JP2984344B2 - Cu-based alloy powder for laser cladding - Google Patents
Cu-based alloy powder for laser claddingInfo
- Publication number
- JP2984344B2 JP2984344B2 JP2253744A JP25374490A JP2984344B2 JP 2984344 B2 JP2984344 B2 JP 2984344B2 JP 2253744 A JP2253744 A JP 2253744A JP 25374490 A JP25374490 A JP 25374490A JP 2984344 B2 JP2984344 B2 JP 2984344B2
- Authority
- JP
- Japan
- Prior art keywords
- powder
- laser
- alloy
- molten pool
- less
- 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 - Lifetime
Links
- 239000000843 powder Substances 0.000 title claims description 59
- 229910045601 alloy Inorganic materials 0.000 title claims description 39
- 239000000956 alloy Substances 0.000 title claims description 39
- 238000004372 laser cladding Methods 0.000 title claims description 7
- 229910052750 molybdenum Inorganic materials 0.000 claims description 12
- 229910001122 Mischmetal Inorganic materials 0.000 claims description 8
- 229910052735 hafnium Inorganic materials 0.000 claims description 8
- 229910052719 titanium Inorganic materials 0.000 claims description 8
- 229910052726 zirconium Inorganic materials 0.000 claims description 8
- 229910052782 aluminium Inorganic materials 0.000 claims description 7
- 229910052727 yttrium Inorganic materials 0.000 claims description 7
- 229910052804 chromium Inorganic materials 0.000 claims description 5
- 239000012535 impurity Substances 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- 229910052796 boron Inorganic materials 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 230000007547 defect Effects 0.000 description 16
- 239000011324 bead Substances 0.000 description 15
- 229910052721 tungsten Inorganic materials 0.000 description 14
- 229910052751 metal Inorganic materials 0.000 description 13
- 239000002184 metal Substances 0.000 description 13
- 230000015572 biosynthetic process Effects 0.000 description 9
- 229910021332 silicide Inorganic materials 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 8
- 238000002844 melting Methods 0.000 description 8
- 238000004544 sputter deposition Methods 0.000 description 8
- 230000008018 melting Effects 0.000 description 7
- FVBUAEGBCNSCDD-UHFFFAOYSA-N silicide(4-) Chemical compound [Si-4] FVBUAEGBCNSCDD-UHFFFAOYSA-N 0.000 description 7
- 238000005260 corrosion Methods 0.000 description 6
- 230000007797 corrosion Effects 0.000 description 6
- 230000004927 fusion Effects 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 229910052759 nickel Inorganic materials 0.000 description 6
- 230000002950 deficient Effects 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 238000007711 solidification Methods 0.000 description 5
- 230000008023 solidification Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 238000003466 welding Methods 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 229910002482 Cu–Ni Inorganic materials 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- 238000009689 gas atomisation Methods 0.000 description 2
- 239000011812 mixed powder Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 238000002310 reflectometry Methods 0.000 description 2
- 229910052684 Cerium Inorganic materials 0.000 description 1
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- 229910017816 Cu—Co Inorganic materials 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 229910000905 alloy phase Inorganic materials 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229910021478 group 5 element Inorganic materials 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000002076 thermal analysis method Methods 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Landscapes
- Laser Beam Processing (AREA)
- Powder Metallurgy (AREA)
Description
〔産業上の利用分野〕 本発明はレーザ粉末肉盛溶接に用いるCu基肉盛合金粉
末に関するものである。 〔従来の技術〕 従来公知の耐摩耗性、耐食性に優れた肉盛用粉末とし
て、本発明者らの一人がすでに、Si0.1〜６％,B0.1〜
４％,Ni10〜40％,Cr,Mo及びＷの１種又は２種以上の合
計が1/4Ni≧Cr＋1/2Mo＋1/3.5Wを満足する範囲で含有
し、残部はCuであるCu基自溶性合金粉末（特公昭50−46
08）、前記合成粉末と、少なくともB0.1〜４％、Si0.
1〜６％を含有するCo基合金粉末とを1:9〜7:3の割合で
混合してなる粉末肉盛溶接用Cu−Co系自溶性合金粉末
（特公昭49−11979）などを提案している。 近年、金属基体上にレーザ、プラズマアークや電子ビ
ームなどの高エネルギー密度の加熱源を用いて、しかも
自動的に粉末を肉盛溶接する技術が進歩している。 特に、レーザパワーの高出力化にともなって、レーザ
粉末肉盛技術の工業的な適用が活発となっている。とこ
ろが、前述した従来公知の粉末を用いた場合、スパッタ
リングの発生やビード形状の不良、欠肉、融合不良、ピ
ンホール及びブローホール等の欠陥を生じ、レーザ粉末
肉盛溶接がうまくできない場合があった。特に混合粉で
は、個々の粉末のレーザビーム吸収率の違いにより、不
均一なビードを生じやすくなる問題点がみられ、工業的
に、しかも自動化された工程でレーザ粉末肉盛部品を製
品する際、不良品が出来やすく、製造の安定性に欠ける
欠点があった。 〔発明が解決すべき問題点〕 本発明者らは、レーザ粉末肉盛溶接においてスパッタ
リングがなく、ビード形状が良好で、欠肉、融合不良、
ピンホール及びブローホール等の欠陥を発生しないCu基
合金粉末の組成を種々検討した結果、前述した従来公知
の合金の特性を損なうことなく、又、粉末製造に支障を
来すことのない範囲で有効な微量の添加元素及び微量の
酸素を含有することにより、前記問題点が解決されるこ
とを見出し、本発明を完成したものである。 〔問題を解決するための手段〕 本発明は、（１）Ni10〜40％,Si0.1〜６％を必須成分
とし、残部がCu及び不可避不純物からなる合金におい
て、 Al,Y,ミッシュメタル,Ti,Zr,Hfのうちの１種又は２種
以上の合計が0.01〜0.1％、[Industrial Application Field] The present invention relates to a Cu-based overlay alloy powder used for laser powder overlay welding. [Prior art] One of the present inventors has already found that 0.1 to 6% Si, 0.1 to 0.1% B, as a conventionally known overlaying powder having excellent wear resistance and corrosion resistance.
4%, Ni 10-40%, Cr, Mo and W contain at least one or more of them in a range satisfying 1 / 4Ni ≧ Cr + 1 / 2Mo + 1 / 3.5W, with the balance being Cu-based self-solubility. Alloy powder (JP-B 50-46)
08), at least 0.1 to 4% B0, Si0.
Proposal of Cu-Co based self-fluxing alloy powder for powder overlay welding (Japanese Patent Publication No. 49-11979) made by mixing Co-based alloy powder containing 1 to 6% in a ratio of 1: 9 to 7: 3 doing. 2. Description of the Related Art In recent years, the technology of automatically overlaying powder on a metal substrate using a high energy density heating source such as a laser, a plasma arc, and an electron beam has been advanced. In particular, with the increase in the output of the laser power, the industrial application of the laser powder overlaying technique has become active. However, when the above-mentioned conventionally known powder is used, the generation of sputtering, defects in bead shape, underfill, poor fusion, defects such as pinholes and blowholes occur, and laser powder overlay welding may not be performed well. Was. In particular, in the case of mixed powder, there is a problem that uneven bead tends to be generated due to the difference in laser beam absorptivity of each powder, and it is necessary to produce laser powder overlay parts industrially and in an automated process. Defective products are likely to be formed, and there is a defect that manufacturing stability is lacking. [Problems to be Solved by the Invention] The present inventors have found that there is no sputtering in laser powder overlay welding, the bead shape is good, the underfill, poor fusion,
As a result of various examinations of the composition of the Cu-based alloy powder that does not generate defects such as pinholes and blowholes, without impairing the characteristics of the previously known alloys described above, and within a range that does not hinder powder production. The present inventors have found that the above problems can be solved by containing an effective trace amount of additive element and trace amount of oxygen, and have completed the present invention. [Means for Solving the Problems] The present invention relates to (1) an alloy comprising 10 to 40% of Ni and 0.1 to 6% of Si as essential components and the balance being Cu and unavoidable impurities, comprising Al, Y, misch metal, The total of one or more of Ti, Zr, and Hf is 0.01 to 0.1%,
〔０〕0.01〜0.1％ を含有することを特徴とするレーザ肉盛用Cu基合金粉
末。 （２）Ni10〜40％,Si0.1〜６％を必須成分とし、Co20％
以下、Mo又は／及びＷの合計が20％以下、Fe20％以下、
Cr10％以下,B0.5％以下、残部がCu及び不可避不純物か
らなる合金において、 Al,Y,ミッシュメタル,Ti,Zr,Hfのうちの１種又は２種
以上の合計が0.01〜0.1％、[0] A Cu-based alloy powder for laser cladding comprising 0.01 to 0.1%. (2) Ni 10-40%, Si 0.1-6% as essential components, Co 20%
In the following, the total of Mo or / and W is 20% or less, Fe 20% or less,
Cr10% or less, B0.5% or less, the balance is an alloy consisting of Cu and unavoidable impurities, the total of one or more of Al, Y, misch metal, Ti, Zr, Hf is 0.01 to 0.1%,
〔０〕0.01〜0.1％ を含有することを特徴とするレーザ肉盛用Cu基合金粉末
である。 〔作用〕 レーザ粉末肉盛における溶融〜凝固の機構は以下のよ
うに考えられる。まずレーザビームは粉末に吸収される
と同時に母材表面に熱を供給し、溶融プールが形成され
る。次に金属基体が移動することにより溶融プールが相
対的に移動するため、溶融プールは定常かつ連続的に冷
却・凝固して、肉盛層が形成される。 熱源にレーザビームを用いた場合の大きな特徴は、レ
ーザビームが粉末及び溶融プールに吸収されることによ
り、光→熱エネルギーに交換され、この熱エネルギーに
よって、加熱・溶融が起こることである。このため粉末
及び溶融プールのレーザビーム吸収率が非常に大切であ
る。 Cu合金のように反射率の高いものでは、粉末及び溶融
プールでレーザビームを効率よく吸収させることが、特
に重要である。 ところで、レーザ肉盛時における溶融プールの形成の
良否がレーザ肉盛層の良否に極めて大きな影響を及ぼし
ている。以下、この点につき詳述する。 溶融プール形成不良現象を分類すると、溶融プール
部への入熱不足によって引き起こされる、粉末の未溶融
又は溶融不足や金属基体との濡れ不良、及び入熱量は
適正で溶融はしているにもかかわらず、溶融プール内の
溶融金属の撹拌がはげしたために引き起こされる、溶融
プールの“表面撹乱”とがある。 溶融プールの形成不良が、上記に起因したとき、レ
ーザ肉盛層に与える影響は次の通りである。 溶融プールは、溶融不足等の影響で、溶融プール表面
では常に一定の溶融金属自由表面を保つことができない
ため、冷却・凝固の際、定常かつ連続的凝固を行うこと
ができなくなり、肉盛層表面に大きな凹凸を残したまま
凝固してしまう。この結果、ビード形状の不良や欠肉を
発生させる。さらにまた、溶融不足等の影響で、肉盛層
の内部ではピンホールが、また金属基体との界面では融
合不良が発生する。 一方、溶融プールの形成不良が上記に起因したと
き、レーザ肉盛層に与える影響は次のとおりである。 溶融プールは、激しい“表面撹乱”の影響で、溶融プ
ール表面では常に一定の溶融金属自由表面を保つことが
できないため、冷却・凝固の際、前記と同様に定常かつ
連続的な凝固を行うことができなくなり、肉盛層表面に
大きな凹凸を残したまま凝固してしまう。この結果、ビ
ード形状の不良や欠肉を発生させる。さらに、溶融プー
ルの激しい撹拌により、周囲のガスが溶融プール内に巻
き込まれる。巻き込まれたガスは加熱され、内部圧力を
高めながら膨張をし、溶融プール外へ脱出しようとす
る。脱出の際、ガスは溶融金属の一部を吹き飛ばしなが
ら出て行くため、スパッタリング現象が発生する。さら
にまた、巻き込まれたガスが抜ききらずに溶融プールに
残ったままで凝固してしまうとブローホールが発生す
る。 以上のごとく、レーザ肉盛時における溶融プール形成
の不良は、ビード形状の不良、欠肉、融合不良、ピンホ
ール及びブローホール等の種々の欠陥を発生させる原因
となる。なお、念のために述べると、ビード形状の不良
は、他の肉盛欠陥、即ち、欠肉、融合不良、ピンホール
及びブローホールをも引き起していることを示唆してい
る。従って、ビード形状不良を防止することは極めて重
要な点である。さらに、肉盛層の欠陥ではないがスパッ
タリング発生の原因にもなっている、このスパッタリン
グの発生は、レーザ肉盛作業において、ミラーや周辺機
具を汚染し、操業を継続して行うことを妨げる。従っ
て、スパッタリング発生を防止することは極めて重要な
点である。 本発明の第１の特徴は、レーザ粉末肉盛を行った際の
スパッタリングの発生やビード形状の不良、欠肉、融合
不良、ピンホール及びブローホール等の欠陥を防止する
目的で、微量成分（Al,Y,ミッシュメタル,Ti,Zr,Hf）の
添加及び微量の酸素を含有していることであり、レーザ
ビームを照射すると、それらの微量成分の酸化皮膜が粉
末表面あるいは溶融プールの表面に形成されることであ
る。この酸化皮膜は熱的に安定で、かつレーザビームを
効率よく吸収するため、粉末及び溶融プールへの熱エネ
ルギーは安定で、かつ効率よく供給され、適正な溶融プ
ールが形成される。さらにまた、この酸化皮膜が溶融プ
ールの見掛けの溶融粘度を高め、前述した“表面撹乱”
を鎮静化する。以上のごとき理由により、本発明の第一
の特徴は、上記肉盛不良を防止する作用がある。 さらに本発明の第２の特徴は、従来公知の合金の特性
を損なうことなく、又、粉末製造に支障を来すことのな
い範囲の粒子個々の組成が均一な合金粉末の形態とした
ことである。このことで、混合粉末をレーザ粉末肉盛に
使用した際の問題点、即ち、個々の粉末の吸収率の違い
による肉盛不安定さが改善され、工業的に、しかも自動
化された工程で、レーザ粉末肉盛を行う際に、より安定
で、効率が良くなる作用がある。 以下、本発明における必須成分の限定理由を説明す
る。 （Ni） NiはCuに溶解しCu−Ni合金相として、又、一部は珪化
物を形成してマトリックスを強化するとともに、後述す
る耐摩耗性を向上させる選択成分であるCo,Mo,W,Fe,Cr
及びＢを含有せしめるために必要な成分である。Ni10％
未満では従来のCu−Ni合金の特性、特に耐食性、耐摩耗
性が出現できず、さらに、上記選択成分、特にCr,Mo及
びＷを添加できる量が少なくなる。一方、Niの増加によ
り合金の溶解性は良くなるが、合金中のCuの固溶体相が
減少し、耐摩耗性が悪くなるため上限を40％とした。従
って、Niは10〜40％の範囲内とした。 （Si） SiはNiとの珪化物を形成すると同時に後述する各選択
成分と合金化して珪化物を形成させるために欠くことの
できない成分であり、さらにSiはＢと共存する場合には
合金の自溶性を高めて溶着性を向上させる作用を果た
す。Siが0.1％未満では目的とする珪化物が充分に形成
されず、耐摩耗性が低下し、Siが６％を超えると過剰の
珪化物の晶出及び合金の融点上昇を来たし、粉末の製造
ができなくなる。従って、Siは0.1〜６％の範囲内とし
た。 （Al,Y,ミッシュメタル,Ti,Zr,Hf） 本発明において、レーザ粉末肉盛を行う際に上記微量
添加元素及び[0] A Cu-based alloy powder for laser cladding characterized by containing 0.01 to 0.1%. [Action] The mechanism of melting to solidification in the laser powder overlay is considered as follows. First, the laser beam is absorbed by the powder and simultaneously supplies heat to the surface of the base material to form a molten pool. Next, the molten pool relatively moves as the metal base moves, so that the molten pool cools and solidifies steadily and continuously, forming a build-up layer. A major feature of the case where a laser beam is used as a heat source is that the laser beam is exchanged from light to heat energy by being absorbed by the powder and the molten pool, and the heat energy causes heating and melting. For this reason, the laser beam absorptivity of the powder and the molten pool is very important. In the case of a material having a high reflectance such as a Cu alloy, it is particularly important to efficiently absorb the laser beam in the powder and the molten pool. By the way, the quality of the formation of the molten pool at the time of laser cladding has an extremely large influence on the quality of the laser cladding layer. Hereinafter, this point will be described in detail. When the molten pool formation failure phenomenon is classified, the powder is not melted or insufficiently melted due to insufficient heat input to the molten pool, poor wetting with the metal substrate, and the heat input is appropriate and the amount of melting is appropriate. However, there is "surface disturbance" of the molten pool caused by agitation of the molten metal in the molten pool. When the formation failure of the molten pool is caused by the above, the influence on the laser overlay is as follows. Since the molten pool cannot maintain a constant free surface of molten metal on the surface of the molten pool due to insufficient melting, etc., steady and continuous solidification cannot be performed during cooling and solidification. It solidifies while leaving large irregularities on the surface. As a result, defects in the bead shape and underfill are generated. Furthermore, pinholes occur inside the build-up layer and poor fusion occurs at the interface with the metal substrate due to the influence of insufficient melting or the like. On the other hand, when the formation failure of the molten pool is caused by the above, the influence on the laser overlay is as follows. Because the molten pool cannot maintain a constant free surface of molten metal on the surface of the molten pool due to severe "surface disturbance", solid and continuous solidification must be performed during cooling and solidification as described above. And solidifies while leaving large irregularities on the surface of the buildup layer. As a result, defects in the bead shape and underfill are generated. In addition, vigorous stirring of the molten pool causes ambient gases to be entrained in the molten pool. The entrained gas is heated and expands with increasing internal pressure, attempting to escape out of the molten pool. At the time of escape, the gas exits while blowing off a part of the molten metal, so that a sputtering phenomenon occurs. Furthermore, if the entrained gas is solidified while remaining in the molten pool without being exhausted, blowholes are generated. As described above, the defect in the formation of the molten pool during the laser cladding causes various defects such as a defective bead shape, a lack of a wall, a defective fusion, a pinhole and a blowhole. It should be noted that, as a reminder, a bead-shaped defect suggests that other build-up defects have also been caused, ie, underfill, poor fusion, pinholes and blowholes. Therefore, it is extremely important to prevent a bead shape defect. Furthermore, the occurrence of sputtering, which is not a defect of the build-up layer, causes contamination of the mirror and peripheral equipment in the laser build-up operation, and prevents continuous operation. Therefore, it is extremely important to prevent the occurrence of sputtering. The first feature of the present invention is to prevent the occurrence of spattering during laser powder overlaying, defects in bead shape, underfill, poor fusion, defects such as pin holes and blow holes, etc. Al, Y, misch metal, Ti, Zr, Hf) and containing a trace amount of oxygen. When irradiated with a laser beam, an oxide film of these trace components forms on the powder surface or the surface of the molten pool. Is to be formed. Since this oxide film is thermally stable and efficiently absorbs the laser beam, the thermal energy to the powder and the molten pool is supplied stably and efficiently, and an appropriate molten pool is formed. Furthermore, this oxide film increases the apparent melt viscosity of the molten pool, and the "surface disturbance" described above.
To calm down. For the above reasons, the first feature of the present invention is to prevent the above-mentioned poor build-up. Further, a second feature of the present invention is that the composition of the individual particles is in the form of a uniform alloy powder without impairing the properties of the conventionally known alloy and within a range that does not hinder the powder production. is there. By this, the problem when using the mixed powder for laser powder overlay, namely, the build-up instability due to the difference in the absorptivity of each powder is improved, industrially, and in an automated process, When performing laser powder overlaying, there is an operation that is more stable and improves efficiency. Hereinafter, the reasons for limiting the essential components in the present invention will be described. (Ni) Ni is dissolved in Cu to form a Cu-Ni alloy phase, and partly forms silicide to strengthen the matrix and is a selective component for improving wear resistance, which will be described later, such as Co, Mo, and W. , Fe, Cr
And B are necessary components. Ni10%
If it is less than 1, the characteristics of the conventional Cu-Ni alloy, particularly corrosion resistance and wear resistance, cannot be exhibited, and the amount of the above-mentioned selected components, especially Cr, Mo and W, can be reduced. On the other hand, the solubility of the alloy is improved by the increase of Ni, but the solid solution phase of Cu in the alloy is reduced and the wear resistance is deteriorated, so the upper limit was set to 40%. Therefore, Ni was set in the range of 10 to 40%. (Si) Si is an essential component to form silicide with Ni and at the same time to form a silicide by alloying with each of the selected components described later. Further, when Si coexists with B, It acts to enhance self-solubility and improve weldability. If the Si content is less than 0.1%, the desired silicide will not be formed sufficiently, and the wear resistance will be reduced. Can not be done. Therefore, Si is set in the range of 0.1 to 6%. (Al, Y, misch metal, Ti, Zr, Hf) In the present invention, when performing laser powder overlaying,
〔０〕が極めて重要な働きをする。 III族元素であるAl,Y,ミッシュメタル（La,Ce）及びI
V族元素であるTi,Zr,Hfは、いずれもその他の成分元素
に比べ酸化物生成標準自由エネルギーが大きいため、微
量添加すると、酸素と結合して安定した酸化皮膜を形成
する。この酸化皮膜の形成はレーザ粉末肉盛時に起こ
り、粉末及び溶融プール表面に安定した酸化皮膜を形成
し、レーザビームを有効に吸収して、適正な溶融プール
を形成するとともに、溶解プールの表面撹乱を鎮静化す
る。なお、この作用は上記各微量添加元素を単体で添加
した場合でも、２種以上の複合添加でも、その合計で同
様に論ずることができる。 上記微量添加元素の合計が0.01％未満では形成する酸
化皮膜が少なく、レーザビームの反射率が高くなるた
め、溶融プールの形成が不良となり、ビード形状等、前
述の種々欠陥を発生する危険性が大きくなる。一方、0.
1％を超えると酸化皮膜が多くなることにより、レーザ
ビーム吸収率の上昇による加熱のため母材希釈量の増加
を来す危険性が高くなる。また、粉末製造時の溶湯の流
動性が悪くなり、粉末製造が困難となる。従って、Al,
Y,ミッシュメタル,Ti,Zr,Hfの１種又は２種以上の合計
は0.01〜0.1％の範囲内とした。 （〔Ｏ〕） 〔Ｏ〕は前記微量添加元素と結合して安定な酸化皮膜
を形成させるため必要な成分である。〔Ｏ〕が0.01％未
満では形成する酸化皮膜が少なく、レーザビームの反射
率が高くなるため、溶融プールの形成が不良となり、ビ
ード形状等前述の種々の欠陥を発生する危険性が大きく
なる。一方、〔Ｏ〕が0.1％を超えると熱的に不安定な
酸化皮膜が多くなることにより、スパッタリングを生じ
たり、レーザビーム吸収率の上昇による加熱のため母材
希釈量の添加を来す危険性が高くなる。従って、〔Ｏ〕
は0.01〜0.1％の範囲内とした。 次に、選択成分であるCo,Mo,W,Fe,Cr及びＢはCu基肉
盛合金の主に耐摩耗性を向上させる成分として従来より
よく知られている。従って、できるだけ多く含有させる
ことが望ましい。しかし、これら選択成分を含有させる
と全て２液相分離型合金となり、含有量によっては粉末
製造に支障をきたすこともでてくることがわかった。そ
こで、各成分をできるだけ含有させることのできる合金
組成を種々検討した。その結果、合金粉末製造に支障を
来すことのない上限を規定するに到った。 以下、各選択成分の限定理由を説明する。 （Co） CoはCu中にはほとんど溶解せずNiと合金化し、共に珪
化物相を形成して耐摩耗性、さらに耐熱性、耐食性を向
上させるとともに、Mo及びＷを有効に含有せしめるため
に必要な成分である。Coが20％を超えると合金の溶解性
は良くなるが、上記特性の向上が少なく、Co地金は高価
であることからコストの上昇を紹くため好ましくない。
従って、Coは20％以下とした。 （Mo及びＷ） Mo及びＷはCuに対して溶解度がないので、Ni及びCoと
合金化する。また、Mo及びＷリッチの珪化物を晶出する
ことにより、耐摩耗性、耐熱性をさらに向上させる有効
な成分である。MO,WはNi及びCoに対して同様の溶解度が
あり、同じ働きをするため、各々の単体添加でも複合添
加でも同一の限定理由を論ずることができる。即ち、Mo
及びＷの１種あるいは２種の合計が20％を超えると、高
融点珪化物の過剰晶出により溶解度の限界を超え、粉末
が製造できなくなる。従って、Mo及びＷの１種又は２種
の合計は20％以下とした。 （Fe） Feは合金の溶解性において、Ni,Coと同様の働きを
し、それらの一部と置き換えることができ、加えてコス
トの低下による経済効果をもたらすが、Feが20％を超え
ると合金の耐食性を劣化させるおそれがある。従って、
Feは20％以下とした。 （Cr） CrはCuには溶解せず、Ni及びCoと合金化する。Ni及び
Co部に溶解することにより珪化物を形成して耐摩耗性を
向上させるとともに、合金の耐食性、耐熱性を向上させ
る。Crが10％を超えると、Mo及びＷ珪化物の有効晶出量
を減少させるおそれがある。従って、Crは10％以下とし
た。 （Ｂ） ＢはCuとほとんど溶解せずNiと合金化して耐摩耗性を
向上させるとともに、溶湯の流動性を良くし、自溶性を
付与する成分であるが、Ｂが0.5％を超えるとCr,Mo,Wと
の高融点ホウ化物を形成し、晶出するため、粉末製造が
困難となる。従って、Ｂは0.5％以下とした。 以下、本発明の実施例を示す。 〔実施例・比較例〕 それぞれ第１表に示される成分組成になるように配合
した本発明合金、比較例合金について、まず粉末製造作
業性の判断基準として、熱分析法による初晶晶出温度を
測定し、1500℃の溶湯を５φmm×100mmlのシェルモード
へ鋳湯することにより流動性を調査した。次に、各々の
合金溶湯をN2ガスを使用したガスアトマイズ法により粉
化し、そのままN2ガス雰囲気中で冷却してレーザ粉末肉
盛用Cu基合金粉末を得た。以上のようにして得られた粉
末をそれぞれ−80〜＋280メッシュに篩分け、下記の条
件でレーザ粉末肉盛を行い、スパッリングの有無及びビ
ード形状を観察した。それらの結果を第１表に示す・ （レーザ粉末肉盛条件） ・金属基体 ;SS41 ・レーザ出力;1.8kw ・ぼかし量 ;ab値1.4（線状ビーム） ・処理速度 ;100mm/min 第１表に示すように、No.1〜９の本発明のレーザ粉末
肉盛用Cu基合金粉末は、通常のガスアトマイズ法で問題
なく合金粉末を製造できる組成であり、本粉末を用いて
レーザ粉末肉盛を行うと、スパッタリングは発生せず、
ビード形状が良好で、レーザ粉末肉盛性が良好である。
これに対して、No.10〜15の比較例合金は、微量添加元
素及び〔Ｏ〕量がはずれたもので、その中でNo.10〜13
はスパッタリングの発生かもしくはビード形状の不均一
が認 められ、No.14,15はレーザ粉末肉盛性が不良であると同
時に溶湯流動性が悪く、粉末製造困難な組成である。以
上の結果、微量添加元素及び〔Ｏ〕量がレーザ粉末肉盛
性に重要な影響を及ぼすことが明らかである。 〔発明の効果〕 以上詳述したように、本発明のCu基合金粉末は耐摩耗
性、耐食性、耐熱性を向上させる成分を有効に含有して
おり、レーザ粉末肉盛を行うに際して、スパッタリング
が発生せず、良好なビードが得られ、工業的にしかも自
動化された工程においても、安定で効率の良い肉盛部品
を製造できる効果を有する。 なお、本発明によるCu基合金粉末はプラズマアークを
熱源とする粉末肉盛材としても良好な肉盛ができること
が確認されている。[0] plays a very important role. Group III elements Al, Y, misch metal (La, Ce) and I
Group V elements Ti, Zr, and Hf all have a larger standard free energy for oxide formation than other component elements, and therefore, when added in a small amount, combine with oxygen to form a stable oxide film. The formation of this oxide film occurs when the laser powder is laid, forms a stable oxide film on the surface of the powder and the molten pool, effectively absorbs the laser beam, forms an appropriate molten pool, and disturbs the surface of the melting pool. To calm down. This effect can be similarly discussed in the case where each of the above-mentioned trace addition elements is added alone or in the case where two or more kinds are added in combination. If the total of the above-mentioned trace addition elements is less than 0.01%, the oxide film to be formed is small and the reflectivity of the laser beam is high, so that the formation of the molten pool becomes defective and there is a danger of generating the above-mentioned various defects such as bead shape. growing. On the other hand, 0.
If it exceeds 1%, the amount of the oxide film increases, and the risk of increasing the base material dilution amount due to heating due to an increase in the laser beam absorptivity increases. In addition, the fluidity of the molten metal during powder production deteriorates, and powder production becomes difficult. Therefore, Al,
The total of one or more of Y, misch metal, Ti, Zr, and Hf is in the range of 0.01 to 0.1%. ([O]) [O] is a component necessary for forming a stable oxide film by combining with the trace addition element. When [O] is less than 0.01%, the oxide film to be formed is small and the reflectivity of the laser beam is high, so that the formation of the molten pool becomes defective and the risk of generating the above-mentioned various defects such as a bead shape increases. On the other hand, when [O] exceeds 0.1%, the thermally unstable oxide film increases, which may cause sputtering or increase the laser beam absorptivity to increase the base material dilution due to heating. The nature becomes high. Therefore, [O]
Was in the range of 0.01 to 0.1%. Next, Co, Mo, W, Fe, Cr and B, which are selected components, have been well known as components which mainly improve the wear resistance of the Cu-based overlay alloy. Therefore, it is desirable to contain as much as possible. However, it was found that the inclusion of these optional components all resulted in a two-liquid phase separation type alloy, which could hinder powder production depending on the content. Therefore, various investigations were made on alloy compositions that can contain each component as much as possible. As a result, an upper limit that does not hinder the production of the alloy powder has been defined. Hereinafter, the reasons for limiting each selected component will be described. (Co) Co hardly dissolves in Cu and alloys with Ni to form a silicide phase together to improve wear resistance, heat resistance, corrosion resistance, and to effectively contain Mo and W. Necessary component. If Co exceeds 20%, the solubility of the alloy is improved, but the improvement in the above properties is small, and Co metal is expensive.
Therefore, Co is set to 20% or less. (Mo and W) Since Mo and W have no solubility in Cu, they alloy with Ni and Co. Further, it is an effective component for further improving abrasion resistance and heat resistance by crystallizing Mo and W rich silicides. MO and W have similar solubilities in Ni and Co, and have the same function. Therefore, the same limitation reason can be argued whether each of them is added alone or in combination. That is, Mo
If the total of one or two of W and W exceeds 20%, the solubility exceeds the limit of solubility due to excessive crystallization of high-melting silicide, and powder cannot be produced. Therefore, the total of one or two of Mo and W is set to 20% or less. (Fe) Fe acts in the same way as Ni and Co in dissolving the alloy, and can replace some of them. In addition, it brings economic effects due to cost reduction, but when Fe exceeds 20%, The corrosion resistance of the alloy may be degraded. Therefore,
Fe was set to 20% or less. (Cr) Cr does not dissolve in Cu but alloys with Ni and Co. Ni and
By dissolving in the Co part, silicide is formed to improve wear resistance, and also to improve corrosion resistance and heat resistance of the alloy. If the Cr content exceeds 10%, the effective crystallization amount of Mo and W silicides may be reduced. Therefore, Cr is set to 10% or less. (B) B hardly dissolves in Cu and is alloyed with Ni to improve wear resistance, improve the flowability of the molten metal, and impart self-solubility. , Mo and W form a high melting point boride and crystallize, making powder production difficult. Therefore, B is set to 0.5% or less. Hereinafter, examples of the present invention will be described. [Examples / Comparative Examples] For the alloys of the present invention and comparative alloys blended so as to have the component compositions shown in Table 1, respectively, first, as a criterion for determining powder workability, the primary crystallization temperature by thermal analysis was determined. Was measured, and fluidity was investigated by casting a molten metal at 1500 ° C. into a shell mode of 5 mm × 100 mml. Next, each of the molten alloy was powdered by gas atomizing method using N 2 gas, to obtain a Cu-based alloy powder for laser powder cladding was cooled as it N 2 gas atmosphere. The powders obtained as described above were sieved to -80 to +280 mesh, respectively, and laser powder overlay was performed under the following conditions, and the presence or absence of spattering and the bead shape were observed. The results are shown in Table 1.-(Laser powder overlay condition)-Metal substrate; SS41-Laser output; 1.8 kw-Blur amount; ab value 1.4 (linear beam)-Processing speed; 100 mm / min Table 1 As shown in No. 1 to 9, the Cu-based alloy powders for laser powder overlay of the present invention of Nos. 1 to 9 have compositions that can produce alloy powders by ordinary gas atomizing method without any problem. Do not cause sputtering,
Good bead shape and good laser powder build-up.
On the other hand, the alloys of Comparative Examples Nos. 10 to 15 had the trace added elements and [O] amounts deviated, and among them, No. 10 to 13
Indicates that sputtering has occurred or the bead shape is not uniform. Nos. 14 and 15 have poor laser powder build-up properties and poor melt flowability, and are difficult to produce powder. From the above results, it is clear that the trace amount of the added element and the amount of [O] have an important influence on the buildability of the laser powder. [Effects of the Invention] As described in detail above, the Cu-based alloy powder of the present invention effectively contains components that improve wear resistance, corrosion resistance, and heat resistance. No bead is generated, a good bead is obtained, and there is an effect that a stable and efficient overlay part can be manufactured even in an industrial and automated process. It has been confirmed that the Cu-based alloy powder according to the present invention can form a good build-up as a powder build-up material using a plasma arc as a heat source.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 寺本 隆郎 京都府宇治市木幡西中33番地 (72)発明者 山口 英司 愛知県一宮市浅井町西浅井字水附11番地 審査官 長者 義久 (58)調査した分野(Int.Cl.6，ＤＢ名) C22C 9/00 - 9/10 B23K 26/00 B23K 35/30 B22F 1/00 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Takao Teramoto 33, Kibashi Nishinaka, Uji City, Kyoto Prefecture (72) Inventor Eiji Yamaguchi 11th character, Mizuzumi, Nishi-Asai, Asaimachi, Ichinomiya, Aichi Prefecture Yoshihisa Chief Examiner (58) Surveyed field (Int.Cl. 6 , DB name) C22C 9/00-9/10 B23K 26/00 B23K 35/30 B22F 1/00
Claims (2)
６％を必須成分とし、残部がCu及び不可避不純物からな
る合金において、 Al,Y,ミッシュメタル,Ti,Zr,Hfのうちの１種又は２種
以上の合計が0.01〜0.1％、 〔０〕0.01〜0.1％ を含有することを特徴とするレーザ肉盛用Cu基合金粉
末。1. Ni10 to 40% (% by weight, the same applies hereinafter), Si0.1 to
In an alloy containing 6% as an essential component and the balance being Cu and unavoidable impurities, the total of one or more of Al, Y, misch metal, Ti, Zr, and Hf is 0.01 to 0.1%, [0] A Cu-based alloy powder for laser cladding comprising 0.01 to 0.1%.
Co20％以下、Mo又は／及びＷの合計が20％以下、Fe20％
以下、Cr10％以下,B0.5％以下、残部がCu及び不可避不
純物からなる合金において、 Al,Y,ミッシュメタル,Ti,Zr,Hfのうちの１種又は２種
以上の合計が0.01〜0.1％、 〔０〕0.01〜0.1％ を含有することを特徴とするレーザ肉盛用Cu基合金粉
末。2. An essential component comprising 10 to 40% of Ni and 0.1 to 6% of Si.
Co 20% or less, Mo or / and W total 20% or less, Fe 20%
Hereinafter, in an alloy consisting of Cr 10% or less, B 0.5% or less, and the balance consisting of Cu and inevitable impurities, the total of one or more of Al, Y, misch metal, Ti, Zr, and Hf is 0.01 to 0.1. %, [0] 0.01 to 0.1%.
Priority Applications (1)
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|---|---|---|---|
| JP2253744A JP2984344B2 (en) | 1990-09-21 | 1990-09-21 | Cu-based alloy powder for laser cladding |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2253744A JP2984344B2 (en) | 1990-09-21 | 1990-09-21 | Cu-based alloy powder for laser cladding |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04131341A JPH04131341A (en) | 1992-05-06 |
| JP2984344B2 true JP2984344B2 (en) | 1999-11-29 |
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ID=17255538
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| JP4888769B2 (en) * | 2006-10-16 | 2012-02-29 | 新東工業株式会社 | Copper powder and method for producing the same |
| DE102007060964A1 (en) * | 2007-12-14 | 2009-06-18 | Sieber Forming Solutions Gmbh | Method and device for producing annular, rotationally symmetrical workpieces made of metal and / or ceramic powder |
| CN106334883A (en) * | 2016-11-09 | 2017-01-18 | 沈阳有色金属研究所有限公司 | High-strength corrosion-resistant high-temperature copper-based brazing material and manufacturing method thereof |
| JP7195710B2 (en) * | 2017-04-28 | 2022-12-26 | 古河電気工業株式会社 | Copper alloy particles, surface-coated copper-based particles and mixed particles |
| CN107354455B (en) * | 2017-07-13 | 2018-05-11 | 山东胜利万德胜石油技术服务有限公司 | A kind of laser cladding powder and preparation method |
| JP7194087B2 (en) * | 2019-07-23 | 2022-12-21 | 山陽特殊製鋼株式会社 | Cu-based alloy powder |
| CN113020585B (en) * | 2021-03-01 | 2022-04-05 | 南京理工大学 | Low-melting-point multi-component alloy additive for laser additive manufacturing of aluminum alloy |
-
1990
- 1990-09-21 JP JP2253744A patent/JP2984344B2/en not_active Expired - Lifetime
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7850795B2 (en) * | 2004-03-15 | 2010-12-14 | Toyota Jidosha Kabushiki Kaisha | Build-up wear-resistant copper alloy and valve seat |
| JP2018058093A (en) * | 2016-10-07 | 2018-04-12 | 株式会社豊田中央研究所 | Padding alloy and padding member |
| CN110366459A (en) * | 2017-08-21 | 2019-10-22 | Ｊｘ金属株式会社 | Lamination appearance copper alloy powder, the manufacturing method of lamination forming object and lamination forming object |
| US11624103B2 (en) | 2019-12-16 | 2023-04-11 | Hyundai Motor Company | Copper alloy for laser cladding valve seat |
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|---|---|
| JPH04131341A (en) | 1992-05-06 |
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