JP3337087B2 - Copper alloy with excellent high-temperature wear resistance - Google Patents

Copper alloy with excellent high-temperature wear resistance

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Publication number
JP3337087B2
JP3337087B2 JP01477293A JP1477293A JP3337087B2 JP 3337087 B2 JP3337087 B2 JP 3337087B2 JP 01477293 A JP01477293 A JP 01477293A JP 1477293 A JP1477293 A JP 1477293A JP 3337087 B2 JP3337087 B2 JP 3337087B2
Authority
JP
Japan
Prior art keywords
copper alloy
wear resistance
valve
intermetallic compound
resistance
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Fee Related
Application number
JP01477293A
Other languages
Japanese (ja)
Other versions
JPH06228681A (en
Inventor
納 眞 加
木 章 藤
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nissan Motor Co Ltd
Original Assignee
Nissan Motor Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Nissan Motor Co Ltd filed Critical Nissan Motor Co Ltd
Priority to JP01477293A priority Critical patent/JP3337087B2/en
Priority to US08/189,780 priority patent/US5468310A/en
Publication of JPH06228681A publication Critical patent/JPH06228681A/en
Priority to US08/610,913 priority patent/US6037067A/en
Application granted granted Critical
Publication of JP3337087B2 publication Critical patent/JP3337087B2/en
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

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Description

【発明の詳細な説明】DETAILED DESCRIPTION OF THE INVENTION

【0001】[0001]

【産業上の利用分野】本発明は、高温での耐摩耗性に優
れた熱伝導率の大きい銅合金に関し、とくに、エンジン
用などの摺動部材、例えば、バルブシート(弁座),バ
ルブガイド(弁案内部材)などの素材として好適に利用
される耐酸化性および高温耐摩耗性に優れた銅合金に関
するものである。
BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a copper alloy having excellent wear resistance at high temperatures and a high thermal conductivity, and particularly to a sliding member for an engine or the like, for example, a valve seat (valve seat), a valve guide. The present invention relates to a copper alloy excellent in oxidation resistance and high-temperature wear resistance that is suitably used as a material such as a (valve guide member).

【0002】[0002]

【従来の技術】近年、自動車のエンジンは、高性能化・
高出力化が進み、このため、エンジンのバルブシート,
バルブガイドが高温になり、摺動面圧も従来よりさらに
大きくなる傾向にある。加えて、高出力と良好な燃費と
を両立させるために、バルブシート,バルブガイドにお
いて良好な熱伝達が必要となってきている。
2. Description of the Related Art In recent years, automobile engines have been improved in performance.
As the output has increased, the engine valve seat,
The temperature of the valve guide tends to be high, and the sliding surface pressure tends to be higher than before. In addition, in order to achieve both high output and good fuel economy, good heat transfer is required in valve seats and valve guides.

【0003】したがって、これらの部品の素材として
は、耐摩耗性と熱伝導率の良い材料が要求されるように
なってきている。
[0003] Therefore, as a material for these components, a material having good wear resistance and thermal conductivity has been required.

【0004】従来から、これらの材料は、Cu合金を中
心に研究・開発されてきており、例えば、アルミニウム
青銅系にNi,Feを添加して強化したJIS Al
BC1〜4、とくに、Al BC 3(『非鉄金属材
料』 椙山正孝著 コロナ社昭和53年 第14版 第
73頁)や、同系列のAISI C95500(『Me
tals Handbook 9th Edition
Vol.2』American Society f
or Metals 1979 第433頁)などがバ
ルブシート等の素材として採用されている実績がある。
[0004] Conventionally, these materials have been researched and developed mainly on Cu alloys. For example, JIS Al which is strengthened by adding Ni and Fe to aluminum bronze is used.
BC1-4, in particular, AlBC3 ("Non-ferrous metal materials", Masataka Sugiyama, Corona Publishing Co., Ltd., 1973, 14th edition, p. 73), and AISI C95500 ("Me
tals Handbook 9th Edition
Vol. 2] American Society f
or Metals 1979, p. 433) has been used as a material for valve seats and the like.

【0005】ところで、これらの従来合金では、近年の
上記したごとき特性が要求されるエンジンのバルブシー
ト,バルブガイドの素材として利用した場合、高温での
耐摩耗性が十分でないため、厳しい条件下の実用に際し
ては摩耗が著しく、十分満足に対応することができがた
いという問題点があった。
When these conventional alloys are used as materials for valve seats and valve guides of engines that require the above-mentioned characteristics in recent years, their wear resistance at high temperatures is not sufficient, so that they are used under severe conditions. At the time of practical use, there was a problem that wear was remarkable and it was difficult to respond sufficiently.

【0006】そこで、本発明者らは、先に、重量%で、
Al:1.0〜15.0%、Ti:0.3〜8.0%、
Co:0.5〜10.0%、残部Cuおよび不純物から
なる組成を有し、Al,Ti,Co,Cuの2種以上か
らなる金属間化合物、例えば、Al−Ti,Cu−T
i,Co−Ti,Al−Ti−Co,Al−Ti−Cu
等よりなる金属間化合物のうち少なくとも1種が分散し
た組織を有するものとした高温耐摩耗性に優れた銅合金
を開発した(本出願時未公開)。
Therefore, the present inventors first described that, by weight%,
Al: 1.0 to 15.0%, Ti: 0.3 to 8.0%,
Co: 0.5 to 10.0%, having a composition consisting of the balance Cu and impurities, and an intermetallic compound consisting of two or more of Al, Ti, Co, and Cu, for example, Al-Ti, Cu-T
i, Co-Ti, Al-Ti-Co, Al-Ti-Cu
A copper alloy excellent in high-temperature abrasion resistance having a structure in which at least one kind of an intermetallic compound composed of the above-mentioned intermetallic compounds is dispersed has been developed (not disclosed at the time of filing this application).

【0007】[0007]

【発明が解決しようとする課題】上記発明に係わる銅合
金は、Cu合金中にAl,Ti等を含有させることによ
りAl−Ti,Cu−Ti,Al−Ti−Co等の金属
間化合物を微細かつ均一に分散した組織としていること
によって、高温での耐摩耗性に優れていると共に熱伝導
率も大きく、バルブシートやバルブガイド等の素材とし
て好適なものとしているが、酸素のゲッター剤としても
用いられるIVa族元素のTiが必須の構成元素として
含有されているため、このような合金組成を有する粉末
から大気中でレーザ肉盛りした場合に、Tiが選択酸化
されたときに脆化する可能性があったり、有鉛ガソリン
等の燃料を用いた場合に、腐食燃焼成分によりTiが選
択腐食されたときに摩耗が促進される可能性があったり
するという課題があった。
SUMMARY OF THE INVENTION The copper alloy according to the above-mentioned invention is characterized in that Al, Ti and the like are contained in a Cu alloy to reduce intermetallic compounds such as Al-Ti, Cu-Ti and Al-Ti-Co. By having a uniformly dispersed structure, it has excellent wear resistance at high temperatures and high thermal conductivity, making it suitable as a material for valve seats and valve guides, but also as a getter agent for oxygen. Since Ti of the IVa group element to be used is contained as an essential constituent element, when the powder having such an alloy composition is laser clad in the air, the powder may become brittle when selectively oxidized. The problem is that when fuel such as leaded gasoline is used, wear may be promoted when Ti is selectively corroded by corrosive combustion components. Was Tsu.

【0008】[0008]

【発明の目的】本発明は、このような従来の課題にかん
がみてなされたものであって、とくに高温での耐摩耗性
に優れていて、高温での耐摩耗性と熱伝導率に優れてい
ることが要求されるエンジンのバルブシートやバルブガ
イドの素材として好適であり、IVa族元素であるTi
を必須の構成元素として含有していないため、Tiが選
択酸化されたりあるいは選択腐食されたりすることがな
い耐久性能に優れたバルブシートやバルブガイドを得る
ことが可能である高温耐摩耗性銅合金を提供することを
目的としている。
SUMMARY OF THE INVENTION The present invention has been made in view of such conventional problems, and has excellent wear resistance at high temperatures, and has excellent wear resistance and thermal conductivity at high temperatures. Ti is a suitable material for valve seats and valve guides of engines that require
High-temperature wear-resistant copper alloy capable of obtaining valve seats and valve guides having excellent durability without Ti being selectively oxidized or selectively corroded because it does not contain Ti as an essential constituent element It is intended to provide.

【0009】[0009]

【課題を解決するための手段】本発明者らがなした先の
発明においては、アルミニウム青銅合金をベースに、重
量%で、Al:1.0〜15.0%、Ti:0.3〜
8.0%、Co:0.5〜10.0%、残部Cuおよび
不純物からなる組成を有する銅合金とすることで、Ti
とCu,Co,Alとからなる二元系もしくは三元系の
金属間化合物のうち少なくとも1種が均一に分散した組
織が得られ、その結果、優れた高温耐摩耗性を示すこと
が見い出された。
In the prior invention made by the present inventors, based on an aluminum bronze alloy, Al: 1.0 to 15.0% and Ti: 0.3 to 0.3% by weight.
By using a copper alloy having a composition of 8.0%, Co: 0.5 to 10.0%, the balance of Cu and impurities, Ti
It has been found that a structure in which at least one of binary or ternary intermetallic compounds composed of Al and Cu, Co, and Al is uniformly dispersed is obtained, and as a result, excellent high-temperature wear resistance is exhibited. Was.

【0010】この結果は、銅合金において、高温硬度が
高いアルミニウム青銅合金成分の基地中に非常に硬い上
記成分系の微細な金属間化合物が均一に分散した組織
が、バルブシートやバルブガイドの重要な摩耗要因であ
る凝着摩耗やアブレーシブ摩耗の抑制に有効であること
を示している。
[0010] This result indicates that in the copper alloy, the structure in which the very hard fine intermetallic compound of the above-mentioned component system is uniformly dispersed in the matrix of the aluminum bronze alloy component having a high high-temperature hardness is important for the valve seat and the valve guide. It shows that it is effective in suppressing adhesive wear and abrasive wear, which are important wear factors.

【0011】しかしながら、これらの金属間化合物の析
出が期待できるTiおよびこれのみならずZr等のIV
a族元素では、耐酸化性や耐食性が問題となる。
[0011] However, Ti, which can be expected to precipitate these intermetallic compounds, and not only IV, such as Zr, but also
In the case of group a elements, oxidation resistance and corrosion resistance are problematic.

【0012】そこで、本発明においては、Va族元素で
あるV,Nb,TaをTiの代わりに含有させた場合
に、耐酸化性および耐摩耗性の抑制に効果があるかどう
か、さらには、高温耐摩耗性への影響はどうであるかを
一連の研究を通じて鋭意調べていった結果、以下の組成
および金属間化合物の粒径が全ての特性を満足できるこ
とを見い出した。
Therefore, in the present invention, whether V, Nb, or Ta, which is a Group Va element, is contained in place of Ti is effective in suppressing the oxidation resistance and wear resistance. As a result of a series of studies on the effects on the high-temperature wear resistance, it was found that the following composition and the particle size of the intermetallic compound can satisfy all the characteristics.

【0013】すなわち、本発明の請求項1に係わる高温
耐摩耗性に優れた銅合金は、重量%で、Al:1.0〜
15.0%、元素周期表Va族元素であるV,Nb,T
aのうち少なくとも1種:0.1〜5.0%、残部Cu
および不純物から構成され、また、本発明の請求項2に
係わる高温耐摩耗性に優れた銅合金は、Al:1.0〜
15.0%、Co:0.5〜10.0%、元素周期表V
a族元素であるV,Nb,Taのうち少なくとも1種:
0.1〜5.0%、残部Cuおよび不純物から構成され
る。
That is, the copper alloy excellent in high-temperature wear resistance according to the first aspect of the present invention has an Al content of 1.0 to 1.0% by weight.
15.0%, V, Nb, T, which are elements of group Va in the periodic table
at least one of a: 0.1 to 5.0%, with the balance being Cu
And a copper alloy having excellent high-temperature wear resistance according to claim 2 of the present invention,
15.0%, Co: 0.5 to 10.0%, Periodic Table of Elements V
At least one of group a elements V, Nb and Ta:
0.1 to 5.0%, with the balance being Cu and impurities.

【0014】この組成からなる銅合金のインゴットもし
くは粉末においては、Va族元素の1種以上とCu,A
l,Co元素の1種以上からなる金属間化合物のうち少
なくとも1種が粒径10μm程度の球状ないしは塊状物
として析出分散した組織を有する結果、先願の成分系材
料と同等以上の優れた耐摩耗性を示すと共に、耐酸化性
の向上により大気中でのレーザ肉盛り性の大幅な改善な
らびにバルブシートとしては有鉛ガソリン等での腐食摩
耗の抑制に大きな効果が見い出された。
In a copper alloy ingot or powder having the above composition, one or more of Va group elements and Cu, A
At least one of the intermetallic compounds consisting of one or more of the l and Co elements has a structure in which the particles are precipitated or dispersed as spheres or aggregates having a particle size of about 10 μm. In addition to exhibiting abrasion properties, it has been found that laser build-up in the atmosphere is greatly improved by improving oxidation resistance, and that a valve seat has a great effect in suppressing corrosion and abrasion in leaded gasoline and the like.

【0015】また、先願と同様に、本発明の請求項3に
係わる高温耐摩耗性に優れた銅合金は、請求項1または
2の銅合金にさらにFeおよびNiの1種または2種を
0.5〜12.0%含有したものとし、本発明の請求項
4に係わる高温耐摩耗性に優れた銅合金は、請求項1,
2または3の銅合金にさらにMnを1.0〜10.0%
含有したものとすることで、耐摩耗性をより一層向上さ
せることができる。
Further, as in the prior application, the copper alloy excellent in high-temperature wear resistance according to claim 3 of the present invention is obtained by further adding one or two types of Fe and Ni to the copper alloy of claim 1 or 2. The copper alloy excellent in high-temperature wear resistance according to claim 4 of the present invention is contained in 0.5 to 12.0%.
Mn is further added to the copper alloy of 2 or 3 by 1.0 to 10.0%.
By containing it, the wear resistance can be further improved.

【0016】そして、これらの銅合金は、製造性が良
く、優れた耐摩耗性と耐腐食摩耗性を有し、種々の高性
能内燃機関用の摺動部材に適していることを確認し、な
かでも、バルブフェースの着座部であるバルブシート
や、バルブステムと摺動するバルブガイドには、優れた
性能を示すことが確かめられた。
These copper alloys were confirmed to have good manufacturability, excellent abrasion resistance and corrosion resistance, and suitable for various high-performance sliding members for internal combustion engines. Above all, it was confirmed that the valve seat, which is the seat portion of the valve face, and the valve guide that slides with the valve stem exhibited excellent performance.

【0017】次に、本発明に係わる銅合金の成分組成
(重量%)を上記の通りに限定した理由を説明する。
Next, the reason why the component composition (% by weight) of the copper alloy according to the present invention is limited as described above will be described.

【0018】Al:本発明の銅合金中におけるAlは、
基地に固溶して高温強度および高温硬度を増大させるこ
とで、高温耐摩耗性を向上させる作用があり、さらに、
後述の周期律表Va族元素,Co,Fe,Ni等と結合
して複合金属間化合物を析出させ、これによって耐熱
性,耐摩耗性を向上させる作用があるが、その含有量が
1.0%未満では前記作用が十分に得られず、一方、そ
の含有量が15.0%を超えると脆化し、熱伝導性が低
下するようになることから、Al含有量を1.0〜1
5.0%とした。
Al: Al in the copper alloy of the present invention is
By increasing the high-temperature strength and high-temperature hardness by forming a solid solution in the matrix, there is an effect of improving high-temperature wear resistance,
It has the effect of bonding with a group Va element of the periodic table, Co, Fe, Ni, etc., which will be described later, to precipitate a composite intermetallic compound, thereby improving heat resistance and abrasion resistance. %, The effect is not sufficiently obtained. On the other hand, if the content is more than 15.0%, embrittlement is caused and thermal conductivity is reduced.
5.0%.

【0019】Co:本発明の銅合金中におけるCoは、
基地に固溶して耐熱性を向上させる作用があり、Cuと
金属間化合物を形成したり、Va族元素とCu,Al元
素とともに種々の複合金属間化合物を形成して、耐熱
性,耐摩耗性を向上させる作用がある。しかし、その含
有量が0.5%未満では前記作用が十分に得られず、一
方、その含有量が10.0%を超えると熱伝導性が低下
するようになることから、Coを添加する場合はその含
有量を0.5〜10.0%と定めた。
Co: Co in the copper alloy of the present invention is
It has the effect of improving the heat resistance by forming a solid solution in the matrix, forming an intermetallic compound with Cu, or forming various complex intermetallic compounds together with a Va group element and Cu and Al elements to provide heat resistance and wear resistance. Has the effect of improving the properties. However, if the content is less than 0.5%, the above effect cannot be sufficiently obtained. On the other hand, if the content exceeds 10.0%, the thermal conductivity decreases, so Co is added. In this case, the content was determined to be 0.5 to 10.0%.

【0020】Va族元素:本発明の銅合金中における
V,Nb,Ta等のVa族元素成分は、Cu,Al,C
oと結合し、粒径が10μm程度の球状ないしは塊状の
Va族元素リッチの金属間化合物と、粒径が1μm程度
の非常に微細な析出物が樹脂状ないしは花びら状に並ん
だVa族元素量の少ない金属間化合物を形成し、高温耐
摩耗性ならびに耐アブレーシブ摩耗性の向上に大きな効
果を与える作用がある。しかし、Va族元素の合計含有
量が0.1%未満では前記作用が十分に得られず、一
方、5.0%を超えるとアルミニウム青銅系の母材に溶
けず偏析してしまうので、Va族元素の含有量を0.1
〜5.0%とした。
Group Va element: The group Va element components such as V, Nb and Ta in the copper alloy of the present invention are Cu, Al, C
o, a spherical or massive Va-group element-rich intermetallic compound having a particle size of about 10 μm, and an amount of a Va-group element in which very fine precipitates having a particle size of about 1 μm are arranged in a resin or petal shape. And has an effect of significantly increasing the high-temperature wear resistance and abrasive wear resistance. However, if the total content of the Va group element is less than 0.1%, the above effect cannot be sufficiently obtained. On the other hand, if the total content is more than 5.0%, it is not dissolved in the aluminum bronze base material and segregates. Group element content 0.1
To 5.0%.

【0021】Fe,Ni:本発明の銅合金中におけるF
e,Niは、主として、AlやVa族元素と金属間化合
物を形成して、銅合金の耐熱性,耐摩耗性を向上させる
作用がある。しかし、その含有量が0.5%未満では前
記作用が十分に得られず、一方、12.0%を超えると
熱伝導性が悪くなりかつまた脆化するので、Fe,Ni
を添加する場合は1種または2種の合計含有量を0.5
〜12.0%と定めた。
Fe, Ni: F in the copper alloy of the present invention
e and Ni mainly form an intermetallic compound with an Al or Va group element to improve the heat resistance and wear resistance of the copper alloy. However, if the content is less than 0.5%, the above effect cannot be sufficiently obtained. On the other hand, if the content exceeds 12.0%, the thermal conductivity deteriorates and the material becomes brittle.
Is added, the total content of one or two is 0.5
112.0%.

【0022】Mn:本発明の銅合金中におけるMnは、
アルミニウム青銅の組織を粒状化して強度を向上させる
と共に合金の徐冷脆化を防ぐ作用もある。また、基地に
固溶して強度,耐摩耗性をも向上させる作用がある。し
かし、その含有量が1.0%未満では前記作用が十分に
得られず、一方、10.0%を超えると脆化するので、
Mnを添加する場合はその含有量を1.0〜10.0%
と定めた。
Mn: Mn in the copper alloy of the present invention is
It also has the effect of increasing the strength by granulating the structure of aluminum bronze and preventing the alloy from being slowly cooled and embrittled. Further, it has the effect of forming a solid solution in the matrix to improve the strength and wear resistance. However, if the content is less than 1.0%, the above effect cannot be sufficiently obtained, while if the content exceeds 10.0%, embrittlement occurs.
When Mn is added, its content is 1.0 to 10.0%
It was decided.

【0023】[0023]

【発明の作用】本発明に係わる銅合金は、Al:1.0
〜15.0%、元素周期表Va族元素であるV,Nb,
Taのうち少なくとも1種:0.1〜5.0%、場合に
よってはCo:0.5〜10.0%、同じく場合によっ
てはFeおよびNiの1種または2種:0.5〜12.
0%、同じく場合によってはMn:1.0〜10.0%
を含有し、残部Cuおよび不純物からなる組成を有し、
Al,Co,Fe,Ni,Cuの1種以上とVa族元素
の1種以上とからなる金属間化合物、例えば、Al−
V,Cu−V,Al−Nb,Cu−Nb,Al−Ta,
Cu−Ta,Al−Cu−V,Al−Co−V,Cu−
Co−V,Al−Cu−Nb,Al−Co−Nb,Cu
−Co−Nb,Al−Cu−Ta,Al−Co−Ta,
Cu−Co−Ta等よりなる金属間化合物のうち少なく
とも1種が粒径10μm程度の球状ないしは塊状物とし
て分散し、場合によってはAl,Co,Fe,Ni,C
uの2種以上からなる金属間化合物、例えば、Cu−C
o,Fe−Al,Ni−Al,Al−Fe−Ni等より
なる金属間化合物が粒径10μm程度の球状ないしは塊
状物として分散した組織を有するものとなっているの
で、高温で優れた耐摩耗性を示すと共に、耐酸化性およ
び耐腐食摩耗性が向上したものとなり、バルブシートを
レーザ肉盛りにより形成する場合において大気中でのレ
ーザ肉盛り性が大幅に改善されると共に、有鉛ガソリン
等による腐食摩耗が大幅に抑制されることとなり、さら
には、デポジットや摩耗粉によるアブレーシブ摩耗に対
しての大幅な改善効果がもたらされ、バルブシートに限
らずエンジン等の各種高温環境下での摺動部材として適
したものとなる。
The copper alloy according to the present invention has an Al content of 1.0
1515.0%, V, Nb,
At least one of Ta: 0.1 to 5.0%, in some cases Co: 0.5 to 10.0%, and in some cases, one or two of Fe and Ni: 0.5 to 12.
0%, and in some cases, Mn: 1.0 to 10.0%
Having a composition consisting of the balance Cu and impurities,
An intermetallic compound composed of at least one of Al, Co, Fe, Ni, and Cu and at least one of Va group elements, for example, Al-
V, Cu-V, Al-Nb, Cu-Nb, Al-Ta,
Cu-Ta, Al-Cu-V, Al-Co-V, Cu-
Co-V, Al-Cu-Nb, Al-Co-Nb, Cu
-Co-Nb, Al-Cu-Ta, Al-Co-Ta,
At least one of the intermetallic compounds made of Cu—Co—Ta or the like is dispersed as spheres or aggregates having a particle size of about 10 μm, and in some cases, Al, Co, Fe, Ni, C
intermetallic compound consisting of two or more kinds of u, for example, Cu-C
O, Fe-Al, Ni-Al, Al-Fe-Ni and other intermetallic compounds have a structure in which they are dispersed as spheres or aggregates having a particle size of about 10 μm, so that they have excellent wear resistance at high temperatures. In addition to exhibiting oxidation resistance and corrosion and wear resistance, when the valve seat is formed by laser cladding, laser cladding in the atmosphere is greatly improved, and leaded gasoline etc. Corrosion and abrasion due to deposits and abrasion powder are greatly improved, and the sliding wear is not limited to valve seats and is not limited to various types of high-temperature environments such as engines. It becomes suitable as a moving member.

【0024】[0024]

【実施例】実施例1〜6;比較例1,2 高周波誘導溶解炉を用い、黒鉛るつぼ内で、表1の実施
例1〜6および表2の比較例1,2に示す組成を有する
Cu合金溶湯を溶製し、鋳造してインゴットとした後、
各インゴットに対し780℃で熱間鍛造および熱間押出
し加工を施し、次いで、各押出し素材に切削加工を施す
ことによって、本発明例1〜6のバルブシートおよび比
較例1,2のバルブシートを製作した。そして、これら
のバルブシートを実機エンジン用アルミニウム合金製シ
リンダヘッドの排気側に圧入した。
Examples 1 to 6; Comparative Examples 1 and 2 Cu having the composition shown in Examples 1 to 6 of Table 1 and Comparative Examples 1 and 2 of Table 2 was placed in a graphite crucible using a high-frequency induction melting furnace. After smelting the molten alloy and casting it into an ingot,
Each of the ingots is subjected to hot forging and hot extrusion at 780 ° C., and then the extruded material is subjected to cutting to obtain the valve seats of Examples 1 to 6 of the present invention and the valve seats of Comparative Examples 1 and 2. Made. These valve seats were pressed into the exhaust side of an aluminum alloy cylinder head for a real engine.

【0025】実施例7;比較例3 高周波誘導溶解炉を用い、黒鉛るつぼ内で、表1の実施
例7および表2の比較例3に示す組成を有するCu合金
溶湯を溶製し、各合金溶湯をガスアトマイズによって粉
末化し、脱水処理および粒度分布調整を行って、粉末冶
金用の粉末とした後、各粉末に潤滑剤を添加し、成形し
た後脱ろうおよび焼結を行って、本発明例7のバルブシ
ートと比較例3のバルブシートを製作した。そして、こ
れらのバルブシートについても、実機エンジン用アルミ
ニウム合金製シリンダヘッドの排気側に圧入した。
Example 7 Comparative Example 3 Using a high-frequency induction melting furnace, a Cu alloy melt having the composition shown in Example 7 in Table 1 and Comparative Example 3 in Table 2 was melted in a graphite crucible, and each alloy was melted. The molten metal was powderized by gas atomization, subjected to dehydration treatment and particle size distribution adjustment to obtain powder for powder metallurgy, a lubricant was added to each powder, and dewaxing and sintering were performed after molding. 7 and the valve seat of Comparative Example 3 were produced. These valve seats were also pressed into the exhaust side of an aluminum alloy cylinder head for a real engine.

【0026】実施例8,9;比較例4 高周波誘導溶解炉を用い、黒鉛るつぼ内で、表2の実施
例8,9および比較例4に示す組成を有するCu合金溶
湯を溶製し、各合金溶湯をガスアトマイズによって粉末
化し、脱水処理および脱ガス処理ならびに粒度調整を行
って肉盛り用の粉末とした。そして、これらの粉末を5
kWのCOガスレーザを用いて直ちにアルミニウム合
金製シリンダヘッドの排気バルブシート部を加工した凹
部に3mm以上の厚さで肉盛りした。その後、機械加工
を行って、実施例8,9および比較例4のバルブシート
をそなえたシリンダヘッドを作製した。
Examples 8 and 9; Comparative Example 4 Using a high-frequency induction melting furnace, molten Cu alloys having the compositions shown in Examples 8 and 9 of Table 2 and Comparative Example 4 were melted in a graphite crucible. The molten alloy was pulverized by gas atomization, dewatered and degassed, and subjected to particle size adjustment to prepare powder for overlay. And these powders
Immediately using a kW CO 2 gas laser, the exhaust valve seat portion of the aluminum alloy cylinder head was overlaid with a thickness of 3 mm or more in the processed recess. Thereafter, machining was performed to produce a cylinder head provided with the valve seats of Examples 8 and 9 and Comparative Example 4.

【0027】組織観察例 このようにして製作した実施例1〜9,比較例1〜4の
各バルブシートにおいて、析出金属間化合物を調べたと
ころ、表3および表4に示す結果であり、また、析出金
属間化合物の体積率を調べたところ、同じく表3および
表4に示す結果であった。
Structure Observation Examples The intermetallic compounds deposited in the valve seats of Examples 1 to 9 and Comparative Examples 1 to 4 manufactured as described above were examined. The results are shown in Tables 3 and 4. When the volume ratio of the precipitated intermetallic compound was examined, the results are also shown in Tables 3 and 4.

【0028】そして、以上の実施例を通じて、Va族元
素であるV,Nb,Ta等を主体とする金属間化合物の
析出量としては、体積率で1%以上50%以下が好まし
いことが認められた。
Through the above examples, it has been found that the deposition amount of the intermetallic compound mainly composed of Va elements such as V, Nb, Ta, etc. is preferably 1% to 50% by volume. Was.

【0029】[0029]

【表1】 [Table 1]

【0030】[0030]

【表2】 [Table 2]

【0031】[0031]

【表3】 [Table 3]

【0032】[0032]

【表4】 [Table 4]

【0033】実機エンジン耐久試験例 次に、上記実施例1〜9,比較例1〜4で得た実機エン
ジン用シリンダヘッドを実機エンジンに組み込み、下記
の表5に示す耐久試験を行った。
The actual engine durability test Examples built above Examples 1-9, the actual cylinder head engines obtained in Comparative Examples 1 to 4 in an actual engine, a durability test was carried out as shown in Table 5 below.

【0034】[0034]

【表5】 [Table 5]

【0035】耐久試験後に各バルシートの摩耗量(摩耗
深さ)を測定すると共に摩擦面を観察した結果を表3お
よび表4に示す。ただし、比較例4のバルブシートで
は、耐久60hにて肉盛り部がアルミニウム合金製シリ
ンダヘッドより剥離脱落してエンジンが止まったので、
摩耗量を測定することはできなかった。
Tables 3 and 4 show the results of measuring the amount of wear (wear depth) of each valve sheet and observing the friction surface after the durability test. However, in the valve seat of Comparative Example 4, the build-up portion was peeled off and dropped off from the aluminum alloy cylinder head at the endurance of 60 hours, and the engine stopped.
The amount of wear could not be measured.

【0036】表1ないし表4に示した結果より明らかな
ように、本発明例1〜9のバルブシートでは、いずれも
摩耗量が少ないものとなっていて優れた耐摩耗性を示す
とともに、走査電子顕微鏡による摩擦面観察において
も、すべりで生じた浅い摩耗痕が見られるだけで、腐食
等の異常な形態は認められなかった。
As is evident from the results shown in Tables 1 to 4, all of the valve seats of Examples 1 to 9 of the present invention have a small amount of abrasion, exhibit excellent abrasion resistance, and have a high scanning performance. In the observation of the friction surface with an electron microscope, only a shallow wear mark caused by slip was observed, but no abnormal form such as corrosion was observed.

【0037】また、焼結材である実施例7のバルブシー
トでは、溶製材である実施例6のバルブシートに比べて
耐摩耗性には大差がないが、製品が最終形状に近い(n
ear−net−shape)で製作できるため、量産
時の加工効率や材料歩留りが高いといったメリットがあ
る。
Further, in the valve seat of Embodiment 7 which is a sintered material, there is not much difference in abrasion resistance as compared with the valve seat of Embodiment 6 which is an ingot material, but the product is close to the final shape (n
Since it can be manufactured by ear-net-shape, there is an advantage that the processing efficiency and material yield during mass production are high.

【0038】一方、レーザ肉盛り材である実施例8,9
のバルブシートでは、上記焼結材および溶製材に比べて
さらに優れた耐摩耗性を示している。これは、レーザに
よる肉盛りにおいて、溶融された合金粉末が熱伝導度の
高いアルミニウム合金製シリンダヘッド材上に盛られる
と瞬時に急冷凝固するために、溶製材や焼結材に比べ硬
くなることが一つの要因と考えられる。
On the other hand, Embodiments 8 and 9 which are laser overlay materials
The valve seat of No. 1 shows more excellent wear resistance than the above-mentioned sintered material and ingot material. This is because, when the molten alloy powder is put on a cylinder head material made of aluminum alloy with high thermal conductivity, it is rapidly cooled and solidified instantaneously in laser cladding, so that it becomes harder than the molten material or sintered material. Is considered as one factor.

【0039】これら本発明例のバルブシートに対して、
比較例1〜4のバルブシートにおいては、溶製材である
比較例1,2のバルブシートおよび焼結材である比較例
3のバルブシートで明らかなように、かなり大きく摩耗
してしまうと共に、肉盛り材である比較例4のバルブシ
ートでは耐久途中で剥離するという不具合を生じた。
With respect to these valve seats of the present invention,
As is clear from the valve seats of Comparative Examples 1 and 2 which are ingot materials and the valve seats of Comparative Example 3 which is a sintered material, the valve seats of Comparative Examples 1 to 4 were considerably worn, In the valve seat of Comparative Example 4 which was a filling material, there was a problem that the valve sheet was peeled off during the durability.

【0040】そして、比較例1〜3のバルブシートにつ
いて摩擦面を走査電子顕微鏡で観察してみると、いずれ
のバルブシートにおいても虫くい状のピットが多く認め
られた。さらに、これらのピット部についてTi元素お
よびCl,Br元素の特性X線像を見ると、ピット周辺
にこれらの元素が偏析していた。
When the friction surfaces of the valve seats of Comparative Examples 1 to 3 were observed with a scanning electron microscope, a large number of pits were found in all of the valve seats. Further, when a characteristic X-ray image of the Ti element and the Cl and Br elements was observed in these pit portions, these elements were segregated around the pits.

【0041】この結果から、比較例のバルブシートに含
まれるTi元素が、有鉛ガソリン燃料に含まれる掃鉛剤
である二塩化エチレンや二臭化エチレンが燃焼生成物で
あるPbClやPbBrとしてガスに混入し、シー
ト面に堆積してこれらのClやBrと摩擦面にてトライ
ボケミカル(tribo−chemical)反応する
ことで、選択的に腐食されてピット(孔食)が形成され
たものと考えられる。
From these results, it was found that the Ti element contained in the valve seat of the comparative example was composed of PbCl 2 and PbBr 2 , which are combustion products of ethylene dichloride and ethylene dibromide, which are the lead scavengers contained in the leaded gasoline fuel. As pits (pitting) formed by mixing in the gas, depositing on the sheet surface and reacting with these Cl and Br on the friction surface by a tribo-chemical reaction. it is conceivable that.

【0042】また、肉盛り材である比較例4のバルブシ
ートでは、大気中におけるレーザ肉盛り時のTiの酸化
と耐久試験中のハロゲン腐食作用とが重なって、肉盛り
部が著しく脆化したために剥離脱落したものと思われ
る。
In addition, in the valve seat of Comparative Example 4, which is a build-up material, the oxidation of Ti during laser build-up in the atmosphere and the halogen corrosion action during the durability test overlapped, and the build-up portion was significantly embrittled. It is thought that it peeled off.

【0043】いずれにしても、酸素のゲッター剤として
も用いられるTiが含まれる比較例のバルブシートで
は、ハロゲン元素に対する耐食性や大気中肉盛り時の耐
酸化性に劣るために、上記問題を生じたことが明らかで
ある。
In any case, the valve seat of the comparative example containing Ti, which is also used as a getter agent for oxygen, is inferior in corrosion resistance to a halogen element and oxidation resistance when building up in the air, thus causing the above problem. It is clear that

【0044】一方、本発明例のバルブシートにおいて
は、IVa族のTiが含まれていないために、このよう
な問題は生じていない。
On the other hand, in the valve seat of the present invention, such a problem does not occur because Ti of the IVa group is not contained.

【0045】また、耐摩耗性の向上に大きな役割を示す
硬い金属間化合物の析出を促進するために、本発明では
Cu合金中にVa族の元素であるV,Nb,Taを含有
させた結果、比較例のバルブシートには見られない粒径
10μm程度の球状ないしは塊状の金属間化合物が形成
された。
In order to promote the precipitation of a hard intermetallic compound which plays a major role in improving the wear resistance, the present invention results from the inclusion of V, Nb and Ta, which are elements of the Va group, in the Cu alloy. A spherical or massive intermetallic compound having a particle size of about 10 μm, which was not found in the valve seat of the comparative example, was formed.

【0046】代表的な組織として、図1に比較例2のバ
ルブシートの光学顕微鏡による観察結果(400倍)を
示し、図2に本発明例6のバルブシートの走査電子顕微
鏡による観察結果(1000倍)を示す。
As a representative structure, FIG. 1 shows the observation result (400 times) of the valve sheet of Comparative Example 2 by an optical microscope, and FIG. 2 shows the observation result of the valve sheet of Example 6 of the present invention by a scanning electron microscope (1000 times). Times).

【0047】図2において符号Bで示される微細金属間
化合物は、図1において見られる金属間化合物と類似の
形態を示している。一方、図2において符号Aで示され
る粒径10μm程度の球状金属間化合物は、図1におい
ては存在しない。したがって、図2において存在する大
きな球状析出物が、デポジットや摩耗粉によるアブレー
シブ摩耗に対しての大幅な改善効果をもたらしたこと
も、本発明例のバルブシートにおいて優れた耐摩耗性を
示す結果につながっているものと考えられる。
The fine intermetallic compound denoted by reference symbol B in FIG. 2 has a form similar to that of the intermetallic compound shown in FIG. On the other hand, the spherical intermetallic compound having a particle diameter of about 10 μm shown by the symbol A in FIG. 2 does not exist in FIG. Therefore, the large spherical precipitates present in FIG. 2 also provided a significant improvement effect on abrasive wear caused by deposits and wear powder, which also indicates that the valve seat of the present invention example shows excellent wear resistance. It is thought that they are connected.

【0048】このように、本発明実施例の銅合金は、高
温で優れた耐摩耗性、耐酸化性,耐腐食性を示した。ま
た、この実施例では、バルブシートを中心に例示して説
明したが、鋳造−鍛造−押出し加工の工程や、焼結など
によって、バルブガイドを製作することもでき、その他
同様の特性が要求されるエンジン用等々の摺動部材にも
適用することが可能であって、利用範囲は大きいもので
ある。
As described above, the copper alloys of the examples of the present invention exhibited excellent wear resistance, oxidation resistance and corrosion resistance at high temperatures. In this embodiment, the valve seat has been described as an example. However, a valve guide can be manufactured by a casting-forging-extrusion process or sintering, and other similar characteristics are required. The present invention can be applied to sliding members for engines and the like, and has a wide range of use.

【0049】[0049]

【発明の効果】本発明に係わる銅合金は、Al:1.0
〜15.0%、元素周期表Va族元素であるV,Nb,
Taのうち少なくとも1種:0.1〜5.0%、場合に
よってはCo:0.5〜10.0%、同じく場合によっ
てはFeおよびNiの1種または2種:0.5〜12.
0%、同じく場合によってはMn:1.0〜10.0%
を含有し、残部Cuおよび不純物からなる組成を有し、
Al,Co,Fe,Ni,Cuの1種以上とVa族元素
の1種以上とからなる金属間化合物のうち少なくとも1
種が粒径10μm程度の球状ないしは塊状物として分散
し、場合によってはAl,Co,Fe,Ni,Cuの2
種以上からなる金属間化合物が粒径10μm程度の球状
ないしは塊状物として分散した組織を有するものとなっ
ているので、高温で優れた耐摩耗性を示すと共に、耐酸
化性および耐腐食摩耗性が向上した熱伝導率の大きい銅
合金となり、とくに、エンジンのバルブシート、バルブ
ガイドの素材として用いた場合に、高温での耐摩耗性に
優れていると共に、相手材バルブに対する攻撃性も小さ
く、高温耐摩耗性に優れているだけでなく熱伝導率も大
きく熱伝導性に優れているため、エンジンの高出力化と
低燃費化にも寄与するものになり、その他同様の特性が
要求される各種摺動部材等の素材として適したものであ
るという著しく優れた効果がもたらされる。
The copper alloy according to the present invention has an Al content of 1.0.
1515.0%, V, Nb,
At least one of Ta: 0.1 to 5.0%, in some cases Co: 0.5 to 10.0%, and in some cases, one or two of Fe and Ni: 0.5 to 12.
0%, and in some cases, Mn: 1.0 to 10.0%
Having a composition consisting of the balance Cu and impurities,
At least one of the intermetallic compounds composed of at least one of Al, Co, Fe, Ni, and Cu and at least one of the Va group elements.
The seeds are dispersed as spheres or aggregates having a particle size of about 10 μm, and in some cases, Al, Co, Fe, Ni, Cu
Since it has a structure in which the intermetallic compound composed of more than one kind is dispersed as a sphere or a lump having a particle size of about 10 μm, it exhibits excellent wear resistance at high temperatures, and has oxidation resistance and corrosion wear resistance. Improved copper alloy with high thermal conductivity.Excellent wear resistance at high temperatures, especially when used as a material for engine valve seats and valve guides. Not only has excellent wear resistance, but also has high thermal conductivity and excellent thermal conductivity, contributing to higher output and lower fuel consumption of the engine. A remarkably excellent effect is obtained that the material is suitable as a material for a sliding member or the like.

【図面の簡単な説明】[Brief description of the drawings]

【図1】比較例2のバルブシートの光学顕微鏡による観
察結果(400倍)を示す写真である。
FIG. 1 is a photograph showing an observation result (400 times) of an optical microscope of a valve seat of Comparative Example 2.

【図2】本発明例6のバルブシートの走査電子顕微鏡に
よる観察結果(1000倍)を示す写真である。
FIG. 2 is a photograph showing a result of observation of a valve seat of Example 6 of the present invention by a scanning electron microscope (× 1000).

フロントページの続き (56)参考文献 特開 平2−108492(JP,A) 特開 平2−50929(JP,A) 特開 昭58−181838(JP,A) 特開 昭61−207539(JP,A) 特公 昭39−9676(JP,B1) (58)調査した分野(Int.Cl.7,DB名) C22C 9/01 Continuation of front page (56) References JP-A-2-108492 (JP, A) JP-A-2-50929 (JP, A) JP-A-58-1881838 (JP, A) JP-A-61-207539 (JP, A) , A) JP 39-9676 (JP, B1) (58) Field surveyed (Int. Cl. 7 , DB name) C22C 9/01

Claims (4)

(57)【特許請求の範囲】(57) [Claims] 【請求項1】 重量%で、Al:1.0〜15.0%、
元素周期表Va族元素であるV,Nb,Taのうち少な
くとも1種:0.1〜5.0%、残部Cuおよび不純物
からなる組成を有し、Al,Cuの1種以上とVa族元
素の1種以上とからなる粒径10μm程度の球状ないし
は塊状の金属間化合物のうち少なくとも1種が分散した
組織を有することを特徴とする高温耐摩耗性に優れた銅
合金。
1. Al: 1.0 to 15.0% by weight,
At least one of V, Nb and Ta, which is a group Va element of the periodic table, has a composition of 0.1 to 5.0%, the balance being Cu and impurities, and at least one of Al and Cu and a group Va element. Of at least about 10 μm in particle diameter
Is a copper alloy excellent in high-temperature abrasion resistance, characterized by having a structure in which at least one kind of massive intermetallic compound is dispersed.
【請求項2】 Co:0.5〜10.0%を含有し、A
l,Co,Cuの1種以上とVa族元素の1種以上とか
らなる金属間化合物のうち少なくとも1種が分散した組
織を有する請求項1に記載の高温耐摩耗性に優れた銅合
金。
2. Co: contains 0.5 to 10.0% of A;
The copper alloy excellent in high-temperature wear resistance according to claim 1, wherein the copper alloy has a structure in which at least one kind of an intermetallic compound composed of at least one kind of l, Co, Cu and at least one kind of Va group element is dispersed.
【請求項3】 FeおよびNiの1種または2種:0.
5〜12.0%を含有し、Al,Co,Fe,Ni,C
uの1種以上とVa族元素の1種以上とからなる金属間
化合物のうち少なくとも1種が分散した組織を有する請
求項1または2に記載の高温耐摩耗性に優れた銅合金。
3. One or two of Fe and Ni: 0.
Al, Co, Fe, Ni, C
3. The copper alloy excellent in high-temperature wear resistance according to claim 1 or 2, having a structure in which at least one kind of an intermetallic compound composed of at least one kind of u and at least one kind of a Va group element is dispersed.
【請求項4】 Mn:1.0〜10.0%を含有した請
求項1、2または3のいずれかに記載の高温耐摩耗性に
優れた銅合金。
4. The copper alloy excellent in high-temperature wear resistance according to claim 1, containing Mn: 1.0 to 10.0%.
JP01477293A 1993-02-01 1993-02-01 Copper alloy with excellent high-temperature wear resistance Expired - Fee Related JP3337087B2 (en)

Priority Applications (3)

Application Number Priority Date Filing Date Title
JP01477293A JP3337087B2 (en) 1993-02-01 1993-02-01 Copper alloy with excellent high-temperature wear resistance
US08/189,780 US5468310A (en) 1993-02-01 1994-02-01 High temperature abrasion resistant copper alloy
US08/610,913 US6037067A (en) 1993-02-01 1996-03-05 High temperature abrasion resistant copper alloy

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP01477293A JP3337087B2 (en) 1993-02-01 1993-02-01 Copper alloy with excellent high-temperature wear resistance

Publications (2)

Publication Number Publication Date
JPH06228681A JPH06228681A (en) 1994-08-16
JP3337087B2 true JP3337087B2 (en) 2002-10-21

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CN109897982B (en) * 2019-01-29 2020-09-29 中南大学 High-airtightness low-free-oxygen-content nano dispersion copper alloy and short-process preparation process

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