US20100266444A1 - Pb-FREE COPPER ALLOY SLIDING MATERIAL - Google Patents

Pb-FREE COPPER ALLOY SLIDING MATERIAL Download PDF

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Publication number
US20100266444A1
US20100266444A1 US12/376,381 US37638107A US2010266444A1 US 20100266444 A1 US20100266444 A1 US 20100266444A1 US 37638107 A US37638107 A US 37638107A US 2010266444 A1 US2010266444 A1 US 2010266444A1
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Prior art keywords
hard particles
bal
phase
copper matrix
sliding
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US12/376,381
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English (en)
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Hiromi Yokota
Daisuke Yoshitome
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Taiho Kogyo Co Ltd
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Taiho Kogyo Co Ltd
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Assigned to TAIHO KOGYO CO., LTD. reassignment TAIHO KOGYO CO., LTD. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: YOSHITOME, DAISUKE, YOKOTA, HIROMI
Publication of US20100266444A1 publication Critical patent/US20100266444A1/en
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    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C9/00Alloys based on copper
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C9/00Alloys based on copper
    • C22C9/02Alloys based on copper with tin as the next major constituent
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22FWORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F5/00Manufacture of workpieces or articles from metallic powder characterised by the special shape of the product
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C1/00Making non-ferrous alloys
    • C22C1/04Making non-ferrous alloys by powder metallurgy
    • C22C1/05Mixtures of metal powder with non-metallic powder
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C32/00Non-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
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C32/00Non-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
    • C22C32/0089Non-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
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F16ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
    • F16CSHAFTS; FLEXIBLE SHAFTS; ELEMENTS OR CRANKSHAFT MECHANISMS; ROTARY BODIES OTHER THAN GEARING ELEMENTS; BEARINGS
    • F16C2204/00Metallic materials; Alloys
    • F16C2204/10Alloys based on copper
    • F16C2204/12Alloys based on copper with tin as the next major constituent

Definitions

  • the present invention relates to a copper-based sintered alloy, more particularly to a Pb-free sintered copper-based alloy sliding material which exhibits improved sliding property notwithstanding being Pb free.
  • Pb which is usually added to a copper alloy for use as a sliding member, expands and is ductile on the sliding surface as temperature rises during sliding. Seizure is prevented by simultaneous functions of Pb, that is, cooling of the sliding surface and excellent self-lubricating properties.
  • Pb forms a soft dispersing phase, excellent conformability and excellent ability to receive foreign matters are provided.
  • Pb is liable to be corroded by acids excepting sulfuric acid and is toxic. Therefore, there have been developed Cu—Bi based sintered alloys for use as a sliding material, in which alloy Bi substitutes for Pb.
  • the copper matrix and Bi phase are separated from one another in the structure of Cu—Bi based sintered alloy.
  • the Bi phase present on the sliding surface effectively provides seizure resistance.
  • Patent Document 1 Japanese Patent No. 3421724 is one of such prior art. It discloses a composition composed of from 0.5 to 15% by weight of Sn, from 1 to 20% by weight of Bi, from 0.1 to 10% by volume of hard particles selected from the group consisting of boride, silicide, oxide, nitride, carbide, intermetallic compound, with the balance being Cu. Average particle diameter of the hard particles is from 1 to 45 ⁇ m.
  • the hard particles are present in the Bi phase, which is dispersed in the copper matrix. Since the hard particles are present in the Bi phase, which is soft, Bi serves as a cushion for the hard particles, to thereby mitigate damage that may be exerted by the hard particles which are exposed on the surface of copper matrix onto a mating member.
  • a property of the Bi phase is such that it contains and holds the hard particles that have been separated.
  • each hard particle is surrounded by the Bi phase on the sliding surface either completely or partially, with the rest of the hard particles being bonded to the copper matrix.
  • Patent Document 2 Japanese Unexamined Patent Publication (kokai) No. 2005-200703 filed by the present applicant.
  • the proposed sintered copper alloy contains, by mass %, from 1 to 15% of Sn, from 1 to 15% of Bi, and from 0.1 to 10% of hard particles having an average particle diameter of 10 to 50 ⁇ m.
  • the percentage of the hard particles, whose contact ratio with Bi phase is 50% or less based on the entire periphery of the hard particles is 70% or more.
  • the contact ratio of hard particles mentioned above is 50%, it means that one hard particle is in contact with the Bi phase at 50% of the peripheral length of the hard particle, whereas the other 50% the hard particle is in contact with the copper matrix.
  • This ratio is referred to in Patent Document 2 to as “the hard-particle contact ratio.” Since the hard-particle contact ratio is 50% or less in Patent Document 2, the length of hard particle(s) in contact with the copper matrix is larger than a contact length with the Bi phase. In Patent Document 2, 70% or more relative to the entire hard particles is such hard particles. This ratio is referred to in Patent Document 2 to as “hard particle presence ratio” and attains 94% at the highest. The balance of 94%, i.e., 6%, corresponds to the hard-particle having 50% to 100% of the hard-particle contact ratio. In the case of 100%, hard particles are completely surrounded by the Bi phase.
  • Patent Document 2 when the individual hard particles are looked at, a half or less of the length of one particle is incorporated in the Bi phase.
  • the structure is controlled such that the ratio at which the hard particles remain in non-contact with the Bi phase, is as high as possible.
  • a high-frequency sintering is carried out for a short period of time.
  • Patent Document 1 Japanese Patent No. 3421724
  • Patent Document 2 Japanese Unexamined Patent Publication (kokai) No. 2005-200703
  • the Bi phase present on the sliding surface is expected to enhance the seizure resistance.
  • the Bi phase is expected to be compatible with a mating shaft during an initial sliding period, then making the surface of the sliding material to become so stable that seizure is difficult to occur.
  • the Cu phase is caused to flow by a mating shaft, and thus covers up the Bi phase.
  • the Bi phase exposed surface of gradually decreases, and, hence the seizure resistance disadvantageously lowers as compared with the initial level. Therefore, an aim of the present invention is to provide a Cu—Sn—Bi hard-particle-based sintered material with which reduction in seizure resistance as time passes can be prevented.
  • the present invention is directed to a sintered alloy which contains, by mass %, from 1 to 15% of Sn, from 1 to 15% of Bi, and from 1 to 10% of hard particles having an average diameter of from 50 to 70 ⁇ m, the balance being Cu and unavoidable impurities, and in which the Bi phase and the hard particles are dispersed in the copper matrix.
  • the Pb-free copper alloy sliding material of the present invention is characterized in that all of the hard particles are bonded to the copper matrix.
  • Sn is an element which strengthens the matrix.
  • Sn enhances a recrystallization temperature and hence exerts an influence upon the sintered structure.
  • the Sn content is less than 1 mass %, the recrystallization temperature of Cu alloy is so low that Bi preferentially covers up the surfaces of copper alloy powder as is described in a paragraph (3) “Sintering Method.”
  • the Sn content is 15 mass % or more, Cu—Sn intermetallic compounds are formed and embrittle the copper alloy matrix. The seizure resistance in the initial sliding period becomes poor.
  • the Sn content is preferably from 2 to 10 mass %, and more preferably from 2 to 6 mass %.
  • Bi is an element which exhibits similar effects to Pb in conventional materials. Bi enhances compatibility and seizure resistance. In addition, Bi forms a liquid phase required for liquid-phase sintering.
  • the Bi content is less than 1 mass %, Bi exposed on the surface during an initial sliding period is too small in amount to attain a satisfactory seizure resistance during the initial sliding period.
  • the Bi content is 15 mass % or more, contact between the hard particles and Bi is likely to occur, so that holding of the hard particles becomes difficult. As a result, it is difficult to prevent flowing of the Cu matrix and thus the seizure resistance decreases.
  • the Bi content is preferably from 2 to 10 mass %, and more preferably from 3 to 8 mass %.
  • Hard particles serve as a component which enhances wear resistance and suppresses flow of the Cu matrix. When the content of hard particles is less than 1 mass %, these effects are not quite satisfactory to attain high seizure resistance. On the other hand, when the content of hard particles is 10 mass % or more, the particle/matrix interface provides a starting point, at which metal fatigue is liable to occur, and, therefore, seizure resistance lowers.
  • hard particles examples include Fe—P based compounds, such as Fe 3 P and Fe 2 P; phosphides, such as Ni 3 P; borides, such as NiB, Ni 3 B, CrB, ZrB 2 , CoB, TiB, TiB 2 , VB 2 , TaB 2 , WB, MoB, and Fe—B; carbides such as Al 4 C 3 , SiC, WC, Fe 3 C, Mo 2 C, and Mn 3 C, intermetallic compounds, such as Ni—Sn based, Fe—W based, Fe—Mo based, Fe—Mn based, Cr—Al based, V—Al based, Ti—Al based, W—Al based, and Si—Mn based intermetallic compounds; Ni-based self fluxing alloys; and Co-based self-fluxing alloys.
  • Most preferable hard particles are Fe—P based compounds, such as Fe 3 P and Fe 2 P, because a diffusion between the copper matrix and this compound is
  • Average particle diameter of these hard particles is preferably from 10 to 50 ⁇ m, more preferably from to 15 to 40 ⁇ m.
  • P can be added as a copper matrix component. Effects of P include enhancing sintering property of the copper matrix and the alloy's bonding property with a backing metal. When P content is less than 0.02 mass %, these effects are small. When the P content exceeds 0.2 mass %, the copper matrix is so hardened that seizure resistance decreases and its bonding property with backing metal also deteriorates. Components other than the above mentioned ones are impurities. In particular, Pb is admissible only at an impurity level.
  • the fundamental structural constituent phases of the Cu—Sn—Bi-hard particle based sintered material according to the present invention are the copper matrix, the Bi phase and the hard particles.
  • the Bi phase and the hard particles are present at the boundaries of constituent particles of the copper matrix. These points are common to the structure of the materials disclosed in Patent Documents 1 and 2.
  • a characteristic structure according to the present invention resides in the point that, on the sliding surface, the hard particles are all bonded to the copper matrix.
  • the hard particles are phosphide, which is liable to mutually diffuse into the copper matrix, and vice versa, mutual diffusion between P of the hard particles and Cu of the matrix occurs, resulting in bonding between the hard particles and the copper matrix without intermediary of the Bi phase.
  • the bonding strength is high.
  • sintering is preferably carried out through electric resistance heating, rather than high frequency induction heating employed in Patent Document 2.
  • bonding formats for the hard particles there are two types of bonding formats: one is bonding with the copper matrix, and the other is bonding with the Bi phase. Bonding strength between the hard particles and the Bi phase is attributable to an anchoring effect that causes the “morphological bonding.” Meanwhile, the bonding strength between the phosphide-based hard particles and the copper matrix is attributable to mutual diffusion that causes the “diffusion bonding,” which is strong. Difficulty in flow of the copper matrix is due to the latter bonding strength. In addition, even when the Bi phase softens due to the rise in temperature on the sliding surface, the copper matrix does not become flowable in the vicinity of hard particle, because the copper matrix bonded to the hard particles and they do not undergo softening at all.
  • the structure outside the scope of the present invention does not exclude the presence of hard particles that are bonded only to the Bi phase.
  • the hard particles are liable to sink in.
  • the bonding strength mentioned above decreases and a mating shaft easily acts on the copper matrix to flow. As a result the copper covers up the Bi phase, thereby decreasing the exposed surface area of the Bi phase.
  • the number of the hard particles is as many as approximately 20 to 80 per mm 2 of field of view.
  • the copper matrix surrounding this one hard particle softens, then the copper matrix in its vicinity starts to flow, thereby leading to minute seizure. Once minute seizure takes place, this grows up to the entire seizure of parts.
  • every one of the hard particles of sintered material can be bonded to the copper matrix by means of the sintering method described below. Nevertheless, there is such a case where a sliding surface of a sliding member is predetermined, and further its sliding surface, that is, a wearing depth of a sliding member during service life is anticipated. For example, when an AT bush has an anticipated wear depth of approximately from 10 to 80 ⁇ m, it is sufficient that a bonding state of interest be ensured in such depth.
  • hard particles of a Fe—P based compound and a Cu—Sn—Bi based alloy are sintered.
  • Raw material powder may be an atomized powder or the like.
  • the structural control of the present invention is also described in comparison with the prior art.
  • the hard particles are present in the Bi phase.
  • Fe—P based compounds are not used as the hard particles.
  • the hard particles include those in contact only with the Bi phase but not in contact with the copper matrix.
  • the structural controlling method of Patent Document 2 when the individual hard particles are looked at, a half or less length of a hard particle is incorporated in the Bi phase.
  • incorporation of individual hard particles in the Bi phase may be or may not be 50% or less but must not be 100% (complete non-contact of the hard particles with the copper matrix).
  • the structural controlling method of Patent Document 2 regulates so as to make the possibly largest proportion of the hard particles to be in non-contact with the Bi phase.
  • a contact proportion with the Bi phase is not limited. All of the hard particles are in contact with the copper matrix. In order to realize contact of the entire hard particles with copper matrix according to the inventive characteristics, it is important to control the following sintering process in an electric furnace.
  • the temperature-elevating gradient falls within a range from 300 to 1000 degrees C./min in a temperature range of room temperature to 600 degrees C.
  • the deoxidizing effect of P is lost during the elevation of temperature.
  • Bi leaves the Cu—Sn—Bi powder and accumulates around the Fe—P based compound hard particles. Such accumulation occurs earlier than activity increase of powder surface occurs.
  • a preliminary copper alloy having a Cu—Sn—Bi composition shown in Table 1 was prepared. This alloy was subjected to atomization procedure to obtain a powder having a particle diameter of 150 ⁇ m or less.
  • the Cu—Sn—Bi alloy powder and the hard particles shown in Table 1 were mixed with a V-type blender under ordinary conditions. The mixed powder was dispersed on a steel sheet of 150 mm (width) ⁇ 2000 mm (length) to lay the powder in a 1-mm thickness. Sintering was carried out in an electric furnace under hydrogen atmosphere. The sintering conditions were as follows.
  • the temperature gradient set at 600 degrees/min in a temperature range of from room temperature to 600 degrees C.; sintering temperature: from 700 to 900 degrees C.; sintering time: from 5 to 30 minutes. Subsequent to sintering, the sintered layer was densified by rolling. The second sintering was then carried out again under the same conditions.
  • Seizure resistance tests were carried out using the following methods and under the following conditions.
  • Comparative Example 1 is free of Bi, initial seizure resistance and resistance after stationary sliding are poor. Since Comparative Example 2 has a high Bi content, initial seizure resistance and seizure resistance after initial sliding are poor as well. Since Comparative Example 3 has a low Sn content, although it has good initial seizure resistance, seizure resistance after stationary sliding is poor. Since Comparative Example 4 has a high Sn content, initial seizure and seizure resistance after stationary sliding are poor. Since the hard particles of Comparative Example 5 are Al 2 O 3 , although initial seizure resistance is good, seizure resistance after stationary sliding is poor.
  • Comparative Example 6 is free of hard particles, although initial seizure resistance is good, seizure resistance after stationary sliding is poor. Since Comparative Example 7 has a high additive content of hard particles, the seizure resistance after stationary sliding is poor. Since the average particle diameter of the hard particles is large in Comparative Example 8, although initial seizure resistance is good, seizure resistance after stationary sliding is poor. Since the average particle diameter of the hard particles is small in Comparative Example 9, although initial seizure resistance is good, the seizure resistance after stationary sliding is poor.
  • FIG. 4 shows the results of Comparative Example 2. As is clear from FIG. 4 , hard particles are completely surrounded by the Bi phase. Since Comparative Example 3 has a low Sn content and hence a low recrystallizing temperature, several hard particles are completely surrounded by the Bi phase.
  • Example 2 P was added to several of the compositions of Example 1 in Table 1. Test Samples were prepared by the same method employed for those in Table 1, and the same test procedure was followed. In Example 2, in which appropriate amount of P is added, the surface pressure, at which the initial surface pressure occurred, and the surface pressure, at which seizure occurred after stationary sliding, were found to be improved over those of Example 1, in which P is not added. This is because added P further promotes diffusion and hence diffusion bonding between the copper matrix and the hard particles, thereby improving holding of the hard particles. Meanwhile, when P is added excessively as shown in Table 2, Comparative Example 2, the seizure surface pressures of initial sliding and after stationary sliding seriously decreases.
  • the material according to the present invention exhibits little deterioration in seizure resistance caused by sliding and hence exhibits stable performance.
  • the material of present invention can provide reliable components, such as an automatic transmission (AT) bush, a piston-pin bush, and a bush for general machines.
  • AT automatic transmission
  • a piston-pin bush a bush for general machines.
  • FIG. 1 An optical microphotograph (magnification: ⁇ 250) of a sintered alloy of inventive example No. 5.
  • FIG. 2 An optical microphotograph (magnification: ⁇ 250) of a sintered alloy of inventive example No. 9.
  • FIG. 3 An optical microphotograph (magnification: ⁇ 250) of a sintered alloy of the inventive example No. 21.
  • FIG. 4 An optical microphotograph (magnification: ⁇ 250) of a sintered alloy of the comparative example No. 2.

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Powder Metallurgy (AREA)
  • Sliding-Contact Bearings (AREA)
US12/376,381 2006-08-05 2007-08-02 Pb-FREE COPPER ALLOY SLIDING MATERIAL Abandoned US20100266444A1 (en)

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
JP2006213986 2006-08-05
JP2006-213986 2006-08-05
JP2006-219709 2006-08-11
JP2006219709 2006-08-11
PCT/JP2007/065125 WO2008018348A1 (fr) 2006-08-05 2007-08-02 Matière de glissement en alliage de cuivre sans plomb

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EP (1) EP2048253B1 (fr)
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KR (1) KR20090028638A (fr)
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WO (1) WO2008018348A1 (fr)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20110224112A1 (en) * 2008-09-10 2011-09-15 Taiho Kogyo Co., Ltd. SLIDING PART MADE OF Pb-FREE Cu-Bi BASED SINTERED ALLOY
GB2489601A (en) * 2011-03-30 2012-10-03 Daido Metal Co Sliding bearing with a layer of a copper-bismuth-tin-phosphorous alloy
US8845776B2 (en) 2009-04-28 2014-09-30 Taiho Kogyo Co., Ltd. Lead-free copper-based sintered sliding material and sliding parts
JP2016079432A (ja) * 2014-10-14 2016-05-16 大豊工業株式会社 すべり軸受用銅合金
US11807926B2 (en) 2019-10-16 2023-11-07 Taiho Kogyo Co., Ltd. Copper alloy sliding material

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US8679641B2 (en) * 2007-01-05 2014-03-25 David M. Saxton Wear resistant lead free alloy bushing and method of making
US20120114971A1 (en) * 2007-01-05 2012-05-10 Gerd Andler Wear resistant lead free alloy sliding element method of making
JP5663500B2 (ja) * 2009-03-03 2015-02-04 ケステック イノベーションズ エルエルシー 無鉛高強度高潤滑性銅合金
JP5058276B2 (ja) * 2010-02-23 2012-10-24 大同メタル工業株式会社 銅系摺動材料
EP2918692B1 (fr) * 2012-02-29 2018-08-01 Diamet Corporation Alliage fritté à résistance supérieure à l'usure
CN103028733A (zh) * 2012-12-14 2013-04-10 浦江汇凯粉体科技有限公司 一种CuSn10Bi3.5铜铋合金粉末制备方法
CN103589901B (zh) * 2013-11-08 2015-05-13 苏州天兼金属新材料有限公司 一种无铅环保铜基合金管及其制造方法
CN103589902B (zh) * 2013-11-08 2015-08-12 苏州天兼金属新材料有限公司 一种无铅环保铜基合金材料及其制造方法
CN110406201B (zh) * 2019-08-21 2020-09-25 大连理工大学 一种自润滑双金属层状复合材料及其制备方法和应用

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US10041148B2 (en) 2018-08-07
JP5328353B2 (ja) 2013-10-30
JPWO2008018348A1 (ja) 2009-12-24
CN101541989A (zh) 2009-09-23
KR20090028638A (ko) 2009-03-18
US20120294750A1 (en) 2012-11-22
EP2048253A4 (fr) 2012-04-11
WO2008018348A9 (fr) 2008-06-12

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