JP2003117686A - Composite material for brazing, and brazed product obtained by using the composite material - Google Patents
Composite material for brazing, and brazed product obtained by using the composite materialInfo
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- JP2003117686A JP2003117686A JP2001312795A JP2001312795A JP2003117686A JP 2003117686 A JP2003117686 A JP 2003117686A JP 2001312795 A JP2001312795 A JP 2001312795A JP 2001312795 A JP2001312795 A JP 2001312795A JP 2003117686 A JP2003117686 A JP 2003117686A
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- brazing
- layer
- composite material
- base material
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Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、ろう付け用複合材
及びそれを用いたろう付け製品に係り、特に、熱交換器
及び燃料電池用部材のろう付けに用いられる複合材及び
それを用いたろう付け製品に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a brazing composite material and a brazing product using the same, and more particularly to a composite material used for brazing heat exchangers and fuel cell members and brazing using the same. It is about products.
【０００２】[0002]
【従来の技術】自動車用オイルクーラの接合材としてス
テンレス基クラッド材が使用されている。これは、基材
であるステンレス鋼板の片面又は両面に、ろう材として
の機能を有するＣｕ材がクラッドされている。2. Description of the Related Art Stainless steel based clad materials are used as joining materials for automobile oil coolers. In this, a Cu material having a function as a brazing material is clad on one side or both sides of a stainless steel plate which is a base material.
【０００３】また、ステンレス鋼や、Ｎｉ基又はＣｏ基
合金などからなる部材のろう付け材として、接合部の耐
酸化性や耐食性に優れる各種Ｎｉろう材が、ＪＩＳ規格
により規定されている。As a brazing material for members made of stainless steel, Ni-based or Co-based alloys, various Ni brazing materials having excellent oxidation resistance and corrosion resistance at the joint are specified by the JIS standard.
【０００４】さらに、熱交換器の接合に用いられるＮｉ
ろう材として、粉末状のＮｉろう材に、Ｎｉ、Ｃｒ、又
はＮｉ−Ｃｒ合金の中から選択される金属粉末を４〜２
２ｗｔ％添加してなる粉末Ｎｉろう材が提案されている
（特開２０００−１０７８８３公報参照）。Further, Ni used for joining heat exchangers.
As a brazing filler metal, a powdered Ni brazing filler metal and a metal powder selected from Ni, Cr, or a Ni—Cr alloy is used in an amount of 4 to 2
A powdered Ni brazing material added with 2 wt% has been proposed (see Japanese Patent Laid-Open No. 2000-107883).
【０００５】また、基材であるステンレス鋼の表面にＮ
ｉ及びＴｉからなるろう付け層を有する、即ちＮｉ／Ｔ
ｉ／ステンレス鋼というろう付け層構造を有する自己ろ
う付け性複合材がある（特開平７−２９９５９２号公報
参照）。Further, N is formed on the surface of the stainless steel which is the base material.
with a brazing layer consisting of i and Ti, ie Ni / T
There is a self-brazing composite material having a brazing layer structure of i / stainless steel (see Japanese Patent Laid-Open No. 7-299592).
【０００６】[0006]
【発明が解決しようとする課題】しかしながら、従来の
ろう材又はろう付け用複合材を、高温・高腐食性のガス
又は液体に晒される熱交換器（排ガス再循環装置（以
下、ＥＧＲ（Exhaust GasRecirculation）と示す）用ク
ーラ）の接合用ろう材として使用する場合、以下に示す
ような問題があった。However, a conventional brazing material or brazing composite material is exposed to a high temperature and highly corrosive gas or liquid (heat exchanger (exhaust gas recirculation device (hereinafter referred to as EGR (Exhaust Gas Recirculation When used as a brazing filler metal for ()))), there were the following problems.
【０００７】 前述したステンレス基クラッド材を自
動車用オイルクーラの接合材として使用する場合、耐熱
性、耐酸化性、及び耐食性について問題が全くないが、
このステンレス基クラッド材をＥＧＲ用クーラの接合材
として使用する場合、ＥＧＲ用クーラ内は高温で、か
つ、腐食性の高い排気ガスが循環されることから、ステ
ンレス基クラッド材のろう材（Ｃｕ材）では、耐熱性、
耐酸化性、及び耐食性が十分でないという問題があっ
た。When the above-mentioned stainless steel-based clad material is used as a joining material for an oil cooler for automobiles, there is no problem in heat resistance, oxidation resistance, and corrosion resistance.
When this stainless steel-based clad material is used as a joining material for an EGR cooler, a brazing material (Cu material) of the stainless steel-based clad material is used because the exhaust gas with high temperature and high corrosiveness is circulated in the EGR cooler. ), Heat resistance,
There is a problem that the oxidation resistance and the corrosion resistance are not sufficient.
【０００８】 前述した各種Ｎｉろう材は粉末状であ
ることから、各接合部に粉末Ｎｉろう材をそれぞれ塗布
するという作業が必要になる。つまり、ろう付け作業に
多大な労力を要するため、ろう付け製品の生産性が著し
く低く、その結果、製造コストの上昇を招くという問題
があった。Since the various Ni brazing materials described above are powdery, it is necessary to apply the powder Ni brazing material to each joint. That is, there is a problem that the brazing work requires a great deal of labor, so that the productivity of the brazing product is extremely low, resulting in an increase in manufacturing cost.
【０００９】 前述した自己ろう付け性複合材は、耐
熱性及び耐食性については十分な効果を発揮するもの
の、ろう付けする際に、基材のステンレス鋼が溶融ろう
付け層により激しく侵食され、ろう付け後の製品の性能
（強度、疲労特性）が大きく低下するという問題があっ
た。具体的には、Ｎｉ層及びＴｉ層はろう付けする際の
熱処理によって溶融するが、Ｔｉの反応性が著しく高い
ことから、Ｔｉと基材であるステンレス鋼の反応が過大
となる。これは、基材であるステンレス鋼のＦｅ成分と
Ｔｉが反応し、Ｆｅリッチな固溶体相及びＦｅ2Ｔｉ、
ＦｅＴｉなどの金属間化合物が生じやすいためである。
その結果、基材のＦｅ成分がろう付け層中へ溶出（溶融
・分散）することから、基材において著しい侵食が生
じ、ろう付け前の基材の厚さ・体積を確保することがで
きず、接合部の接合強度の低下、即ちろう付け製品の信
頼性の低下が生じる。Although the above-described self-brazing composite material exerts a sufficient effect on heat resistance and corrosion resistance, when brazing, the stainless steel of the base material is severely eroded by the molten brazing layer and There has been a problem that the performance (strength, fatigue characteristics) of the subsequent product is greatly reduced. Specifically, the Ni layer and the Ti layer are melted by the heat treatment during brazing, but the reactivity of Ti with the base material stainless steel becomes excessive because the reactivity of Ti is extremely high. This is because the Fe component of the base material stainless steel reacts with Ti, and the Fe-rich solid solution phase and Fe 2 Ti,
This is because intermetallic compounds such as FeTi are likely to occur.
As a result, the Fe component of the base material elutes (melts / disperses) into the brazing layer, causing significant erosion in the base material, and the thickness / volume of the base material before brazing cannot be secured. , The joint strength of the joint part is lowered, that is, the reliability of the brazed product is lowered.
【００１０】以上の事情を考慮して創案された本発明の
一の目的は、ろう付け特性が良好で、かつ、ろう付け時
における基材の侵食の割合が低いろう付け用複合材を提
供することにある。An object of the present invention, which was devised in view of the above circumstances, is to provide a brazing composite material having good brazing characteristics and having a low base material erosion rate during brazing. Especially.
【００１１】また、本発明の他の目的は、接合部の信頼
性が良好で、製造コストが安価なろう付け製品を提供す
ることにある。Another object of the present invention is to provide a brazed product having a good joint reliability and a low manufacturing cost.
【００１２】[0012]
【課題を解決するための手段】上記目的を達成すべく本
発明に係るろう付け用複合材は、基材表面にろう付け層
を形成してなるろう付け用複合材において、上記基材表
面に、基材側から順に第１Ｎｉ又はＮｉ合金層、Ｔｉ又
はＴｉ合金層、及び第２Ｎｉ又はＮｉ合金層の三層から
なるろう付け層を形成したものである。In order to achieve the above object, a brazing composite material according to the present invention is a brazing composite material in which a brazing layer is formed on the surface of a base material. A brazing layer composed of three layers of a first Ni or Ni alloy layer, a Ti or Ti alloy layer, and a second Ni or Ni alloy layer is formed in this order from the base material side.
【００１３】ここで、上記第２Ｎｉ又はＮｉ合金層を、
少なくともＰを０．０２〜１０ｗｔ％含有するＮｉ−Ｐ
合金で形成してもよい。Here, the second Ni or Ni alloy layer is
Ni-P containing at least 0.02 to 10 wt% P
It may be formed of an alloy.
【００１４】また、上記第１Ｎｉ又はＮｉ合金層の層厚
を、第２Ｎｉ又はＮｉ合金層の層厚よりも厚く形成して
もよい。The layer thickness of the first Ni or Ni alloy layer may be made thicker than the layer thickness of the second Ni or Ni alloy layer.
【００１５】また、上記基材を、ステンレス鋼で形成し
てもよい。The substrate may be made of stainless steel.
【００１６】以上によれば、ろう付け特性が良好で、か
つ、ろう付け時における基材の侵食の割合が低いろう付
け用複合材が得られる。According to the above, it is possible to obtain a brazing composite material having good brazing characteristics and having a low base material erosion rate during brazing.
【００１７】一方、本発明に係るろう付け製品は、上記
ろう付け用複合材を用いて接合したものである。On the other hand, the brazing product according to the present invention is obtained by joining the brazing composite material.
【００１８】以上によれば、接合部の信頼性が良好で、
製造コストが安価なろう付け製品が得られる。According to the above, the reliability of the joint is good,
A brazed product with a low manufacturing cost is obtained.
【００１９】[0019]
【発明の実施の形態】以下、本発明の好適一実施の形態
を添付図面に基いて説明する。DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT A preferred embodiment of the present invention will be described below with reference to the accompanying drawings.
【００２０】本発明者らは、従来の自己ろう付け性複合
材（Ｎｉ−Ｔｉ系ろう材）と同等の耐熱性、耐酸化性、
及び耐食性を有し、ろう付け時に、基材であるステンレ
ス鋼のＴｉによる侵食（ろう付け層中へ溶融・分散）が
少なく、かつ、ろう付け加工が容易なろう付け用複合材
の構成について種々検討した結果、ろう付け層を基材側
から順に第１Ｎｉ又はＮｉ合金層、Ｔｉ又はＴｉ合金
層、及び第２Ｎｉ又はＮｉ合金層の三層で構成すること
で、上記の特性を満足するろう付け用複合材を得ること
ができた。The inventors of the present invention have the same heat resistance, oxidation resistance and heat resistance as the conventional self-brazing composite material (Ni-Ti type brazing material).
In addition, it has corrosion resistance, little corrosion of Ti, which is the base material of stainless steel (melting / dispersion into the brazing layer) during brazing, and various brazing composite materials that are easy to braze. As a result of examination, brazing satisfying the above-mentioned characteristics by forming the brazing layer from three layers of a first Ni or Ni alloy layer, a Ti or Ti alloy layer, and a second Ni or Ni alloy layer in order from the base material side. The composite material could be obtained.
【００２１】本発明に係るろう付用複合材の第１実施形
態の断面図を図１に、図１の第１変形例、第２変形例、
及び第３変形例の断面図を、図２、図３、及び図４に示
す。FIG. 1 is a sectional view of a first embodiment of a brazing composite material according to the present invention, and FIG. 1 shows a first modified example, a second modified example,
2 and 3 and 4 are sectional views of the third modification.
【００２２】図１に示すように、第１実施形態のろう付
用複合材１０は、ステンレス鋼板からなる基材１１の表
面（図１中では上面のみ）に、基材１１側から順に、第
１Ｎｉ又はＮｉ合金層１２、Ｔｉ又はＴｉ合金層１３、
及び第２Ｎｉ又はＮｉ合金層１４の三層からなるろう付
け層１５を形成し、Ｔｉ層をＮｉ層で挟んだ構造とした
ものである。ここで言う基材１１の表面は、外部に露出
する全ての面を示している。As shown in FIG. 1, the brazing composite material 10 according to the first embodiment has a base material 11 made of a stainless steel plate, and a surface (only an upper surface in FIG. 1) of the base material 11 in order from the base material 11 side. 1 Ni or Ni alloy layer 12, Ti or Ti alloy layer 13,
Also, a brazing layer 15 composed of three layers of the second Ni or Ni alloy layer 14 is formed, and a Ti layer is sandwiched between Ni layers. The surface of the base material 11 mentioned here indicates all the surfaces exposed to the outside.
【００２３】ここで、基材１１の構成材は、Ｆｅを主成
分とするＦｅ基合金が好ましく、特にステンレス鋼が好
ましい。Here, the constituent material of the base material 11 is preferably an Fe-based alloy containing Fe as a main component, and particularly preferably stainless steel.
【００２４】第１（又は第２）Ｎｉ又はＮｉ合金層１２
（又は１４）を構成するＮｉ合金としては、Ｎｉ−Ｐ系
合金や、Ｎｉ−Ｃｒ−Ｆｅ系耐食耐熱超合金（例えば、
インコネル（登録商標）等）が好ましい。これらの合金
を用いることで、ろう付け時の湯流れ性や濡れ性の改善
を図ることができ、また、基材１１としてＦｅ基合金
（例えば、ステンレス鋼）を用いた場合、基材１１のＦ
ｅ成分がろう付け層１５中に溶出するのを低減すること
ができる。First (or second) Ni or Ni alloy layer 12
As the Ni alloy constituting (or 14), a Ni-P alloy or a Ni-Cr-Fe corrosion-resistant heat-resistant superalloy (for example,
Inconel (registered trademark) or the like) is preferable. By using these alloys, it is possible to improve the flowability and wettability of the molten metal during brazing, and when an Fe-based alloy (for example, stainless steel) is used as the base material 11, F
It is possible to reduce elution of the e component into the brazing layer 15.
【００２５】ろう付け層１５（又は２５）の最外層であ
る第２Ｎｉ又はＮｉ合金層１４を、Ｐ、Ｂ、又はＳｉか
ら選択される少なくとも一種を含有するＮｉ合金で構成
してもよい。Ｎｉ合金にこれらの元素を含有させると共
に、これらの元素の含有量を調整することで、ろう材の
融点、濡れ性、靭性、及び接合強度を調整することがで
きる。特に、Ｎｉ合金に、Ｐを０．０２〜１０ｗｔ％含
有させることで、ろう材の湯流れ性、濡れ性、及び耐食
性を著しく改善することができる。Ｐの含有量を０．０
２〜１０ｗｔ％と規定したのは、０．０２ｗｔ％未満だ
と、湯流れ性の向上が期待できないという不都合が生じ
るためであり、逆に１０ｗｔ％を超えると、ろう付け層
が脆化し振動疲労特性及び接合強度が著しく低下すると
いう不都合が生じるためであり、好ましい含有量は０．
５〜８ｗｔ％である。The second Ni or Ni alloy layer 14, which is the outermost layer of the brazing layer 15 (or 25), may be made of a Ni alloy containing at least one selected from P, B, and Si. The melting point, the wettability, the toughness, and the bonding strength of the brazing filler metal can be adjusted by making the Ni alloy contain these elements and adjusting the contents of these elements. In particular, by containing 0.02 to 10 wt% of P in the Ni alloy, it is possible to remarkably improve the molten metal flowability, the wettability, and the corrosion resistance of the brazing material. P content of 0.0
The reason for defining 2 to 10 wt% is that if it is less than 0.02 wt%, the inconvenience that the improvement of the flowability of the molten metal cannot be expected occurs, while if it exceeds 10 wt%, the brazing layer becomes brittle and vibration fatigue occurs. This is because the disadvantage that the characteristics and the bonding strength are significantly reduced occurs, and the preferable content is 0.
It is 5 to 8 wt%.
【００２６】ろう付け層１５全体のＴｉ濃度は、特に限
定するものではないが、好ましくは２０〜６０ｗｔ％、
より好ましくは３０〜５０ｗｔ％、特に好ましくは４０
ｗｔ％前後である。The Ti concentration of the entire brazing layer 15 is not particularly limited, but is preferably 20 to 60 wt%,
More preferably 30 to 50 wt%, particularly preferably 40
It is around wt%.
【００２７】ろう付け層１５の形成方法は、特に限定す
るものではなく、例えば、板材を積層した後、圧延によ
り一体化する方法等が挙げられる。The method for forming the brazing layer 15 is not particularly limited, and examples thereof include a method in which plate materials are laminated and then integrated by rolling.
【００２８】また、図１に示した本実施形態のろう付用
複合材１０は、第１Ｎｉ又はＮｉ合金層１２と第２Ｎｉ
又はＮｉ合金層１４の層厚を同じに形成しているが、図
２に示すように、基材１１側の第１Ｎｉ又はＮｉ合金層
１２の層厚を、第２Ｎｉ又はＮｉ合金層１４の層厚より
も厚く形成してもよい。The brazing composite material 10 of the present embodiment shown in FIG. 1 has a first Ni or Ni alloy layer 12 and a second Ni layer.
Alternatively, the Ni alloy layer 14 is formed to have the same layer thickness, but as shown in FIG. 2, the layer thickness of the first Ni or Ni alloy layer 12 on the base material 11 side is set to the layer of the second Ni or Ni alloy layer 14. It may be formed thicker than the thickness.
【００２９】図１（又は図２）に示した複合材１０（又
は２０）は、基材１１の片面（図１、図２中では上面）
のみにろう付け層１５（又は２５）を形成しているが、
図３に示すように、基材１１の両面（図３中では上・下
面）にろう付け層１５，１５を形成し、ろう付け用複合
材３０としてもよい。The composite material 10 (or 20) shown in FIG. 1 (or FIG. 2) is one side of the base material 11 (upper surface in FIGS. 1 and 2).
The brazing layer 15 (or 25) is formed only on
As shown in FIG. 3, brazing layers 15 and 15 may be formed on both surfaces (upper and lower surfaces in FIG. 3) of the base material 11 to form the brazing composite material 30.
【００３０】これらの複合材１０，２０，３０（以下、
複合材１０〜３０と示す）はクラッド材であるが、その
形成方法は特に限定するものではなく、クラッド材形成
のための慣用の方法が全て適用可能であり、例えば、板
材の積層・圧延を繰り返して形成する方法、又は全板材
を積層した後にまとめて圧延する方法等が挙げられる。These composite materials 10, 20, 30 (hereinafter,
Composite materials 10 to 30) are clad materials, but the forming method is not particularly limited, and any conventional method for forming a clad material can be applied. Examples thereof include a method of repeatedly forming, a method of laminating all plate materials and then rolling together.
【００３１】図１〜図３に示した複合材１０〜３０は、
板状の基材１１の表面にろう付け層１５（又は２５或い
は１５，１５）を形成しているが、図４に示すように、
棒状又はワイヤ状の基材４１の表面にろう付け層１５を
形成し、ろう付け用複合材４０としてもよい。この場合
のろう付け層１５の形成は、メッキ法、押出法、造管法
などによって行う。The composite materials 10 to 30 shown in FIGS. 1 to 3 are
The brazing layer 15 (or 25 or 15, 15) is formed on the surface of the plate-shaped substrate 11, but as shown in FIG.
The brazing layer 15 may be formed on the surface of the rod-shaped or wire-shaped base material 41 to form the brazing composite material 40. In this case, the brazing layer 15 is formed by a plating method, an extrusion method, a pipe forming method, or the like.
【００３２】次に、本実施の形態の作用について説明す
る。Next, the operation of this embodiment will be described.
【００３３】本実施の形態の複合材１０，２０，３０，
４０（以下、複合材１０〜４０と示す）においては、基
材１１のＦｅ成分（ステンレス鋼）とろう付け層１５に
おけるＴｉ又はＴｉ合金層１３のＴｉ成分の反応を極力
抑制するために、Ｔｉ又はＴｉ合金層１３の両面にＮｉ
又はＮｉ合金層１２，１４を設け、基材１１とＴｉ又は
Ｔｉ合金層１３の間にバリア層として第１Ｎｉ又はＮｉ
合金（例えば、Ｎｉ−Ｃｒ−Ｆｅ系合金）層１２を形成
することで、基材１１とＴｉ又はＴｉ合金層１３が直接
接触するのを防いでいる。ここで、基材１１とＴｉ層の
間にＮｉ層を形成するのは、ＮｉとＦｅ（ステンレス
鋼）の拡散速度（Ｎｉに対するＦｅの拡散速度）が、Ｔ
ｉとＦｅ（ステンレス鋼）の拡散速度（Ｔｉに対するＦ
ｅの拡散速度）に比べて著しく遅いためであり、これに
よって、溶融したろう付け層１５におけるＴｉ成分とス
テンレス鋼中のＦｅ成分の反応が抑制され、延いては基
材１１とＴｉ又はＴｉ合金層１３の間に、金属間化合物
が生成するのを防ぐことができる。The composite materials 10, 20, 30 of the present embodiment
In 40 (hereinafter referred to as composite materials 10 to 40), in order to suppress the reaction between the Fe component (stainless steel) of the base material 11 and the Ti component of the brazing layer 15 or the Ti component of the Ti alloy layer 13 as much as possible, Ti Or Ni on both sides of the Ti alloy layer 13
Alternatively, the Ni alloy layers 12 and 14 are provided, and the first Ni or Ni is used as a barrier layer between the base material 11 and the Ti or Ti alloy layer 13.
By forming the alloy (for example, Ni—Cr—Fe based alloy) layer 12, direct contact between the base material 11 and the Ti or Ti alloy layer 13 is prevented. Here, the Ni layer is formed between the base material 11 and the Ti layer because the diffusion rate of Ni and Fe (stainless steel) (the diffusion rate of Fe with respect to Ni) is T
i and diffusion rate of Fe (stainless steel) (F to Ti)
This is because the reaction of the Ti component in the molten brazing layer 15 and the Fe component in the stainless steel is suppressed, and by extension, the base material 11 and the Ti or Ti alloy. It is possible to prevent the formation of intermetallic compounds between the layers 13.
【００３４】また、図２に示した複合材２０において
は、Ｔｉ又はＴｉ合金層１３の両面に形成するＮｉ又は
Ｎｉ合金層２２，１４の内、基材１１側の第１Ｎｉ又は
Ｎｉ合金層２２の層厚を第２Ｎｉ又はＮｉ合金層１４の
層厚よりも厚く形成することで、基材１１のＦｅ成分が
ろう付け層２５におけるＴｉ又はＴｉ合金層１３のＴｉ
成分と反応するのを更に抑制することができる。すなわ
ち、ろう付けする際の熱処理により、Ｔｉ又はＴｉ合金
層１３のＴｉ成分は、その両面に隣接するＮｉ又はＮｉ
合金層２２，１４に同じ拡散速度で拡散していくが、基
材１１側の第１Ｎｉ又はＮｉ合金層２２の方が第２Ｎｉ
又はＮｉ合金層１４よりも層厚が厚い分、拡散が進行し
にくくなり、その結果、ステンレス鋼の侵食がより生じ
にくくなる。Further, in the composite material 20 shown in FIG. 2, among the Ni or Ni alloy layers 22 and 14 formed on both sides of the Ti or Ti alloy layer 13, the first Ni or Ni alloy layer 22 on the base material 11 side is formed. Is formed thicker than the layer thickness of the second Ni or Ni alloy layer 14, the Fe component of the base material 11 is Ti in the brazing layer 25 or Ti of the Ti alloy layer 13.
It is possible to further suppress the reaction with the components. That is, due to the heat treatment during brazing, the Ti component of the Ti or Ti alloy layer 13 is Ni or Ni adjacent to both surfaces thereof.
Although it diffuses into the alloy layers 22 and 14 at the same diffusion rate, the first Ni or the Ni alloy layer 22 on the base material 11 side is the second Ni.
Alternatively, since the layer thickness is larger than that of the Ni alloy layer 14, diffusion is less likely to proceed, and as a result, corrosion of stainless steel is less likely to occur.
【００３５】さらに、複合材１０〜４０は、基材１１，
４１の表面にろう付け層１５（又は２５）を一体に設け
ているため、ろう付けの際、従来の各種Ｎｉろう材のよ
うに、各接合部に粉末Ｎｉろう材をそれぞれ塗布すると
いう作業を必要とせず、ろう付け作業に多大な労力を要
することはない（ろう付け作業性が良好となる）。その
結果、ろう付け製品の歩留まり・生産性が良好となり、
延いては製造コストの低減を図ることができる。Further, the composite materials 10 to 40 are composed of the base material 11,
Since the brazing layer 15 (or 25) is integrally provided on the surface of 41, it is necessary to apply powdered Ni brazing material to each joint at the time of brazing, like various conventional Ni brazing materials. It is not necessary and does not require much labor for the brazing work (the brazing workability is good). As a result, the yield and productivity of brazed products are improved,
As a result, the manufacturing cost can be reduced.
【００３６】また、複合材１０〜４０は、Ｎｉ又はＮｉ
合金層１２，１４（又は２２，１４）を構成するＮｉ合
金に、適宜、添加元素を加えることで、ろう付け層１５
（又は２５）の湯流れ性が良好となる。このため、複合
材１０〜４０を、ろう付け接合部の形状が複雑なろう付
け部材のろう付けに適用した場合、接合部においては、
良好な接合面及び十分な接合強度を得ることができ、延
いてはろう付け製品の接合部の信頼性が高まる。The composite materials 10 to 40 are made of Ni or Ni.
The brazing layer 15 is formed by appropriately adding an additional element to the Ni alloy forming the alloy layers 12 and 14 (or 22 and 14).
(Or 25) has good flowability. Therefore, when the composite materials 10 to 40 are applied to brazing of a brazing member having a complicated brazing joint shape,
A good joint surface and a sufficient joint strength can be obtained, which in turn increases the reliability of the joint portion of the brazed product.
【００３７】さらに、複合材１０〜４０においては、ろ
う付け層１５（又は２５）をＮｉ又はＮｉ合金層１２
（又は２２），１４とＴｉ又はＴｉ合金層１３で構成し
ているため、ろう付けの際、Ｔｉろう材中にＮｉろう材
のＮｉ元素が混入する（溶け込む）。これによって、耐
熱性及び耐食性に優れるものの、その融点の高さからろ
う材として機能させることが困難であったＴｉ又はＴｉ
合金からなるＴｉろう材の融点を下げることができ、Ｔ
ｉろう材を用いたろう付けを１２００℃近傍で行うこと
が可能となる。その結果、従来の自己ろう付け性複合材
（Ｎｉ−Ｔｉ系ろう材）と同等の優れた耐熱性及び耐食
性を有し、かつ、優れたろう付け性を有するＴｉ基ろう
付け部（接合部）を得ることができる。Further, in the composite materials 10 to 40, the brazing layer 15 (or 25) is replaced with the Ni or Ni alloy layer 12
(Or 22), 14 and Ti or the Ti alloy layer 13, the Ni element of the Ni brazing material mixes (melts) into the Ti brazing material during brazing. As a result, although Ti and Ti are excellent in heat resistance and corrosion resistance, it is difficult to function as a brazing material due to their high melting point.
The melting point of Ti brazing material made of alloy can be lowered, and T
Brazing using the i brazing material can be performed at around 1200 ° C. As a result, a Ti-based brazing part (joint part) having excellent heat resistance and corrosion resistance equivalent to those of the conventional self-brazing composite material (Ni-Ti type brazing material) and having excellent brazing property is obtained. Obtainable.
【００３８】また、複合材１０〜４０を用いたろう付け
製品は、複合材１０〜４０のろう付け層１５（又は２
５）と接合を行うろう付け部材（図示せず）を重ね合わ
せて加熱することで、または、接合を行う一組のろう付
け部材の内、一方のろう付け部材を基材１１（又は４
１）として複合材１０〜４０を形成し、この複合材１０
〜４０と他方のろう付け部材を重ね合わせて加熱するこ
とで得られる。A brazing product using the composite materials 10 to 40 is a brazing layer 15 (or 2) of the composite materials 10 to 40.
5) and a brazing member (not shown) for joining are superposed and heated, or one of the brazing members for joining is joined to the base material 11 (or 4).
As 1), composite materials 10 to 40 are formed.
-40 and the other brazing member are overlapped and heated.
【００３９】本実施の形態の複合材１０〜４０は、ＥＧ
Ｒ用クーラなどの高温・高腐食性のガス又は液体に晒さ
れる熱交換器のみに、その用途を限定するものではな
く、その他にも、例えば、燃料電池の改質器用クーラ
や、燃料電池部材などの各種用途にも適用可能である。
特に、複合材４０は、ＥＧＲ用クーラや、燃料電池の改
質器用クーラ等の熱交換器、燃料電池部材などの他に
も、オイルクーラ、ラジエータ、二次電池部材などにも
適用可能である。The composite materials 10 to 40 of this embodiment are EG
The use is not limited to heat exchangers such as R coolers that are exposed to high temperature and highly corrosive gases or liquids, and in addition, for example, coolers for reformers of fuel cells and fuel cell members. It is also applicable to various uses such as.
In particular, the composite material 40 is applicable to an EGR cooler, a heat exchanger such as a cooler for a reformer of a fuel cell, a fuel cell member, an oil cooler, a radiator, a secondary battery member, and the like. .
【００４０】以上、本発明の実施の形態は、上述した実
施の形態に限定されるものではなく、他にも種々のもの
が想定されることは言うまでもない。It is needless to say that the embodiments of the present invention are not limited to the above-mentioned embodiments but various other embodiments are possible.
【００４１】[0041]
【実施例】（実施例１）ＳＵＳ３０４（ＪＩＳ規格）か
らなり、厚さ２．５ｍｍ、幅１５０ｍｍのステンレス鋼
条材の表面に、そのステンレス鋼条材側から順に厚さ
０．０７６ｍｍの第１Ｎｉ条材、厚さ０．２ｍｍのＴｉ
条材、及び厚さ０．０７６ｍｍの第２Ｎｉ条材を圧延法
によりクラッドし、ろう付け層の各層の重量比（第２Ｎ
ｉ／Ｔｉ／第１Ｎｉ）が30Ni-40Ti-30Ni（ｗｔ％）であ
る複合基材を作製した。その後、この複合基材に対して
圧延を繰り返し行い、ろう付け層全体の厚さが７０μｍ
（０．０７ｍｍ）のろう付け用複合材を作製した。Example 1 A first Ni sheet made of SUS304 (JIS standard) and having a thickness of 2.5 mm and a width of 150 mm is formed on the surface of a stainless steel strip material in order from the stainless steel strip side to have a thickness of 0.076 mm. Strip material, Ti with a thickness of 0.2 mm
A strip material and a second Ni strip material having a thickness of 0.076 mm are clad by a rolling method, and the weight ratio of each layer of the brazing layer (second N
A composite substrate in which i / Ti / first Ni) was 30Ni-40Ti-30Ni (wt%) was prepared. After that, rolling is repeatedly performed on the composite base material so that the entire brazing layer has a thickness of 70 μm.
A (0.07 mm) brazing composite material was produced.
【００４２】（実施例２）実施例１と同じステンレス鋼
条材の表面に、そのステンレス鋼条材側から順に厚さ
０．１ｍｍの第１Ｎｉ条材、厚さ０．２ｍｍのＴｉ条
材、及び厚さ０．０５ｍｍの第２Ｎｉ条材を圧延法によ
りクラッドし、ろう付け層の各層の重量比（第２Ｎｉ／
Ｔｉ／第１Ｎｉ）が20Ni-40Ti-40Ni（ｗｔ％）である複
合基材を作製した。その後、この複合基材に対して圧延
を繰り返し行い、ろう付け層全体の厚さが７０μｍ
（０．０７ｍｍ）のろう付け用複合材を作製した。(Example 2) On the surface of the same stainless steel strip as in Example 1, the first Ni strip having a thickness of 0.1 mm, the Ti strip having a thickness of 0.2 mm, in this order from the stainless steel strip side, And a second Ni strip having a thickness of 0.05 mm is clad by a rolling method, and the weight ratio of each brazing layer (second Ni /
A composite substrate was prepared in which Ti / first Ni) was 20Ni-40Ti-40Ni (wt%). After that, rolling is repeatedly performed on the composite base material so that the entire brazing layer has a thickness of 70 μm.
A (0.07 mm) brazing composite material was produced.
【００４３】（比較例１）実施例１と同じステンレス鋼
条材の表面に、そのステンレス鋼条材側から順に厚さ
０．１５２ｍｍのＮｉ条材及び厚さ０．２ｍｍのＴｉ条
材を圧延法によりクラッドし、ろう付け層の各層の重量
比（Ｎｉ／Ｔｉ）が60Ni-40Ti（ｗｔ％）である複合基
材を作製した。その後、この複合基材に対して圧延を繰
り返し行い、ろう付け層全体の厚さが７０μｍ（０．０
７ｍｍ）のろう付け用複合材を作製した。Comparative Example 1 On the surface of the same stainless steel strip as in Example 1, a Ni strip having a thickness of 0.152 mm and a Ti strip having a thickness of 0.2 mm were rolled in order from the stainless steel strip side. A composite base material was produced in which the brazing layer was clad by the method and the weight ratio (Ni / Ti) of the brazing layers was 60Ni-40Ti (wt%). Then, rolling is repeatedly performed on the composite base material so that the entire brazing layer has a thickness of 70 μm (0.0
7 mm) of a brazing composite material was prepared.
【００４４】（従来例１）実施例１と同じステンレス鋼
条材の表面に、厚さ０．３ｍｍのＣｕ条材を圧延法によ
りクラッドして複合基材を作製した。その後、この複合
基材に対して圧延を繰り返し行い、ろう付け層（Ｃｕ
層）の厚さが７０μｍのろう付け用複合材を作製した。(Conventional Example 1) A Cu base material having a thickness of 0.3 mm was clad on the surface of the same stainless steel base material as in Example 1 by a rolling method to prepare a composite base material. After that, rolling is repeatedly performed on the composite base material so that the brazing layer (Cu
A brazing composite material having a layer thickness of 70 μm was produced.
【００４５】（従来例２）実施例１と同じステンレス鋼
条材の表面に、市販の粉末Ｎｉろう材（平均粒径３５μ
ｍ）を合成樹脂（ポリマー系樹脂）のバインダで溶いた
混練物を塗布し、ろう付け用複合材を作製した。(Prior Art Example 2) A commercially available powdered Ni brazing material (average particle size: 35 μm) was formed on the surface of the same stainless steel strip as in Example 1.
The kneaded material in which m) was melted with a binder of synthetic resin (polymer resin) was applied to prepare a brazing composite material.
【００４６】実施例１，２、比較例１、及び従来例１，
２の複合材の層構造及びろう付け層の各層の重量比を表
１に示す。Examples 1 and 2, Comparative Example 1, and Conventional Example 1,
Table 1 shows the layer structure of the composite material of No. 2 and the weight ratio of each layer of the brazing layer.
【００４７】[0047]
【表１】 [Table 1]
【００４８】次に、各複合材を、真空炉で加熱してろう
付け層を溶融させ、それらのろう付け性能をそれぞれ評
価した。ろう付け性能の評価は、基材であるステンレス
鋼条材の侵食の割合、耐食性、ろう材の濡れ性、ろう付
け生産性（作業性）及びそれらの評価の総合評価により
行った。評価結果を表２に示す。Next, each of the composite materials was heated in a vacuum furnace to melt the brazing layer, and their brazing performances were evaluated. The brazing performance was evaluated by a comprehensive evaluation of the corrosion rate of the stainless steel strip as the base material, the corrosion resistance, the wettability of the brazing material, the brazing productivity (workability), and the evaluation thereof. The evaluation results are shown in Table 2.
【００４９】ここで、侵食の割合の評価は、各複合材を
真空炉中で加熱してろう付け層を溶融させた後、各複合
材の断面を観察し、基材であるステンレス鋼条材の板厚
残存率（熱処理後の板厚×１００／熱処理前の板厚
（％））を測定することによって行った。Here, the rate of erosion is evaluated by heating each composite material in a vacuum furnace to melt the brazing layer, and then observing the cross section of each composite material, the stainless steel strip material as the base material. The remaining plate thickness (plate thickness after heat treatment × 100 / plate thickness before heat treatment (%)) was measured.
【００５０】また、耐食性の評価は、塩素イオン、硝酸
イオン、及び硫酸イオンを含んだ腐食性溶液中に、積層
体又は各複合材を１０００時間浸漬して腐食試験を行
い、その後、積層体又は各複合材を溶液中から取出して
ろう付け部の組織観察を行い、腐食発生の有無を調べる
ことによって行った。The corrosion resistance was evaluated by immersing the laminate or each composite material in a corrosive solution containing chlorine ions, nitrate ions, and sulfate ions for 1000 hours to carry out a corrosion test. Each composite material was taken out of the solution, the structure of the brazed portion was observed, and the presence or absence of corrosion was examined.
【００５１】さらに、ろうの濡れ性の評価は、各複合材
のろう付け層の表面にＳＵＳ３０４からなるステンレス
鋼パイプを乗せ、１１５０℃に加熱してろう付けを行っ
た後の、ろう付け部のフィレット（面取り）形状によっ
て評価を行った。Further, the wettability of the brazing material was evaluated by placing a stainless steel pipe made of SUS304 on the surface of the brazing layer of each composite material and heating at 1150 ° C. to perform brazing. The fillet (chamfer) shape was used for evaluation.
【００５２】[0052]
【表２】 [Table 2]
【００５３】表２に示すように、本発明に係るろう付け
用複合材である実施例１，２の複合材は、ステンレス鋼
条材の板厚残存率が９５％、９８％と高く、かつ、ろう
付け層の耐食性、濡れ性、及びろう付け生産性がいずれ
も良好であり、総合評価は良好であった。特に、ろう付
け層におけるステンレス鋼条材側のＮｉ層厚を厚くした
実施例２の複合材は、板厚残存率が極めて高かった。As shown in Table 2, in the composite materials of Examples 1 and 2 which are the brazing composite materials according to the present invention, the plate thickness residual ratio of the stainless steel strip is high at 95% and 98%, and The corrosion resistance, wettability, and brazing productivity of the brazing layer were all good, and the overall evaluation was good. In particular, the composite material of Example 2 in which the Ni layer thickness on the stainless steel strip side in the brazing layer was increased had a very high plate thickness residual rate.
【００５４】これに対して、比較例１の複合材は、ろう
付け層の耐食性、濡れ性、及びろう付け生産性はいずれ
も良好であるものの、ろう付け層におけるＴｉ層とステ
ンレス鋼条材が直接接触しているため、ステンレス鋼条
材に著しい侵食が生じ（板厚残存率は６５％）、総合評
価は不良であった。On the other hand, the composite material of Comparative Example 1 has good corrosion resistance, wettability and brazing productivity of the brazing layer, but the Ti layer in the brazing layer and the stainless steel strip are Since they were in direct contact, the stainless steel strip was significantly corroded (residual thickness was 65%), and the overall evaluation was poor.
【００５５】従来例１の複合材は、ろうの濡れ性及びろ
う付け生産性はいずれも良好であったものの、ろう付け
層がＣｕろう材のみで形成されるため、ろう付け層の耐
食性が悪く、総合評価は不良であった。The composite material of Conventional Example 1 had good brazing wettability and brazing productivity, but since the brazing layer was formed of only the Cu brazing material, the corrosion resistance of the brazing layer was poor. The overall evaluation was poor.
【００５６】従来例２の複合材は、ろう付け層の耐食性
及びろうの濡れ性はいずれも良好であったものの、ろう
付け層のろう材が粉末Ｎｉろう材であるため、ろう付け
生産性が悪く、総合評価は不良であった。The composite material of Conventional Example 2 had good corrosion resistance of the brazing layer and good wettability of the brazing material, but the brazing material of the brazing layer was powdered Ni brazing material, so that the brazing productivity was high. It was bad and the overall evaluation was poor.
【００５７】以上より、本発明に係るろう付け用複合材
である実施例１，２の複合材は、ろう付け時におけるス
テンレス鋼条材（基材）の侵食の割合が低く、かつ、ろ
う付け層の耐食性、ろうの濡れ性、及びろう付け生産性
がいずれも良好であることから、ろう付け層の信頼性に
優れたろう付け用複合材であることがわかる。As described above, the composite materials of Examples 1 and 2 which are the brazing composite material according to the present invention have a low rate of corrosion of the stainless steel strip (base material) during brazing and the brazing. Since the corrosion resistance of the layer, the wettability of the brazing material, and the brazing productivity are all good, it can be seen that the brazing composite material has excellent brazing layer reliability.
【００５８】[0058]
【発明の効果】以上要するに本発明によれば、次のよう
な優れた効果を発揮する。
（１） ろう付け特性が良好で、かつ、ろう付け時にお
ける基材の侵食の割合が低いろう付け用複合材を得るこ
とができる。
（２） 接合部の信頼性が良好で、製造コストが安価な
ろう付け製品を得ることができる。In summary, according to the present invention, the following excellent effects are exhibited. (1) It is possible to obtain a brazing composite material having good brazing characteristics and having a low base material erosion rate during brazing. (2) It is possible to obtain a brazed product having a good joint reliability and a low manufacturing cost.
【図１】本発明に係るろう付用複合材の第１実施形態の
断面図である。FIG. 1 is a cross-sectional view of a first embodiment of a brazing composite material according to the present invention.
【図２】図１の第１変形例を示す断面図である。FIG. 2 is a sectional view showing a first modification of FIG.
【図３】図１の第２変形例を示す断面図である。FIG. 3 is a sectional view showing a second modification of FIG.
【図４】図１の第３変形例を示す断面図である。FIG. 4 is a sectional view showing a third modification of FIG.
１０，２０，３０，４０ ろう付け用複合材 １１，４１ 基材 １２，２２ 第１Ｎｉ又はＮｉ合金層 １３ Ｔｉ又はＴｉ合金層 １４ 第２Ｎｉ又はＮｉ合金層 １５，２５ ろう付け層 10, 20, 30, 40 Brazing composite material 11,41 Base material 12,22 First Ni or Ni alloy layer 13 Ti or Ti alloy layer 14 Second Ni or Ni alloy layer 15,25 Brazing layer
───────────────────────────────────────────────────── フロントページの続き (72)発明者 佐川 英之 東京都千代田区大手町一丁目６番１号 日 立電線株式会社内 (72)発明者 青山 正義 東京都千代田区大手町一丁目６番１号 日 立電線株式会社内 (72)発明者 白井 枢覚 東京都千代田区大手町一丁目６番１号 日 立電線株式会社内 ─────────────────────────────────────────────────── ─── Continued front page (72) Inventor Hideyuki Sagawa 1-6-1, Otemachi, Chiyoda-ku, Tokyo Standing Wire Co., Ltd. (72) Inventor Masayoshi Aoyama 1-6-1, Otemachi, Chiyoda-ku, Tokyo Standing Wire Co., Ltd. (72) Inventor Shirai Kaku 1-6-1, Otemachi, Chiyoda-ku, Tokyo Standing Wire Co., Ltd.
Claims (5)
う付け用複合材において、上記基材表面に、基材側から
順に第１Ｎｉ又はＮｉ合金層、Ｔｉ又はＴｉ合金層、及
び第２Ｎｉ又はＮｉ合金層の三層からなるろう付け層を
形成したことを特徴とするろう付け用複合材。1. A brazing composite material having a brazing layer formed on the surface of a base material, wherein a first Ni or Ni alloy layer, a Ti or Ti alloy layer, and a first Ni or Ni alloy layer are formed on the base material surface in this order from the base material side. A brazing composite material having a brazing layer formed of three layers of 2Ni or Ni alloy layers.
ともＰを０．０２〜１０ｗｔ％含有するＮｉ−Ｐ合金で
形成した請求項１記載のろう付け用複合材。2. The brazing composite material according to claim 1, wherein the second Ni or Ni alloy layer is formed of a Ni—P alloy containing at least 0.02 to 10 wt% of P.
第２Ｎｉ又はＮｉ合金層の層厚よりも厚く形成した請求
項１又は２記載のろう付け用複合材。3. The layer thickness of the first Ni or Ni alloy layer,
The brazing composite material according to claim 1 or 2, wherein the brazing composite material is formed thicker than the second Ni or Ni alloy layer.
求項１から３いずれかに記載のろう付け用複合材。4. The brazing composite material according to claim 1, wherein the base material is formed of stainless steel.
け用複合材を用いて接合したことを特徴とするろう付け
用複合材を用いたろう付け製品。5. A brazing product using a brazing composite material, which is joined by using the brazing composite material according to claim 1.
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|---|---|---|---|
| JP2001312795A JP3814179B2 (en) | 2001-10-10 | 2001-10-10 | Brazing composite material and brazing product using the same |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001312795A JP3814179B2 (en) | 2001-10-10 | 2001-10-10 | Brazing composite material and brazing product using the same |
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| Publication Number | Publication Date |
|---|---|
| JP2003117686A true JP2003117686A (en) | 2003-04-23 |
| JP3814179B2 JP3814179B2 (en) | 2006-08-23 |
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|---|---|---|---|---|
| WO2005117493A1 (en) * | 2004-05-27 | 2005-12-08 | Kyocera Corporation | Ceramic heater, and oxygen sensor and hair iron using the ceramic heater |
| JP2006175506A (en) * | 2004-12-24 | 2006-07-06 | Hitachi Cable Ltd | Clad material for brazing, method of brazing with it, and brazed product |
| JP2006334605A (en) * | 2005-05-31 | 2006-12-14 | Hitachi Cable Ltd | Brazing filler metal, and brazed product using the same |
| GB2442614A (en) * | 2004-05-27 | 2008-04-09 | Kyocera Corp | Brazing leads to a ceramic heater assembly |
| JP2008212948A (en) * | 2007-02-28 | 2008-09-18 | Hitachi Cable Ltd | Composite material for brazing, and brazed product using the same |
| JP2008238188A (en) * | 2007-03-26 | 2008-10-09 | Hitachi Cable Ltd | Composite material for brazing, and brazed product using the same |
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|---|---|---|---|---|
| WO2005117493A1 (en) * | 2004-05-27 | 2005-12-08 | Kyocera Corporation | Ceramic heater, and oxygen sensor and hair iron using the ceramic heater |
| GB2442614A (en) * | 2004-05-27 | 2008-04-09 | Kyocera Corp | Brazing leads to a ceramic heater assembly |
| GB2442614B (en) * | 2004-05-27 | 2008-05-21 | Kyocera Corp | Ceramic heater and oxygen sensor and hair iron using the ceramic heater |
| GB2429892B (en) * | 2004-05-27 | 2008-05-21 | Kyocera Corp | Ceramic heater,and oxygen sensor and hair iron using the ceramic heater |
| JP2012253040A (en) * | 2004-05-27 | 2012-12-20 | Kyocera Corp | Ceramic heater and hair iron using the same |
| JP2006175506A (en) * | 2004-12-24 | 2006-07-06 | Hitachi Cable Ltd | Clad material for brazing, method of brazing with it, and brazed product |
| JP4492342B2 (en) * | 2004-12-24 | 2010-06-30 | 日立電線株式会社 | Brazing clad material, brazing method using the same, and brazed product |
| JP2006334605A (en) * | 2005-05-31 | 2006-12-14 | Hitachi Cable Ltd | Brazing filler metal, and brazed product using the same |
| JP2008212948A (en) * | 2007-02-28 | 2008-09-18 | Hitachi Cable Ltd | Composite material for brazing, and brazed product using the same |
| JP2008238188A (en) * | 2007-03-26 | 2008-10-09 | Hitachi Cable Ltd | Composite material for brazing, and brazed product using the same |
| JP2015127736A (en) * | 2013-12-27 | 2015-07-09 | キヤノン株式会社 | Elastic roller manufacturing method and electron beam irradiation apparatus |
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