅合金粒子を得るには、溶湯を入れた容器の底部に設けたノズル孔からその溶湯を流し、その流れに向かって不活性ガスをジェットで吹きつける。不活性ガスを用いるのは、原料が酸化してしまうことを防ぐためである。具体的には、窒素、アルゴンなどを用いることができる。
　上記の不活性ガスの温度は規定しないが溶湯との十分な温度差による急冷が必要となる。具体的には、１０３Ｋ／ｓｅｃ程度か、又はそれ以上の冷却速度であればよい。
　溶湯の流れはジェットで吹きつけられる不活性ガスによって微細化されるとともに急冷して微細粉末となる。この、液滴化と冷却を同時に行うために、粒子は球形に近く均質なものが得られる。この急冷の際に、Ｃｕ５ＦｅＳ４の化合物が一旦合金内に形成される。
　このガスアトマイズ法で生成する原料粉末の粒子径は１５０μｍ以下であると好ましい。粒径が大きすぎると摺動材の製造が効率的に行えないおそれがある。
　こうして得られた原料粉末を焼結して、摺動材として適した銅合金が得られる。この焼結は例えば、摺動層を形成させたい材料上に粉末を散布してから焼結すべき温度に加熱するといった方法で行うとよい。散布してから焼成する場合、一時焼結の後、圧延した後に、二次焼結を行って再度圧延すると、一時焼結だけの場合よりも強固に基材と一体化した摺動層を得ることができる。ここで焼結前の粉末に銅合金など他の合金粉末を混合した後、焼結に使用する事もできる。
　原料粉末を焼結する温度は、８００℃以上９００℃以下が好ましく、特に８３０℃以上８６０℃以下の条件で、５分～６０分焼結を行うことが好ましい。温度が低すぎても時間が短すぎても、温度が高すぎたり時間が長すぎたりしても摺動材として好適な機械的特性を得られなくなるおそれがある。また、焼結は還元雰囲気下で行うことが好ましい。粉末が酸化してしまうおそれがあるためである。なお、焼結炉はバッチ炉でも連続炉でもよい。
　この発明にかかる摺動材用銅合金は、Ｃｕ５ＦｅＳ４を１質量％以上含有すると、必要な摺動性を発揮することができ、２質量％以上であると十分な摺動性を確保できるのでより好ましい。一方、２０質量％を超えて含有させようとしても他の相が生じてしまうために困難であり、１５質量％以下であると摺動材用銅合金として現実的で好ましい。
　以下、この発明について、青銅系銅合金としての具体的な実施例を挙げて説明する。まず、用いる原料について説明する。
（実施例１、２）
　単体のＣｕ、単体のＳｎ、硫化鉄、Ｃｕ－Ｆｅ、ＣｕＰを混合して坩堝に入れ、窒素雰囲気中で加熱し融解させて溶湯を得る。
　この溶湯を、流し出し、その流路上のノズルから常温窒素ガスを噴射し、１０３Ｋ／ｓ程度で急冷するとともに粒子を得た。この粒子の内、粒径が１５０μｍ以下の粉末を後述する試験に用いた。
　アトマイズ法で得る実施例の目標とする材料中元素比は、実施例１ではＳｎが９．０～１１．０質量％、Ｆｅが１．５～２．５質量％、Ｓが０．５～０．７質量％、Ｐが０．０１～０．０３質量％、残部がＣｕと不可避不純物である。また、実施例２では、Ｓｎが９．０～１１．０質量％、Ｆｅが１．５～２．５質量％、Ｓが１．８～２．２質量％、Ｐが０．０１～０．０３質量％残部がＣｕと不可避不純物である。
＜Ｘ線回折試験＞
　こうして得られた粒子の粉末について、粉末Ｘ線回折法による解析を行った。装置はＸ線回折装置（ＸＲＤ、（株）リガク　ＲＩＮＴ－２５００Ｈ／ＰＣ）を用いた。Ｘ線源はＣｏＫα（３０ｋＶ－１００ｍＡ）であり、方式はθ－２θ法である。走査解像度は０．０２°で、走査速度は２°／ｍｉｎで行うよう６０ｒｐｍで試料を回転させた。実施例１の結果を図１に、実施例２の結果を図２に示す。それぞれ（ａ）は全強度グラフ、（ｂ）は拡大グラフである。いずれも、Ｃｕ５ＦｅＳ４の一形態であるＰＤＦ（Ｐｏｗｄｅｒ　Ｄｉｆｆｒａｃｔｉｏｎ　Ｆｉｌｅ（Ｉｎｔｅｒｎａｔｉｏｎａｌ　Ｃｅｎｔｒｅ　ｆｏｒ　Ｄｉｆｆｒａｃｔｉｏｎ　Ｄａｔｅ－ＩＣＤＤ発行））４２－１４０５の回折ピーク（各図下のピーク）に相当する箇所にピークが観測されており、溶湯からの急冷によってＣｕ５ＦｅＳ４が生成していることが確認された。またその他の硫化物及び硫黄単体は検出されなかった。このため、実施例１及び２において、硫黄はほぼ全量がＣｕ５ＦｅＳ４を形成していると考えられる。
　この粒子粉末とＣｕ（８０）―Ｓｎ（２０）合金粉末を混合したものを、厚さ３．２ｍｍのバックメタル（ＳＰＣ鋼板１００ｍｍ×２８ｍｍ）上に厚さ２．５ｍｍとなるように散布し、還元雰囲気下の管状炉にて、８３０～８６０℃の範囲で、１０分間に亘って加熱し一次焼結を行った。その後ローラにて一次圧延を行い、次に一次焼結と同等の条件で二次焼結を行い、総厚さが９０％程度（銅合金層の厚さ２ｍｍ程度）となった焼結試料を得た。この焼結試料について、上記と同様に粉末Ｘ線回折法による解析を行った。実施例１の結果を図３に、実施例２の結果を図４に示す。いずれも、Ｃｕ５ＦｅＳ４の一形態であるＰＤＦ２５－１４２４の回折ピーク（各図下のピーク）に対応する箇所にはっきりとしたピークが観測された。またその他の硫化物及び硫黄単体は検出されなかった。このため、焼結後もＣｕ５ＦｅＳ４の構造が変化しているものの、硫黄はほぼ全量がＣｕ５ＦｅＳ４を形成したままであると考えられる。
＜成分分析＞
　実施例１及び２の焼結した試験片について、成分分析を行った。それぞれの成分の含有率の分析は、Ｓｎ、ＦｅについてはＩＣＰ発光分光分析法により行い、Ｓの含有率の分析は高周波燃焼赤外線吸収法により行い、Ｐの含有率はモリブドバナドりん酸吸光光度法により行い、Ｐｂについては、ＩＣＰ発光分光分析法により行った。なお、ＩＣＰ発光分光分析法にあたっては、ＩＣＰ分析装置として、サーモエレクトロン社製：ＩＲＩＳ　Ａｄｖａｎｔａｇｅ　ＲＰ　ＣＩＤ　検出器を用いた。また、残余分を銅と計算した。その結果を表１に示す。上記の通り、Ｓは全量がＣｕ５ＦｅＳ４を形成していると考えられるので、成分比から、実施例１では２．０３質量％、実施例２では６．３４質量％のＣｕ５ＦｅＳ４が含まれると考えられる。また、比較例１及び２については合金の目標値を表１に記載した。
Figure JPOXMLDOC01-appb-T000001
＜摩擦摩耗試験＞
　次に、上記の実施例１及び２、比較例１として従来の鉛含有摺動材用合金であるＣＡＣ６０３、比較例２としてＣｕ：８８ｗｔ％－Ｓｎ：１２ｗｔ％からなるＣｕ－Ｓｎ合金について、試験片を作製して摩擦摩耗試験を行い、ＰＶ値を測定した。
　まず、試験片の作製について説明する。実施例１，２ではガスアトマイズ法で得られた粒子とＣｕ（８０）－Ｓｎ（２０）合金粉末を混合したもの、比較例２では下記表１に記載の成分比の粉末を用いＸ線回折試験と同じ方法にて試験片を制作した。
　実施例１，２及び比較例２の焼結品を、図５に示す形状のφ５×４ｔで摺動表面はＲａ３．２のバイメタルチップ１１に加工した。なお、図の左側１２が銅合金層で、右側１３がバックメタルである。これを、図６に示す形状の内周がφ５．０であるチップホルダー１５に、セットボルト１６にて固定して試験片とした。また、比較例１のＣＡＣ６０３摺動材については、図７に示す形状のピン１７（非段つき部１９がφ８×２５ｔで、段つき部１８がφ５×６ｔであるように摺動側を段つき加工してある。摺動表面はＲａ３．２。）に加工したものを試験片とした。これらのピンと摺動させるディスクは、図８に示す形状の通り、φ５５×５ｔで試験面がＲａ３．２のＳ４５Ｃ鉄鋼製試料ディスク２１を用いた。
　試験機は、高千穂精機（株）製摩擦摩耗試験機ＲＩ－Ｓ－５００ＮＰを用いた。試験機のディスク２１及びチップ試験片２２は流量２００ｍｌ／ｍｉｎで流れるオイル（昭和シェル（株）製リムラＤ２０Ｗ－２０）に浸漬させており、試験環境の温度は８０±５℃を維持させた。
　試験はディスクの周速を６．２ｍ／ｓとし、３分間のなじみ運転の後、２５ＭＰａずつ荷重（平均面圧）を上昇させるステップ運転とし、各荷重では２分間保持した。試験中に油煙が発生した時点を焼き付きと想定して試験を終了させた。表１に各荷重での平均摩擦係数と焼き付き時の付加における平均面圧と周速の積である最大ＰＶ値を示す。
　実施例１及び２は鉛を有する従来の摺動材ＣＡＣ６０３と同等以上の平均摩擦係数とＰＶ値を示し、有効な摺動特性が発揮することが確かめられた。また実施例１と２を比較するとＣｕ５ＦｅＳ４を多く含む実施例２の方が良好な平均摩擦係数とＰＶ値を示していることがわかる。これに対し、Ｃｕ５ＦｅＳ４を有さない比較例２は一段階目の昇圧後すぐに焼き付きを起こしてしまい、摺動特性を発揮しなかった。
　他の実施例として水アトマイズ法にて製作した粒子粉末を使用して上記と同様に製作した試験片と焼結前の粉末のＸ線回折試験を行ったところ、図示は省略するが両者ともＣｕ５ＦｅＳ４（ＰＤＦ２５－１４２４）の回折ピークに相当する箇所にはっきりとピークが観測され、その他の硫化物や硫黄単体のピークは観測されなかった。
１１　バイメタルチップ
１２　銅合金層
１３　バックメタル
１５　チップホルダー
１６　セットボルト
１７　ピン
１８　段つき部
１９　非段つき部
２１　試料ディスク

Claims (5)

  1. 　Ｃｕ５ＦｅＳ４を含む摺動材用銅合金。
  2. 　Ｓｎを１質量％以上１５質量％以下含む青銅系である請求項１に記載の摺動材用銅合金。
  3. 　アトマイズ法により形成させたＣｕとＦｅとＳを含有する原料粉末を焼結して得られる請求項１又は２に記載の摺動材用銅合金。
  4. 　請求項１乃至３の摺動材用銅合金を摺動面に用いた摺動材。
  5. 　基材上に上記原料粉末を散布したものを、基材とともに焼結して得られる、請求項３の摺動材用銅合金を摺動面に形成させた摺動材。
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WO2014157089A1 (ja) * 2013-03-25 2014-10-02 新日鐵住金株式会社 銅合金粉末、銅合金焼結体および高速鉄道用ブレーキライニング
JPWO2014157089A1 (ja) * 2013-03-25 2017-02-16 新日鐵住金株式会社 銅合金粉末、銅合金焼結体および高速鉄道用ブレーキライニング
KR20160009612A (ko) * 2013-05-08 2016-01-26 페데랄-모굴 비스바덴 게엠베하 구리 합금, 구리 합금의 용도, 구리 합금을 가지는 베어링, 및 구리 합금으로 이루어진 베어링의 제조 방법
KR102309320B1 (ko) 2013-05-08 2021-10-06 페데랄-모굴 비스바덴 게엠베하 구리 합금, 구리 합금의 용도, 구리 합금을 가지는 베어링, 및 구리 합금으로 이루어진 베어링의 제조 방법

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US8906129B2 (en) 2014-12-09
JP2016094661A (ja) 2016-05-26
EP2562279A4 (en) 2014-09-10
CN102844451A (zh) 2012-12-26
EP2562279A1 (en) 2013-02-27
KR101777717B1 (ko) 2017-09-12
US20140331819A1 (en) 2014-11-13
EP2562279B1 (en) 2017-03-22
JP5902615B2 (ja) 2016-04-13
US20130036865A1 (en) 2013-02-14
JPWO2011132703A1 (ja) 2013-07-18
KR20130063487A (ko) 2013-06-14

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