JP4821503B2 - Brazing composite material and brazing product using the same - Google Patents
Brazing composite material and brazing product using the same Download PDFInfo
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- JP4821503B2 JP4821503B2 JP2006227810A JP2006227810A JP4821503B2 JP 4821503 B2 JP4821503 B2 JP 4821503B2 JP 2006227810 A JP2006227810 A JP 2006227810A JP 2006227810 A JP2006227810 A JP 2006227810A JP 4821503 B2 JP4821503 B2 JP 4821503B2
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Description
本発明は、ろう付けの作業性を向上させ、かつ、耐熱性と耐食性を有したろう付け用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り、特に、熱交換器（排ガス再循環装置（ＥＧＲ）用クーラや燃料電池改質器用クーラなど）および燃料電池用部材のろう付け用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。 The present invention relates to a brazing composite material having improved workability of brazing and having heat resistance and corrosion resistance, and a brazing product using the same, and in particular, a heat exchanger (exhaust gas recirculation device ( EGR) coolers, fuel cell reformer coolers, etc.) and fuel cell member brazing composite materials and brazed products using the same.
自動車用オイルクーラの接合材として、ろう付け用ステンレス基クラッド材が使用されている。これは、ステンレス鋼板の片面、或いは両面にろう材としての機能をもつ銅がクラッドされている。また、ステンレス鋼や、ニッケル基又はコバルト基合金などの部品のろう付け材として、接合部の耐食性に優れる各種ニッケルろう材に、Ｎｉ、Ｃｒ、Ｎｉ−Ｃｒ合金の内から選ばれた金属粉末を４ｗｔ％〜３０ｗｔ％添加して構成されるＮｉろう材が提案されている。 Stainless steel clad material for brazing is used as a joining material for oil coolers for automobiles. In this case, copper having a function as a brazing material is clad on one side or both sides of a stainless steel plate. In addition, as a brazing material for parts such as stainless steel and nickel-based or cobalt-based alloys, various kinds of nickel brazing materials having excellent corrosion resistance at joints, metal powders selected from Ni, Cr, Ni-Cr alloys are used. A Ni brazing material constituted by adding 4 wt% to 30 wt% has been proposed.
また、高耐食性を有するろう材として、ＪＩＳ規格に準ずる組成を持つＮｉ、Ｃｒを主成分とするアモルファス箔形状のＮｉろうがある。 Further, as a brazing material having high corrosion resistance, there are Ni brazing having an amorphous foil shape mainly composed of Ni and Cr having a composition conforming to JIS standards.
自動車用オイルクーラの接合材としてのろう付け用ステンレス基クラッド材は、ろう材の機能を持つ銅が、ステンレス鋼板の片面あるいは両面にクラッドされている。オイルクーラに、このろう付け用ステンレス基クラッド材を使用した場合、ろう材としての銅は使用上の耐熱性及び耐食性に全く問題はない。 In a brazing stainless steel base clad material as a joining material of an oil cooler for automobiles, copper having a brazing material function is clad on one side or both sides of a stainless steel plate. When this stainless steel clad material for brazing is used for an oil cooler, copper as a brazing material has no problem in heat resistance and corrosion resistance in use.
しかしながら、このろう付け用ステンレス基クラッド材を、燃料電池用熱交換器、或いはＥＧＲ（Exhaust Gas Recirculation：排ガス再循環装置）クーラ接合用など、耐熱・耐食環境下（高温・腐食性環境下）でろう材として使用した場合、耐熱性及び耐食性に著しい問題が生じる。すなわち、燃料電池用熱交換器やＥＧＲクーラ内には、高温かつ腐食性の高い溶液あるいは排気ガスが循環されるため、従来の銅ろう材においては、耐熱性及び耐食性が十分でなく使用ができない。 However, this stainless steel clad material for brazing is used in heat and corrosion resistant environments (high temperature and corrosive environments) such as fuel cell heat exchangers or EGR (Exhaust Gas Recirculation) cooler joints. When used as a brazing material, significant problems arise in heat resistance and corrosion resistance. That is, since a high-temperature and highly corrosive solution or exhaust gas is circulated in the fuel cell heat exchanger and the EGR cooler, the conventional copper brazing material has insufficient heat resistance and corrosion resistance and cannot be used. .
特許文献２に記載されている粉末Ｎｉろう材、及びＪＩＳに記載のニッケルろう材は、粉末状であるため、接合部毎に粉末ろう材を添付（配置）する作業が必要で多大な労力を費やし、製品の生産性が著しく低く、高コストな製品とならざるを得ない。また、粉末ろう材は、基材に塗布するために有機系のバインダを使用するので、バインダの蒸発工程が必要となる他、バインダの蒸発による異臭発生、ろう付け炉内の汚染の問題が生じる。 Since the powder Ni brazing material described in Patent Document 2 and the nickel brazing material described in JIS are in a powder form, it is necessary to attach (arrange) the powder brazing material for each joint, and a great deal of labor is required. Expensive, product productivity is remarkably low, and must be a high-cost product. In addition, the powder brazing material uses an organic binder to be applied to the base material, so that a binder evaporation step is required, and there is a problem of generation of a strange odor due to the evaporation of the binder and contamination in the brazing furnace. .
また、市販のアモルファス箔ニッケルろう材は脆いため、加工及びろう付け組み立て時の取り扱いが難しく、加工コストが高いという問題があった。 Moreover, since the commercially available amorphous foil nickel brazing material is fragile, it is difficult to handle during processing and brazing assembly, and the processing cost is high.
そこで本発明の目的は、取扱い性に優れ、かつ、所望の耐熱性及び耐食性を有するろう付け用複合材及びそれを用いたろう付け製品を提供することにある。 Accordingly, an object of the present invention is to provide a brazing composite material having excellent handleability and having desired heat resistance and corrosion resistance, and a brazed product using the same.
上記目的を達成するために、請求項１の発明は、ろう材の一成分である金属Ａと、上記ろう材の残りの成分である金属Ｂ及び金属Ｃとを複合一体化してなり、それらを複合させたものの層構造が対称構造を有し、上記層構造が中心材としての金属Ｃの層を、厚さの等しい２枚の金属Ｂの層で挟み、さらにその上を厚さの等しい２枚の金属Ａの層で挟んだ５層構造からなり、上記金属Ａが鉄−ニッケル合金で構成され、上記金属Ｂがチタン或いはチタン合金で構成され、上記金属Ｃがニッケルで構成され、上記ろう材中のＦｅ濃度が２０〜５０ｍａｓｓ％であることを特徴とするろう付け用複合材である。 To achieve the above object, the invention of claim 1, and the metal A is a component of the brazing material, and a metal B and the metal C is a remaining component of the brazing material becomes complexed integrated them layer structure but complexed will have a symmetrical structure, the layer structure is a layer of metal C as a central material, sandwiched between the two layers of metal B equal thickness equals further on the thickness of the 2 The metal A is made of an iron-nickel alloy, the metal B is made of titanium or a titanium alloy, the metal C is made of nickel, It is a composite material for brazing , wherein the Fe concentration in the material is 20 to 50 mass% .
請求項２の発明は、請求項１に記載のろう付け用複合材を用い、組み立てられた被ろう付け材同士をろう付け接合したことを特徴とするろう付け製品である。 The invention of claim 2 is a brazed product characterized by using the composite material for brazing according to claim 1 and brazing and joining the brazed materials assembled together.
本発明によれば、取扱い性に優れ、かつ、所望の耐熱性及び耐食性を有するろう付け用複合材を得ることができる。 ADVANTAGE OF THE INVENTION According to this invention, the composite material for brazing which is excellent in handleability and has desired heat resistance and corrosion resistance can be obtained.
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。 DESCRIPTION OF EXEMPLARY EMBODIMENTS Hereinafter, a preferred embodiment of the invention will be described with reference to the accompanying drawings.
前述した目的を達成するために、本発明者らが鋭意研究し、耐熱性、耐腐食性を有し、さらにろう付け作業時のコストを低減させるろう付け用複合材の構成について種々検討した結果、ろう材としての材料を所定の構成及び組成に選定したろう付け用複合材を完成するに至った。 In order to achieve the above-mentioned object, the present inventors have intensively studied and variously examined the composition of the composite material for brazing which has heat resistance and corrosion resistance and further reduces the cost during the brazing operation. The present inventors have completed a brazing composite material in which a material as a brazing material is selected to have a predetermined configuration and composition.
すなわち、本発明の好適一実施の形態に係るろう付け用複合材は、ろう材の一成分である金属Ａと、ろう材のもう一方の成分であり、少なくとも一種の金属からなる金属Ｂを複合一体化してなるものであり、具体的には、金属Ａ，Ｂの各層を積層、複合一体化してなるものである。 That is, the composite material for brazing according to a preferred embodiment of the present invention is composed of a composite of metal A, which is one component of the brazing material, and metal B, which is the other component of the brazing material, and is composed of at least one metal. Specifically, the layers of the metals A and B are laminated and combined and integrated.
この積層体の層構造は対称構造を有しており、中心材としての金属Ｂの層を、厚さの等しい２枚の金属Ａの層で挟んだ３層構造となっている。金属Ａ，Ｂの組み合わせは、例えば、図１に示すように、金属ＡとしてＦｅ−Ｎｉ合金の層１、金属ＢとしてＴｉ（又はＴｉ合金）の層２が挙げられ、積層構造がＦｅ−Ｎｉ合金層１／Ｔｉ層２／Ｆｅ−Ｎｉ合金層１の３層構造とされる。 The layer structure of this laminated body has a symmetric structure, and has a three-layer structure in which a metal B layer as a central member is sandwiched between two metal A layers having the same thickness. As shown in FIG. 1, the combination of metals A and B includes, for example, a layer 1 of Fe—Ni alloy as metal A, and a layer 2 of Ti (or Ti alloy) as metal B, and the laminated structure is Fe—Ni. A three-layer structure of alloy layer 1 / Ti layer 2 / Fe—Ni alloy layer 1 is adopted.
ろう付け用複合材に、リンを０．０２〜１０ｍａｓｓ％程度添加すると、ろうの湯流れ性や耐酸化性が更に向上する。リンの添加量が増えると（１０ｍａｓｓ％よりも多いと）、接合される基材（被ろう付け材）の種類によっては、強度低下が発生する。好ましいリンの添加量の範囲は０．０２〜５．０ｍａｓｓ％である。 When phosphorus is added to the brazing composite material in an amount of about 0.02 to 10 mass%, the brazing metal flowability and oxidation resistance are further improved. When the amount of phosphorus added increases (greater than 10 mass%), the strength decreases depending on the type of base material to be joined (the material to be brazed). The range of the preferable addition amount of phosphorus is 0.02 to 5.0 mass%.
また、ろう付け用複合材に、銅、マンガンを含ませることで湯流れ性は更に向上し、また、アルミ、クロム、シリコンを含ませることで耐酸化性を向上させることができる。 Moreover, the hot metal flowability is further improved by including copper and manganese in the brazing composite material, and the oxidation resistance can be improved by including aluminum, chromium and silicon.
ステンレス鋼をはじめとする鉄系合金の基材（以下、Ｆｅ基材という）のろう付けを行う場合、ろう付け用複合材中にＦｅを添加することが望ましい。これは、Ｆｅを添加することで、Ｆｅ基材の食われを低減することができるためである。Ｆｅの添加量は、５０ｍａｓｓ％以下が望ましく、好ましくは２０〜５０ｍａｓｓ％とされる。これは、Ｆｅ添加量が５０ｍａｓｓ％を超えると、耐食性及びろうの湯流れ性が低下するためである。 When brazing a base material of an iron-based alloy such as stainless steel (hereinafter referred to as an Fe base material), it is desirable to add Fe to the brazing composite material. This is because the biting of the Fe base material can be reduced by adding Fe. The amount of Fe added is desirably 50 mass% or less, and preferably 20 to 50 mass%. This is because when the amount of Fe added exceeds 50 mass%, the corrosion resistance and the flowability of brazing metal decrease.
本実施の形態においては、図１に示したように、ろう付け用複合材が３層構造の場合を例に挙げて説明を行ったが、ろう付け用複合材は、５層構造、或いは６層以上の層構造であってもよい。例えば、５層構造の場合、図２に示すように、金属ＡとしてＦｅ−Ｎｉ合金の層１、金属ＢとしてＴｉ（又はＴｉ合金）の層２、金属ＣとしてＮｉの層３が挙げられ、積層構造がＦｅ−Ｎｉ合金層１／Ｔｉ層２／Ｎｉ層３／Ｔｉ層２／Ｆｅ−Ｎｉ合金層１とされる。また、金属の種類としては、金属Ａ，Ｂ，Ｃの３種に限らず、金属Ａ，Ｂ，Ｃ，Ｄ…と４種以上を用いてもよい。 In the present embodiment, as shown in FIG. 1, the case where the brazing composite material has a three-layer structure has been described as an example. However, the brazing composite material has a five-layer structure, or 6 It may be a layer structure of more than one layer. For example, in the case of a five-layer structure, as shown in FIG. 2, a layer 1 of Fe-Ni alloy as the metal A, a layer 2 of Ti (or Ti alloy) as the metal B, and a layer 3 of Ni as the metal C, The laminated structure is Fe—Ni alloy layer 1 / Ti layer 2 / Ni layer 3 / Ti layer 2 / Fe—Ni alloy layer 1. Moreover, as a kind of metal, you may use not only three types of metal A, B, C, but metal A, B, C, D ... and 4 types or more.
また、本実施の形態においては、図１に示したように、ろう付け用複合材が箔状の積層体である場合を例に挙げて説明を行ったが、ろう付け用複合材は、棒状又はワイヤ状であってもよい。例えば、図３に示すように、金属ＢとしてＴｉ（又はＴｉ合金）のワイヤ５、金属ＡとしてＦｅ−Ｎｉ合金の被覆層６が挙げられ、金属Ｂの周りを金属Ａで被覆、複合一体化してなり、それらの複合体の層構造が対称構造（ワイヤ中心から同心状に被覆層６を配置した構造）とされる。また、図４に示すように、金属ＣとしてＮｉのワイヤ７、金属ＢとしてＴｉ（又はＴｉ合金）の被覆層８、金属ＡとしてＦｅ−Ｎｉ合金の被覆層６が挙げられ、金属Ｃの周りを金属Ｂで被覆し、さらにその上を金属Ａで被覆、複合一体化してなり、それらの複合体の層構造を対称構造（ワイヤ中心から同心状に被覆層８，６を配置した構造）とされる。 Further, in the present embodiment, as shown in FIG. 1, the case where the brazing composite material is a foil-like laminate has been described as an example. However, the brazing composite material is a rod-shaped composite material. Or it may be a wire shape. For example, as shown in FIG. 3, the metal B may be a Ti (or Ti alloy) wire 5, and the metal A may be a Fe—Ni alloy coating layer 6. Thus, the layer structure of these composites is a symmetric structure (a structure in which the coating layer 6 is arranged concentrically from the wire center). Further, as shown in FIG. 4, a Ni wire 7 as the metal C, a Ti (or Ti alloy) coating layer 8 as the metal B, and a Fe—Ni alloy coating layer 6 as the metal A can be cited. Is coated with metal B, and further is coated with metal A and combined and integrated, and the layer structure of these composites is symmetrical (structure in which coating layers 8 and 6 are arranged concentrically from the center of the wire). Is done.
所定の被ろう付け材同士を組み立ててなる組み立て材において、所望のろう付け接合箇所に、上述した本実施の形態に係るろう付け用複合材を配置し、ろう付けすることで、被ろう付け材同士がろう付け接合部を介してろう付けされ、本実施の形態に係るろう付け製品が得られる。 In an assembly material obtained by assembling predetermined brazing materials, the brazing composite material according to the present embodiment described above is disposed and brazed at a desired brazing joint location, thereby brazing the material. The parts are brazed via a brazed joint, and the brazed product according to the present embodiment is obtained.
次に、本実施の形態の作用を説明する。 Next, the operation of the present embodiment will be described.
ろう付け用複合材には、基材付き（有り）のものと、基材レス（無し）のものとがあるが、基材レスの場合では、基材付きと比較して、「ろう部の組成均一性」がろう付け層の積層構造に依存する度合いが高い。この「ろう部の組成均一性」は、ろう付け特性を左右する特性の１つである。 There are two types of composite materials for brazing: those with a base material (existing) and those without a base material (with no base material). The degree of “composition uniformity” is highly dependent on the laminated structure of the brazing layer. This “composition uniformity of the brazing part” is one of the characteristics that influence the brazing characteristics.
よって、基材レスのろう付け用複合材である本実施の形態に係るろう付け用複合材は、中心材としての金属Ｂの層を、厚さの等しい２枚の金属Ａの層で挟み、積層体の層構造（各層の組成及び厚さ）を対称構造としている。これにより、異種金属Ａ，Ｂ間の反応（拡散反応）が金属Ａと金属Ｂの各界面において均一に起こり、ろう材の溶融、流れが均一となる。その結果、ろう付け後におけるろう部（ろう付け接合部）の組成が均一となり、良好な耐熱性及び耐食性が得られる。 Therefore, the brazing composite material according to the present embodiment, which is a baseless brazing composite material, sandwiches the metal B layer as the central material between two metal A layers having the same thickness, The layer structure (composition and thickness of each layer) of the laminate is a symmetric structure. Thereby, the reaction (diffusion reaction) between the different metals A and B occurs uniformly at each interface between the metal A and the metal B, and the melting and flow of the brazing material become uniform. As a result, the composition of the brazed portion (brazed joint) after brazing becomes uniform, and good heat resistance and corrosion resistance can be obtained.
更に、このろう付け用複合材は、自由な形状、大きさに加工が可能であるため、一度目のろう付け後、ろう付け接合部における未接合の箇所、或いはろう材が不足している箇所にこのろう付け用複合材を配置し、補修用ろう付け材として二度目のろう付けに利用することができ、補修用途の部材としても利用価値が高い。 Furthermore, since this brazing composite material can be processed into a free shape and size, after brazing for the first time, an unjoined place in the brazed joint or a place where the brazing material is insufficient. This brazing composite material can be used for the second brazing as a brazing material for repairing, and it is highly useful as a member for repairing purposes.
本実施の形態に係るろう付け用複合材は、ＥＧＲ用クーラや燃料電池改質器用クーラなどの熱交換器や、燃料電池用部材のろう材のみに限定されるものではなく、高耐食性が要求される接合分野においては、その用途が限定されないのは言うまでもない。 The brazing composite material according to the present embodiment is not limited to heat exchangers such as EGR coolers and fuel cell reformer coolers, and brazing materials for fuel cell members, and requires high corrosion resistance. Needless to say, the application is not limited in the joining field.
以下、本発明の実施例を説明する。
（参考例１）
Ｆｅ−７０ｍａｓｓ％Ｎｉ条材（厚さ０．６１ｍｍ）、Ｔｉ条材（厚さ１．０ｍｍ）、Ｆｅ−７０ｍａｓｓ％Ｎｉ条材（厚さ０．６１ｍｍ）を圧延法によりクラッドし、ろう付け用複合材（Ｆｅ−Ｎｉ／Ｔｉ／Ｆｅ−Ｎｉ）を作製した。その後、このろう付け用複合材に圧延を繰り返し、全体の合計厚さを５０μｍとした。このろう付け用複合材をステンレス鋼板上に設置し、更にその上にステンレス鋼パイプを載せた後、１２００℃の管状炉で加熱し、ろう付け特性を評価した。
（参考例２）
Ｎｉ条材（厚さ０．０９ｍｍ）、Ｃｕ条材（厚さ１．０２ｍｍ）、Ｎｉ条材（厚さ０．０９ｍｍ）を圧延法によりクラッドし、ろう付け用複合材（Ｎｉ／Ｃｕ／Ｎｉ）を作製した。その後、このろう付け用複合材に圧延を繰り返し、全体の合計厚さを５０μｍとした。このろう付け用複合材をステンレス鋼板上に設置し、更にその上にステンレス鋼パイプを載せた後、１２００℃の管状炉で加熱し、ろう付け特性を評価した。
（実施例１）
インバー（登録商標）条材（厚さ０．３６ｍｍ）、Ｔｉ条材（厚さ０．５ｍｍ）、Ｎｉ条材（厚さ０．５２ｍｍ）、Ｔｉ条材（厚さ０．５ｍｍ）、インバー条材（厚さ０．３６ｍｍ）を圧延法によりクラッドし、ろう付け用複合材（インバー／Ｔｉ／Ｎｉ／Ｔｉ／インバー）を作製した。その後、このろう付け用複合材に圧延を繰り返し、全体の合計厚さを５０μｍとした。このろう付け用複合材をステンレス鋼板上に設置し、更にその上にステンレス鋼パイプを載せた後、１２００℃の管状炉で加熱し、ろう付け特性を評価した。
（実施例２）
インバー（登録商標）条材（厚さ１．１３ｍｍ）、Ｔｉ条材（厚さ０．５ｍｍ）、Ｎｉ条材（厚さ０．０６ｍｍ）、Ｔｉ条材（厚さ０．５ｍｍ）、インバー条材（厚さ１．１３ｍｍ）を圧延法によりクラッドし、ろう付け用複合材（インバー／Ｔｉ／Ｎｉ／Ｔｉ／インバー）を作製した。その後、このろう付け用複合材に圧延を繰り返し、全体の合計厚さを５０μｍとした。このろう付け用複合材をステンレス鋼板上に設置し、更にその上にステンレス鋼パイプを載せた後、１２００℃の管状炉で加熱し、ろう付け特性を評価した。
（比較例１）
Ｆｅ−７０ｍａｓｓ％Ｎｉ条材（厚さ０．７２ｍｍ）、Ｔｉ条材（厚さ１．０ｍｍ）、Ｆｅ−７４ｍａｓｓ％Ｎｉ条材（厚さ０．５ｍｍ）を圧延法によりクラッドし、ろう付け用複合材（Ｆｅ−Ｎｉ／Ｔｉ／Ｆｅ−Ｎｉ）を作製した。その後、このろう付け用複合材に圧延を繰り返し、全体の合計厚さを５０μｍとした。このろう付け用複合材をステンレス鋼板上に設置し、更にその上にステンレス鋼パイプを載せた後、１２００℃の管状炉で加熱し、ろう付け特性を評価した。
（比較例２）
Ｎｉ条材（厚さ０．１３ｍｍ）、Ｃｕ条材（厚さ１．０２ｍｍ）、Ｎｉ条材（厚さ０．０５ｍｍ）を圧延法によりクラッドし、ろう付け用複合材（Ｎｉ／Ｃｕ／Ｎｉ）を作製した。その後、このろう付け用複合材に圧延を繰り返し、全体の合計厚さを５０μｍとした。このろう付け用複合材をステンレス鋼板上に設置し、更にその上にステンレス鋼パイプを載せた後、１２００℃の管状炉で加熱し、ろう付け特性を評価した。
（比較例３）
インバー（登録商標）条材（厚さ０．７２ｍｍ）、Ｔｉ条材（厚さ１．０ｍｍ）、Ｎｉ条材（厚さ０．５２ｍｍ）を圧延法によりクラッドし、ろう付け用複合材（インバー／Ｔｉ／Ｎｉ）を作製した。その後、このろう付け用複合材に圧延を繰り返し、全体の合計厚さを５０μｍとした。このろう付け用複合材をステンレス鋼板上に設置し、更にその上にステンレス鋼パイプを載せた後、１２００℃の管状炉で加熱し、ろう付け特性を評価した。
（比較例４）
インバー（登録商標）条材（厚さ０．３６ｍｍ）、Ｔｉ条材（厚さ１．０ｍｍ）、Ｎｉ条材（厚さ０．５２ｍｍ）、インバー条材（厚さ０．３６ｍｍ）を圧延法によりクラッドし、ろう付け用複合材（インバー／Ｔｉ／Ｎｉ／インバー）を作製した。その後、このろう付け用複合材に圧延を繰り返し、全体の合計厚さを５０μｍとした。このろう付け用複合材をステンレス鋼板上に設置し、更にその上にステンレス鋼パイプを載せた後、１２００℃の管状炉で加熱し、ろう付け特性を評価した。
（比較例５）
インバー（登録商標）条材（厚さ１．３６ｍｍ）、Ｔｉ条材（厚さ０．５ｍｍ）、Ｎｉ条材（厚さ０．０３ｍｍ）、Ｔｉ条材（厚さ０．５ｍｍ）、インバー条材（厚さ１．０ｍｍ）を圧延法によりクラッドし、ろう付け用複合材（インバー／Ｔｉ／Ｎｉ／Ｔｉ／インバー）を作製した。その後、このろう付け用複合材に圧延を繰り返し、全体の合計厚さを５０μｍとした。このろう付け用複合材をステンレス鋼板上に設置し、更にその上にステンレス鋼パイプを載せた後、１２００℃の管状炉で加熱し、ろう付け特性を評価した。
（従来例１）
ステンレス鋼板上に、厚さ５０μｍに圧延したＣｕ箔（ろう材）を設置し、さらにその上にステンレス鋼パイプを載せた後、１１２０℃の管状炉で加熱し、ろう付け特性を評価した。
（従来例２）
ステンレス鋼板の片面に、ＪＩＳ規格のＢＮｉ−５に相当する市販の粉末Ｎｉろう材を合成樹脂バインダで溶いたものを塗布し、さらにその上にステンレス鋼パイプを載せた後、１１８０℃の管状炉で加熱し、ろう付け特性を評価した。
（従来例３）
ステンレス鋼板の片面に、ＪＩＳ規格のＢＮｉ−５に相当する市販のアモルファス箔Ｎｉろう材を設置し、さらにその上にステンレス鋼パイプを載せた後、１１８０℃の管状炉で加熱し、ろう付け特性を評価した。
Examples of the present invention will be described below.
( Reference Example 1 )
Fe-70 mass% Ni strip (thickness 0.61 mm), Ti strip (thickness 1.0 mm), and Fe-70 mass% Ni strip (thickness 0.61 mm) are clad by a rolling method and used for brazing A composite material (Fe—Ni / Ti / Fe—Ni) was produced. Thereafter, the brazing composite material was repeatedly rolled to a total thickness of 50 μm. This brazing composite material was placed on a stainless steel plate, and a stainless steel pipe was further placed thereon, and then heated in a tubular furnace at 1200 ° C. to evaluate the brazing characteristics.
( Reference Example 2 )
A Ni strip (thickness 0.09 mm), a Cu strip (thickness 1.02 mm), and a Ni strip (thickness 0.09 mm) are clad by a rolling method, and a brazing composite (Ni / Cu / Ni) ) Was produced. Thereafter, the brazing composite material was repeatedly rolled to a total thickness of 50 μm. This brazing composite material was placed on a stainless steel plate, and a stainless steel pipe was further placed thereon, and then heated in a tubular furnace at 1200 ° C. to evaluate the brazing characteristics.
( Example 1 )
Invar (registered trademark) strip (thickness 0.36 mm), Ti strip (thickness 0.5 mm), Ni strip (thickness 0.52 mm), Ti strip (thickness 0.5 mm), Invar strip The material (thickness 0.36 mm) was clad by a rolling method to produce a brazing composite material (Invar / Ti / Ni / Ti / Invar). Thereafter, the brazing composite material was repeatedly rolled to a total thickness of 50 μm. This brazing composite material was placed on a stainless steel plate, and a stainless steel pipe was further placed thereon, and then heated in a tubular furnace at 1200 ° C. to evaluate the brazing characteristics.
( Example 2 )
Invar (registered trademark) strip (thickness 1.13 mm), Ti strip (thickness 0.5 mm), Ni strip (thickness 0.06 mm), Ti strip (thickness 0.5 mm), Invar strip The material (thickness 1.13 mm) was clad by a rolling method to produce a brazing composite material (Invar / Ti / Ni / Ti / Invar). Thereafter, the brazing composite material was repeatedly rolled to a total thickness of 50 μm. This brazing composite material was placed on a stainless steel plate, and a stainless steel pipe was further placed thereon, and then heated in a tubular furnace at 1200 ° C. to evaluate the brazing characteristics.
(Comparative Example 1)
Fe-70 mass% Ni strip (thickness 0.72 mm), Ti strip (thickness 1.0 mm), Fe-74 mass% Ni strip (thickness 0.5 mm) are clad by a rolling method for brazing A composite material (Fe—Ni / Ti / Fe—Ni) was produced. Thereafter, the brazing composite material was repeatedly rolled to a total thickness of 50 μm. This brazing composite material was placed on a stainless steel plate, and a stainless steel pipe was further placed thereon, and then heated in a tubular furnace at 1200 ° C. to evaluate the brazing characteristics.
(Comparative Example 2)
A Ni strip (thickness 0.13 mm), a Cu strip (thickness 1.02 mm), and a Ni strip (thickness 0.05 mm) are clad by a rolling method to form a brazing composite (Ni / Cu / Ni). ) Was produced. Thereafter, the brazing composite material was repeatedly rolled to a total thickness of 50 μm. This brazing composite material was placed on a stainless steel plate, and a stainless steel pipe was further placed thereon, and then heated in a tubular furnace at 1200 ° C. to evaluate the brazing characteristics.
(Comparative Example 3)
Invar (registered trademark) strip (thickness 0.72 mm), Ti strip (thickness 1.0 mm), and Ni strip (thickness 0.52 mm) are clad by a rolling method to form a brazing composite (invar / Ti / Ni). Thereafter, the brazing composite material was repeatedly rolled to a total thickness of 50 μm. This brazing composite material was placed on a stainless steel plate, and a stainless steel pipe was further placed thereon, and then heated in a tubular furnace at 1200 ° C. to evaluate the brazing characteristics.
(Comparative Example 4)
Invar (registered trademark) strip (thickness 0.36 mm), Ti strip (thickness 1.0 mm), Ni strip (thickness 0.52 mm), Invar strip (thickness 0.36 mm) Then, a brazing composite material (Invar / Ti / Ni / Invar) was produced. Thereafter, the brazing composite material was repeatedly rolled to a total thickness of 50 μm. This brazing composite material was placed on a stainless steel plate, and a stainless steel pipe was further placed thereon, and then heated in a tubular furnace at 1200 ° C. to evaluate the brazing characteristics.
(Comparative Example 5)
Invar (registered trademark) strip (thickness 1.36 mm), Ti strip (thickness 0.5 mm), Ni strip (thickness 0.03 mm), Ti strip (thickness 0.5 mm), Invar strip The material (thickness: 1.0 mm) was clad by a rolling method to produce a brazing composite material (Invar / Ti / Ni / Ti / Invar). Thereafter, the brazing composite material was repeatedly rolled to a total thickness of 50 μm. This brazing composite material was placed on a stainless steel plate, and a stainless steel pipe was further placed thereon, and then heated in a tubular furnace at 1200 ° C. to evaluate the brazing characteristics.
(Conventional example 1)
A Cu foil (brazing material) rolled to a thickness of 50 μm was placed on a stainless steel plate, and a stainless steel pipe was placed thereon, and then heated in a tubular furnace at 1120 ° C. to evaluate brazing characteristics.
(Conventional example 2)
After applying a commercially available powdered Ni brazing filler metal equivalent to JIS standard BNi-5 with a synthetic resin binder on one side of a stainless steel plate, and further placing a stainless steel pipe thereon, a 1180 ° C. tubular furnace And the brazing properties were evaluated.
(Conventional example 3)
A commercially available amorphous foil Ni brazing material corresponding to JIS standard BNi-5 is installed on one side of a stainless steel plate, and a stainless steel pipe is placed on it, and then heated in a tubular furnace at 1180 ° C., brazing characteristics Evaluated.
また、補修用途としてのろう付けを模擬するため、参考例１のろう付けで得られたろう付け製品を基準材とし、この基準材のろう付け接合部付近に、参考例１、２、実施例１、２、比較例１〜５のろう付け用複合材をそれぞれ配置し、２度目のろう付け熱処理を行い、サンプル１〜９を作製した。これらのサンプルをろう付け一回目と同様の方法で評価した。 Further, in order to simulate brazing as a repair application, the brazed product obtained by brazing in Reference Example 1 is used as a reference material, and Reference Examples 1, 2, and Example 1 are provided in the vicinity of the brazed joint portion of the reference material. 2 and the composite materials for brazing of Comparative Examples 1 to 5 were respectively arranged and subjected to a second brazing heat treatment to prepare Samples 1 to 9. These samples were evaluated in the same manner as in the first brazing.
表１に、参考例１、２、実施例１、２及び比較例１〜５の各ろう付け用複合材、従来例１〜３の各ろう材に対して、ろうの流れ性、ろう付け後におけるろう部の組成の均一性（ろう付け一回目、２度ろう付け後）、腐食発生の有無、ろう付生産性（取扱い性）を比較し、それぞれのろう付け用複合材及びろう材の総合評価を行ったものを示す。 Table 1 shows the flowability of brazing, after brazing, for the brazing composite materials of Reference Examples 1 and 2, Examples 1 and 2 and Comparative Examples 1 to 5, and the brazing materials of Conventional Examples 1 to 3. Comparison of brazing composition uniformity (first and second brazing), presence / absence of corrosion, brazing productivity (handling), and overall composition of brazing and brazing materials It shows what was evaluated.
ここで、ろうの流れ性は、パイプろう付け部のフィレット量（ろう付け接合部へのろうの集まり量）の大きさによって評価した。ろう部の組成均一性については、ろう付け後のろう付け接合部断面のＳＥＭ−ＥＤＸを用いた成分分析及びライン分析により評価した。腐食試験は、塩素イオン、硫酸イオンを含んだ腐食性溶液中に試料を１０００ｈ浸漬し、取り出した後のろう付け部について詳細な観察を行い、腐食の発生の有無を調査した。 Here, the flowability of the brazing was evaluated by the magnitude of the fillet amount of the pipe brazing portion (the amount of brazing gathered at the brazing joint). The composition uniformity of the brazing part was evaluated by component analysis using SEM-EDX and line analysis of the cross section of the brazed joint after brazing. In the corrosion test, the sample was immersed in a corrosive solution containing chlorine ions and sulfate ions for 1000 hours, and the brazed portion after taking out was observed in detail to investigate the presence or absence of corrosion.
表１によれば、参考例１、２、実施例１、２に示す様に、対称構造を有するろう付け用複合材は、異種金属間の反応が均一であるため、ろうの流れ性に優れ、また、ろう付け後におけるろう部の組成のばらつきが小さいことがわかった。また、Ｔｉ−Ｎｉ−Ｆｅ系ろう材の場合、ろう材中のＦｅ濃度を２０〜５０ｍａｓｓ％とすることで、優れた耐食性を確保できることがわかった。さらに、参考例１、２、実施例１、２のろう付け用複合材は、全て圧延、プレスなどの加工が可能であり、また、板状であるため、ろう付け生産性にも優れていると判断できる。 According to Table 1, as shown in Reference Examples 1 and 2 and Examples 1 and 2 , the brazing composite material having a symmetric structure is excellent in the flowability of brazing because the reaction between different metals is uniform. Moreover, it was found that the variation in the composition of the brazing part after brazing was small. Moreover, in the case of a Ti—Ni—Fe brazing filler metal, it was found that excellent corrosion resistance can be secured by setting the Fe concentration in the brazing filler metal to 20 to 50 mass%. Furthermore, the brazing composite materials of Reference Examples 1 and 2 and Examples 1 and 2 can all be processed by rolling, pressing and the like, and are excellent in brazing productivity because they are plate-shaped. It can be judged.
一方、参考例１と同じろう材部組成を持つものの、ろう材部の積層構造が非対称、すなわち両最外層の層厚が異なる（ｔ1，ｔ2）比較例１の場合、異種金属間の反応が均一でないため、ろう付け接合部の位置におけるろう部の組成のばらつきが大きいことがわかった。また、比較例２に示すＣｕ−Ｎｉ系ろう材の場合でも同様に、ろう材部の積層構造が非対称であるため、ろうの流れ性が不足し、ろう部の組成均一性にも問題があることがわかった。 On the other hand, although it has the same brazing material portion composition as in Reference Example 1, the laminated structure of the brazing material portion is asymmetric, that is, the outermost layers are different in thickness (t 1 , t 2 ). Since the reaction was not uniform, it was found that the composition variation of the brazing portion at the position of the brazed joint was large. Similarly, even in the case of the Cu—Ni brazing material shown in Comparative Example 2, since the laminated structure of the brazing material part is asymmetric, the flowability of the brazing is insufficient and the composition uniformity of the brazing part is also problematic. I understood it.
比較例３，４については、実施例１と同一のろう材部組成であるものの、ろう材部の積層構造が非対称であるため、ろうの流れ性が不足し、ろう部の組成均一性にも問題があることがわかった。 For Comparative Examples 3 and 4, the brazing filler metal composition is the same as that of Example 1 , but the brazing filler metal laminate structure is asymmetric, so that the braze flowability is insufficient and the composition uniformity of the brazing filler metal is also low. I found out there was a problem.
比較例５は、ろう材部の積層構造が非対称であることに加え、Ｆｅ濃度が５０ｍａｓｓ％を超えているため、ろうの流れ性が更に悪化し、ろう部の組成均一性も悪いことがわかった。また、ろう材部のＦｅ濃度が５０ｍａｓｓ％を超えると、耐食性に問題が発生することがわかった。このことから、ろう材部のＦｅ濃度は５０ｍａｓｓ％以下であることが望ましいといえる。 Comparative Example 5 shows that in addition to the laminated structure of the brazing filler metal part being asymmetrical, the Fe concentration exceeds 50 mass%, so that the flowability of the braze is further deteriorated and the composition uniformity of the brazing part is also poor. It was. Further, it was found that when the Fe concentration in the brazing filler metal part exceeds 50 mass%, a problem occurs in the corrosion resistance. From this, it can be said that the Fe concentration in the brazing filler metal part is desirably 50 mass% or less.
補修を模擬した２度ろう付け後におけるろう部の組成の均一性の評価結果は、ろう付け一回目と同様であり、参考例１、２、実施例１、２についてのみ良好な結果を得ることができた。この結果からも、本発明のろう付け用複合材は、補修用途の利用にも優れていると判断できる。 The results of evaluation of the uniformity of the composition of the brazing part after brazing twice simulating repair are the same as the first brazing, and good results are obtained only for Reference Examples 1 and 2 and Examples 1 and 2. I was able to. Also from this result, it can be judged that the composite material for brazing of the present invention is excellent in utilization for repair purposes.
従来例１に示すＣｕ箔は、加工性、取り扱い性に優れ、比較的融点が低いため、単体でろう材として利用できるものの、耐食性試験では著しい腐食が発生し、高耐食環境下（高い腐食性環境下）での使用に耐えられないことがわかった。 The Cu foil shown in Conventional Example 1 is excellent in workability and handleability and has a relatively low melting point, so that it can be used alone as a brazing filler metal, but in the corrosion resistance test, significant corrosion occurs, and in a high corrosion resistance environment (high corrosion resistance) It was found that it cannot withstand use in the environment).
従来例２に示す粉末Ｎｉろうは、耐食性に優れているものの、粉末ろう材であることや、有機物系のバインダーを用いることなどから、生産性が著しく低下してしまう。また、この粉末Ｎｉろう材を塗布した後の状態では、加工はもとより、振動が加わるだけでろう材が基材から剥離、脱落してしまうため、取扱いが著しく難しいことがわかった。 Although the powder Ni braze shown in Conventional Example 2 is excellent in corrosion resistance, the productivity is remarkably lowered because it is a powder braze material or uses an organic binder. In addition, in the state after applying this powder Ni brazing material, it was found that the brazing material peels off from the base material only when vibration is applied as well as processing, and thus handling is extremely difficult.
従来例３に示すアモルファス箔Ｎｉろうは、耐食性に優れているものの、箔形状ではあるが非常に脆い箔であることから、取扱い性が著しく低かった。 Although the amorphous foil Ni braze shown in Conventional Example 3 is excellent in corrosion resistance, it has a foil shape but is very brittle, so that the handleability is extremely low.
１ 金属Ａの層
２ 金属Ｂの層
1 layer of metal A 2 layer of metal B
Claims (2)
上記層構造が中心材としての金属Ｃの層を、厚さの等しい２枚の金属Ｂの層で挟み、さらにその上を厚さの等しい２枚の金属Ａの層で挟んだ５層構造からなり、
上記金属Ａが鉄−ニッケル合金で構成され、上記金属Ｂがチタン或いはチタン合金で構成され、上記金属Ｃがニッケルで構成され、上記ろう材中のＦｅ濃度が２０〜５０ｍａｓｓ％であることを特徴とするろう付け用複合材。 And the metal A is a component of the brazing material, and the metal B and the metal C is a remaining component of the brazing material combined integrally, although let them composite layer structure have a symmetrical structure,
The above layer structure has a five-layer structure in which a metal C layer as a central material is sandwiched between two metal B layers having the same thickness and further sandwiched between two metal A layers having the same thickness. Become
The metal A is composed of an iron-nickel alloy, the metal B is composed of titanium or a titanium alloy, the metal C is composed of nickel, and the Fe concentration in the brazing material is 20 to 50 mass%. Composite material for brazing.
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| JP4107553B2 (en) * | 2001-06-07 | 2008-06-25 | 日立電線株式会社 | Brazing composite material and brazing product using the same |
| JP3765533B2 (en) * | 2001-10-11 | 2006-04-12 | 日立電線株式会社 | Brazing composite material and brazing product using the same |
| JP2005088071A (en) * | 2003-09-19 | 2005-04-07 | Hitachi Cable Ltd | Composite material for brazing and brazed product using the same |
| JP2005238807A (en) * | 2004-02-27 | 2005-09-08 | Makoto Suehiro | Take-up spool for calendar |
| 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 |
| JP2006334603A (en) * | 2005-05-31 | 2006-12-14 | Hitachi Cable Ltd | Composite material for brazing, and brazed product using the same |
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2006
- 2006-08-24 JP JP2006227810A patent/JP4821503B2/en not_active Expired - Fee Related
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| Publication number | Publication date |
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| JP2008049368A (en) | 2008-03-06 |
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