JP4690156B2 - Ni brazing alloy - Google Patents
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本発明は、従来に比べて低温でろう付けが可能で、耐食性にも優れ且つ適度な強度を有するバランスの取れた特性を有するＮｉを主成分とするろう材合金に関する。 The present invention relates to a brazing material alloy containing Ni as a main component, which can be brazed at a low temperature as compared with the prior art, has excellent corrosion resistance, and has balanced properties with appropriate strength.
日本工業規格（ＪＩＳ Ｚ３２６５）には、Ｎｉ系のろう材合金として、例えばＮｉ−Ｃｒ−Ｆｅ−Ｓｉ−Ｂ系（ＢＮｉ−２）、Ｎｉ−Ｃｒ−Ｓｉ系（ＢＮｉ−５）、Ｎｉ−Ｃｒ−Ｐ系（ＢＮｉ−７）などが規定されている。 In Japanese Industrial Standard (JIS Z3265), for example, Ni—Cr—Fe—Si—B (BNi-2), Ni—Cr—Si (BNi-5), Ni—Cr as Ni-based brazing alloy. -P system (BNi-7) and the like are defined.
しかしながら、ＢＮｉ−２は融点が比較的低く、強度も問題ないが、Ｂを多く含むために耐食性の問題がある。ＢＮｉ−５においては耐食性が良好であるが、融点が高いため用途が限定されるという問題がある。ＢＮｉ−７は融点が低く、耐食性も良好であるが、Ｐを多く含むため強度が低い点が問題となる。 However, BNi-2 has a relatively low melting point and no problem with strength, but has a problem of corrosion resistance because it contains a large amount of B. Although BNi-5 has good corrosion resistance, there is a problem that its application is limited because of its high melting point. BNi-7 has a low melting point and good corrosion resistance, but has a problem of low strength because it contains a large amount of P.
また、特許文献１に開示されたＮｉ−Ｃｒ−Ｐ−Ｓｉ系のろう材は上記特性のバランスは取れているが、液相線温度がやや高いため、ステンレス鋼と銅をろう付けできない場合がある。更に、Ｃｒを多く含むため連続式水素炉において量産する際に作業性が劣ることがある。
本発明は上記の問題点に着目して為されたものであり、耐食性が良好で、比較的大きな強度を有し、且つＮｉ系の耐熱ろう材の長所を保つと共にステンレス鋼と銅をろう付けできる程度に低い液相線温度を有するＮｉろう材合金を提供することを目的としている。更に、本発明の提供するＮｉろう材合金は連続式水素炉における量産へも使用が可能で、その特性においてバランスの取れたＮｉろう材合金を提供することも目的としている。 The present invention has been made paying attention to the above-mentioned problems, has good corrosion resistance, has a relatively large strength, maintains the advantages of a Ni-based heat-resistant brazing material, and brazes stainless steel and copper. The object is to provide a Ni brazing alloy having a liquidus temperature as low as possible. Furthermore, the Ni brazing alloy provided by the present invention can be used for mass production in a continuous hydrogen furnace, and an object of the present invention is to provide a Ni brazing alloy having a balanced property.
下記の構成により本発明のＮｉろう材合金を提供できる。 The Ni brazing alloy of the present invention can be provided by the following constitution.
（１）質量％で、Ｃｒを５〜１６％、Ｐを２〜９％、Ｓｉを１〜６％、Ｂを０．５〜２．５％含み、残部がＮｉ及び不可避不純物からなるＮｉろう材合金であって、前記残部が７３〜８７質量％であることを特徴とするＮｉろう材合金。 (1) in mass%, a Cr 5 to 16%, 2 to 9% of P, 1 to 6% of Si, wherein the B 0.5 to 2.5%, Ni brazing balance of Ni and unavoidable impurities An Ni brazing alloy characterized in that the balance is 73 to 87% by mass .
（２）Ｐ、Ｓｉ及びＢの合計含有量が８〜１１質量％の範囲にあることを特徴とする（１）記載のＮｉろう材合金。 (2) The Ni brazing alloy according to (1), wherein the total content of P, Si and B is in the range of 8 to 11% by mass .
本発明のＮｉろう材合金において、Ｃｒは耐食性を改善する効果があるが、５％未満では効果が薄く、１６％を超ええると液相線温度が１０５０℃を超え、銅のろう付けができなくなるので、５〜１６％の範囲とした。 In the Ni brazing alloy according to the present invention, Cr has an effect of improving the corrosion resistance. However, if it is less than 5%, the effect is thin, and if it exceeds 16%, the liquidus temperature exceeds 1050 ° C., and copper can be brazed. Since it disappears, it was set as 5 to 16% of range.
Ｐは本発明のＮｉろう材合金の融点を低下させ、流動性が良くなるが、２％未満では効果が十分には発揮できず、９％を超えると合金が脆くなるので、２〜９％の範囲とした。 P lowers the melting point of the Ni brazing alloy of the present invention and improves the fluidity. However, if it is less than 2%, the effect cannot be sufficiently exhibited, and if it exceeds 9%, the alloy becomes brittle. It was made the range.
ＳｉとＢは本発明のＮｉろう材合金の融点を低下させ、フラックス作用を発揮してろう付け作業性を改善するが、Ｓｉが１％未満、Ｂが０．５％未満では効果が発揮されず、Ｓｉが６％、Ｂが２．５％を超えるとＮｉやＣｒとの金属間化合物が過剰に形成され強度や耐食性の低下を招くので、Ｓｉは１〜６％、Ｂは０．５〜２．５％の範囲とした。 Si and B lower the melting point of the Ni brazing alloy of the present invention and exhibit a flux action to improve the brazing workability, but the effect is exhibited when Si is less than 1% and B is less than 0.5%. When Si exceeds 6% and B exceeds 2.5%, an intermetallic compound with Ni or Cr is excessively formed, resulting in a decrease in strength and corrosion resistance. Therefore, Si is 1 to 6% and B is 0.5. It was made into the range of -2.5%.
ＰとＳｉとＢは同じく本発明のＮｉろう材合金の融点及び作業性に影響を及ぼす成分であり、３成分の合計が８％未満では液相線温度が１０５０℃以上となる場合が多く、１１％を超えると強度の低下を招くことが多いので、合計を８〜１１％の範囲とした。 P, Si, and B are components that similarly affect the melting point and workability of the Ni brazing alloy of the present invention. When the total of the three components is less than 8%, the liquidus temperature is often 1050 ° C. or more, If it exceeds 11%, the strength is often lowered, so the total was made 8 to 11%.
不可避不純物を含むＮｉは、本発明のＮｉろう材合金の基本成分であり、上述の各成分とのバランスにより７３〜８７％の範囲に限定される。また本発明のＮｉろう材合金の特性に悪影響を及ぼさない不純物の範囲は、Ｆｅが５％以下、Ｃｏが１％以下、Ｃｕが１％以下、Ｍｎが１％以下、Ｃが０．１５％以下である。 Ni containing inevitable impurities is a basic component of the Ni brazing alloy of the present invention, and is limited to a range of 73 to 87 % depending on the balance with the above-described components. The range of impurities that do not adversely affect the characteristics of the Ni brazing alloy of the present invention is as follows: Fe is 5% or less, Co is 1% or less, Cu is 1% or less, Mn is 1% or less, and C is 0.15%. It is as follows.
本発明によるＮｉろう材合金はその特性のバランスが良く、以下の特徴を有しているので、広範な用途への適用が可能となる。
（１）耐食性が良好。
（２）適度な強度を有する。
（３）ろう付けが比較的低温（１０５０℃以下）で行える。
（４）ろうの流動性が良好。
The Ni brazing filler metal alloy according to the present invention has a good balance of characteristics and has the following characteristics, so that it can be applied to a wide range of uses.
(1) Good corrosion resistance.
(2) It has moderate strength.
(3) Brazing can be performed at a relatively low temperature (1050 ° C. or lower).
(4) The flowability of the wax is good.
ベースのＮｉ、添加成分としてのＣｒ、Ｐ、Ｓｉ、Ｂの夫々が所定の重量％となるように調整した混合物を溶融して液状の合金とした後、アトマイズ法により粉末とするか、所定の型に鋳込んで板状、棒状としてＮｉろう材合金を得ることができる。粉末、板あるいは棒状の合金はそのままろう材として使用できるが、ろう付けする環境、対象物に応じて更に加工したろう材を用いてもよい。例えば粉末にバインダーレジンを混合してペースト状あるいはシート状とすることも可能であり、板は圧延して箔状にしてからろう材として用いることもできる。 A mixture prepared so that each of Ni, the base, and Cr, P, Si, and B as additive components is in a predetermined weight% is melted to form a liquid alloy, and then powdered by an atomizing method, Ni brazing alloy can be obtained by casting into a mold in the form of a plate or rod. Powder, plate, or rod-like alloy can be used as a brazing material as it is, but a brazing material further processed according to the brazing environment and object may be used. For example, a binder resin can be mixed with the powder to form a paste or a sheet, and the plate can be rolled into a foil and used as a brazing material.
上記のように調整した、Ｎｉろう材合金の実施例１〜１３の組成を表１に示す。表１には各実施例の合金のろう付け温度の目安となる液相線温度（℃）及び固相線温度（℃）、合金の強度の指標としての抗析力（ｋｇｆ／ｍｍ）、ろう付作業性及び塩水噴霧試験による耐食性の評価結果を併せて示している。 Table 1 shows the compositions of Examples 1 to 13 of the Ni brazing alloy prepared as described above. Table 1 shows the liquidus temperature (° C.) and the solidus temperature (° C.), which are indicators of the brazing temperature of the alloys of each example, the anti-deposition force (kgf / mm) as an index of the strength of the alloy, and the brazing The results of evaluation of corrosion resistance by the workability and salt spray test are also shown.
液相線及び固相線温度は、Ｎｉろう材合金をアルゴンガス雰囲気の電気炉で溶解し、溶解した合金中に熱伝対を挿入して、合金の冷却曲線を測定し、その曲線を解析して得た。 For liquidus and solidus temperatures, melt the Ni brazing alloy in an electric furnace in an argon gas atmosphere, insert a thermocouple into the melted alloy, measure the cooling curve of the alloy, and analyze the curve. I got it.
抗析力は、電気炉内アルゴンガス雰囲気中で試験すべき合金を溶解し、溶融した合金を内径５ｍｍの石英管に吸い上げて凝固させた後、約３５ｍｍの長さに切断して試験片とした。この試験片を抗析力試験治具（三点支持、支点間距離：２５．４ｍｍ）に設置し、万能試験機により荷重を掛けて破断させ、破断荷重を試験片の断面積で割った値（ｋｇｆ／ｍｍ２）を抗析力として算出した。 The electrodeposition force is obtained by melting an alloy to be tested in an argon gas atmosphere in an electric furnace, sucking and solidifying the molten alloy into a quartz tube having an inner diameter of 5 mm, cutting it to a length of about 35 mm, did. A value obtained by placing this test piece on an anti-deposition force test jig (three-point support, distance between fulcrums: 25.4 mm), applying a load with a universal testing machine to break the load, and dividing the breaking load by the cross-sectional area of the test piece (Kgf / mm 2 ) was calculated as the anti-segregation force.
ろう付作業性は、連続式水素炉を１０５０℃、純水素ガス雰囲気（露天−５０℃）に設定し、メッシュベルト上に設置したろう流れ用の試験片を炉内に挿入し、試験片が実際にろう付けされた状態（拡がり及び濡れ）を目視観察することにより判定した。 Brazing workability is set to 1050 ° C in a continuous hydrogen furnace and pure hydrogen gas atmosphere (open-air -50 ° C), and a test piece for brazing flow installed on a mesh belt is inserted into the furnace. The actual brazed state (spreading and wetting) was determined by visual observation.
耐食性はＪＩＳ Ｚ２３７１の「塩水噴霧試験方法」により、ろう付けを完了した試験片を４８時間塩水噴霧した後、試験片を観察してサビの発生状態を観察し、良否を判定した。４８時間塩水噴霧後、サビの無いものを「良好」、塩水噴霧の途中でサビの発生したものを「不良」とした。 Corrosion resistance was determined by JIS Z2371 “salt water spray test method” after spraying the test piece for which brazing was completed for 48 hours, observing the test piece to observe the state of rust, and determining whether it was good or bad. After spraying with salt water for 48 hours, the sample without rust was evaluated as “good”, and the sample with rust generated during salt spray was determined as “bad”.
本発明による実施例と比較するため、表２には従来から用いているＮｉろう材合金ＢＮｉ−２、ＢＮｉ−７及び本発明の組成範囲外の合金（比較例ａ〜ｄ）の値も併せて示した。 For comparison with the examples according to the present invention, Table 2 also includes values of conventionally used Ni brazing alloy BNi-2 and BNi-7 and alloys outside the composition range of the present invention (comparative examples a to d). Showed.
表１と表２の比較から、本発明による実施例１〜１３は液相線温度が１０４０℃以下で抗析力はＢＮｉ―７の１．５倍以上と強度が大きいことがわかる。 From the comparison between Table 1 and Table 2, it can be seen that Examples 1 to 13 according to the present invention have a liquidus temperature of 1040 ° C. or less and an anti-segregation power of 1.5 times or more that of BNi-7, which is high in strength.
また、１０５０℃での連続水素炉において、従来の合金ＢＮｉ−７はろう拡がりが大きすぎ、ＢＮｉ−２は小さすぎるのに対し、本発明による合金は適度のろう拡がりを示し作業性が良好であることも確認された。 Further, in the continuous hydrogen furnace at 1050 ° C., the conventional alloy BNi-7 has too large brazing and BNi-2 is too small, whereas the alloy according to the present invention exhibits moderate brazing and good workability. It was also confirmed.
塩水噴霧試験においては、ＢＮｉ−７は良好な耐食性を示し、ＢＮｉ−２は耐食性が劣るとの結果となったが、本発明による合金は全て良好な耐食性を示した。比較例ａはＣｒ量が多すぎるために液相線温度が高く、比較例ｂ、ｃはＰ、Ｓｉ、Ｂの合計重量が少ないため液相線温度が高かった。また、比較例ｄはＰ、Ｓｉ、Ｂの合計重量が多すぎるため液相線温度は１０５０℃と比較的低い値であったが、実用に供せないほど強度が著しく低い値を示した。 In the salt spray test, BNi-7 showed good corrosion resistance and BNi-2 showed poor corrosion resistance, but all the alloys according to the present invention showed good corrosion resistance. Comparative Example a had a high liquidus temperature because the amount of Cr was too large, and Comparative Examples b and c had a high liquidus temperature because the total weight of P, Si, and B was small. In Comparative Example d, since the total weight of P, Si, and B was too large, the liquidus temperature was relatively low at 1050 ° C., but the strength was extremely low so that it could not be put to practical use.
以上、述べたように、本発明によるＮｉろう材合金はバランスの取れた特性を有しているので、広範な用途に適用できる。連続水素炉は炉内と大気を遮断する炉心管及びその中を移動する駆動用のメッシュベルトを有しており、通常それらの部材は耐熱系のステンレス鋼やニッケル合金製なので、１１００℃以上で連続的に使用すると極端に寿命が短くなる。従って、本発明によるＮｉろう材合金を使用することにより、１０５０℃以下においてろう付け作業ができるので、水素炉を連続運転して大量生産することが可能となる。また、この温度においてはステンレス鋼と純銅のろう付けが可能となるので、冷凍空調部品、自動車用配管部品などへも適用できる。 As described above, the Ni brazing alloy according to the present invention has balanced characteristics and can be applied to a wide range of applications. A continuous hydrogen furnace has a core tube that shuts off the interior of the furnace and the atmosphere, and a mesh belt for driving that moves through it. Usually, these members are made of heat-resistant stainless steel or nickel alloy, so that the temperature is 1100 ° C or higher. If used continuously, the service life will be extremely shortened. Thus, the use of Ni braze alloy according to the present invention, since it is the brazing operation at 1050 ° C. or less, that Do can be mass-produced continuously operated hydrogen furnace. At this temperature, brazing of stainless steel and pure copper is possible, so that it can be applied to refrigeration and air-conditioning parts, automobile piping parts, and the like.
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| JPH09225679A (en) * | 1996-02-20 | 1997-09-02 | Fukuda Metal Foil & Powder Co Ltd | Ni base heat resistant brazing filter metal excellent in wettability and corrosion resistance |
| JPH10193210A (en) * | 1997-01-09 | 1998-07-28 | Mitsubishi Materials Corp | Cemented carbide-made cutting tool having excellent brazing connection strength in cutting edge piece |
-
2005
- 2005-09-15 JP JP2005268364A patent/JP4690156B2/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH038555A (en) * | 1989-06-06 | 1991-01-16 | Sumitomo Metal Ind Ltd | Method for butt-joining steel |
| JPH06212455A (en) * | 1992-02-11 | 1994-08-02 | Daimler Benz Ag | High loading coating structural member consisting of titanium-aluminide inter- metallic phase |
| JPH09225679A (en) * | 1996-02-20 | 1997-09-02 | Fukuda Metal Foil & Powder Co Ltd | Ni base heat resistant brazing filter metal excellent in wettability and corrosion resistance |
| JPH10193210A (en) * | 1997-01-09 | 1998-07-28 | Mitsubishi Materials Corp | Cemented carbide-made cutting tool having excellent brazing connection strength in cutting edge piece |
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| JP2007075867A (en) | 2007-03-29 |
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