JP5061969B2 - Brazing composites and brazing products - Google Patents
Brazing composites and brazing products Download PDFInfo
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- JP5061969B2 JP5061969B2 JP2008058319A JP2008058319A JP5061969B2 JP 5061969 B2 JP5061969 B2 JP 5061969B2 JP 2008058319 A JP2008058319 A JP 2008058319A JP 2008058319 A JP2008058319 A JP 2008058319A JP 5061969 B2 JP5061969 B2 JP 5061969B2
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Description
本発明は、ろう付け性能、耐熱性および耐食性能の向上が図れるろう付け加工用複合材およびろう付け製品に係り、特に熱交換器（排ガス再循環装置（ＥＧＲ）用クーラや燃料電池用改質器用クーラなど）、燃料電池用部材に適するろう付け加工用複合材およびろう付け製品に関する。 The present invention relates to a brazing composite material and a brazing product capable of improving brazing performance, heat resistance, and corrosion resistance, and in particular, a heat exchanger (exhaust gas recirculation (EGR) cooler and fuel cell reforming). The present invention relates to a brazing composite material and a brazing product suitable for a fuel cell member.
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ろう材が使用されている。これは、ステンレス板の片面ある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およびコバルト基合金などの部品のろう材として、接合部の耐酸化性や耐食性に優れる各種ニッケルろうがＪＩＳ規格により規定されている。さらに、熱交換器接合用ニッケルろう材として特許文献１に記載されているように、粉末状ニッケルろうに、Ｎｉ、Ｃｒ、Ｎｉ−Ｃｒ合金のうち選ばれた金属粉末を４質量％〜２２質量％添加して構成されるニッケルろう材が提案されている。また、自己ろう付け性複合材を作る方法として、特許文献２に記載されているような複合材の製造方法がある。 Stainless steel clad brazing material 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, nickel base and cobalt base alloy, various nickel brazing excellent in oxidation resistance and corrosion resistance of the joint are defined by JIS standards. Furthermore, as described in Patent Document 1 as a nickel brazing material for joining heat exchangers, 4% by mass to 22% by mass of a metal powder selected from Ni, Cr, and Ni—Cr alloy is added to a powdered nickel braze. A nickel brazing material constituted by adding% is proposed. Further, as a method for producing a self-brazing composite material, there is a method for producing a composite material as described in Patent Document 2.
しかし、特許文献２に記載された製造方法で得られる複合材は、そのろう付け品の使用時に、以下のような問題がある。 However, the composite material obtained by the manufacturing method described in Patent Document 2 has the following problems when the brazed product is used.
従来技術におけるろう材は、ろう成分としてチタンを含んでいる。チタンは、その他のろう材成分と比べて酸素との親和性が高い。ろう付け品は、高温での酸化雰囲気下で表面から酸素が侵入し、ろう材内部で酸化するので、酸化は時間の経過とともに進み、酸化層は厚くなる。酸化が著しく進み、酸化層厚が厚くなると、チタンを中心とした酸化層は機械的に硬く脆いため、接合部の構造的強度が低下する危険性がある。 The brazing material in the prior art contains titanium as a brazing component. Titanium has a higher affinity for oxygen than other brazing filler metal components. In the brazed product, oxygen enters from the surface under an oxidizing atmosphere at a high temperature and oxidizes inside the brazing material, so that the oxidation proceeds with time and the oxide layer becomes thick. When oxidation progresses remarkably and the thickness of the oxide layer increases, the oxide layer centered on titanium is mechanically hard and brittle, and there is a risk that the structural strength of the joint is reduced.
さらに、ろう付け時にも、以下の問題がある。 Furthermore, there are the following problems when brazing.
特許文献２に記載された製造方法で得られる複合材は、ろう材全体の融点が高いため、ろう付け温度は約１１５０℃以上で行わなければならない。これは一般の熱処理炉に対して、非常に高い温度であり、炉体および周辺部品に与える熱ダメージ（高温による表面腐食（高温酸化）および構造材料の強度低下）は大きい。近年、高耐食性を有する熱交換器が要望されてきており、それに伴い、ろう付け温度が高い高耐食ろう材が必要となってきている。 Since the composite material obtained by the manufacturing method described in Patent Document 2 has a high melting point of the entire brazing material, the brazing temperature must be about 1150 ° C. or higher. This is a very high temperature with respect to a general heat treatment furnace, and heat damage (surface corrosion (high temperature oxidation) due to high temperature and reduction in strength of structural material) caused to the furnace body and peripheral parts is large. In recent years, a heat exchanger having high corrosion resistance has been demanded, and accordingly, a high corrosion resistance brazing material having a high brazing temperature has been required.
しかし、ろう付けは高真空中で行われるため、ろう付け温度が高いと、ろう材を構成する金属の蒸発がより促される。前記蒸発が促進されると、ろう材内部の組成が変化すると同時に、熱処理炉の内壁などに蒸発した金属が付着、凝固する。炉壁に蒸発金属が付着すると、次回熱処理時の再蒸発および再付着がなされると同時に、炉内の高真空度の維持が困難となる。そのため、ユーザーは炉内のメンテナンスを頻繁に行わなければならず、メンテナンスコストが増大する。また、ろう付け温度が高いと熱処理炉の耐久性が低下する。 However, since brazing is performed in a high vacuum, the higher the brazing temperature, the more the evaporation of the metal constituting the brazing material is promoted. When the evaporation is promoted, the composition inside the brazing material changes, and at the same time, the evaporated metal adheres to the inner wall of the heat treatment furnace and solidifies. If the evaporated metal adheres to the furnace wall, it will be re-evaporated and re-attached during the next heat treatment, and at the same time it will be difficult to maintain a high vacuum in the furnace. For this reason, the user must frequently perform maintenance in the furnace, which increases the maintenance cost. Further, when the brazing temperature is high, the durability of the heat treatment furnace is lowered.
本発明は、前記課題を解決し、ろう付け材をろう付けした後、高温酸化雰囲気中に晒した際のろう付け部の酸化進行を抑制することができる、ろう付け加工用複合材およびろう付け製品を提供することを目的とする。 The present invention solves the above-mentioned problems, and after brazing the brazing material, it can suppress the progress of oxidation of the brazing part when exposed to a high temperature oxidizing atmosphere, and the brazing composite material and brazing The purpose is to provide products.
前記目的を達成するために、本発明のうち、第１の発明は、基材表面に形成されたろう材の各金属層が、基材側から順に、クロムを含んだニッケル合金の第１の層と、アルミニウムまたはアルミニウム合金の第２の層と、クロムを含んだニッケル合金の第３の層とを積層して構成され、前記ろう材中のクロム成分がろう材全体に対して５質量％以上かつ２０質量％以下であり、かつアルミニウム成分が４０質量％以上かつ７０質量％以下であり、残部がニッケル成分であることを特徴とする、ろう付け加工用複合材である。
In order to achieve the above object, the first invention of the present invention is the first layer of a nickel alloy in which each metal layer of the brazing material formed on the substrate surface contains chromium in order from the substrate side. And a second layer of aluminum or aluminum alloy and a third layer of nickel alloy containing chromium, and the chromium component in the brazing material is 5% by mass or more with respect to the entire brazing material And it is 20 mass% or less, and an aluminum component is 40 mass% or more and 70 mass% or less, The remainder is a nickel component, It is a composite material for brazing process characterized by the above-mentioned.
また、前記基材がステンレス鋼であることが好ましい。 Moreover, it is preferable that the said base material is stainless steel.
第２の発明は、請求項１又は２に記載のろう付け加工用複合材を用いてろう付けにより組み立てられたことを特徴とする、ろう付け製品である。
A second invention is a brazed product assembled by brazing using the brazing composite material according to claim 1 or 2 .
本発明によれば、ろう付け材をろう付けした後、高温酸化雰囲気中に晒した際のろう付け部の酸化進行を抑制することができる。 ADVANTAGE OF THE INVENTION According to this invention, after brazing a brazing material, the oxidation progress of the brazing part at the time of exposing in a high temperature oxidizing atmosphere can be suppressed.
以下に、本発明を実施するための最良の形態を添付図面に基いて詳述する。 The best mode for carrying out the present invention will be described below in detail with reference to the accompanying drawings.
図１は本発明の第１実施形態に係るろう付け加工用複合材の横断面図（模式図）である。図１に示すように、本実施形態のろう付け加工用複合材１Ａは、ステンレス鋼からなる基材２の表面に形成されるろう材の各金属層が、基材２側から順に、クロムを含有したニッケル合金の第１の層３と、アルミニウムまたはアルミニウム合金の第２の層４と、クロムを含んだニッケル合金の第３の層５とを積層して構成されている。 FIG. 1 is a cross-sectional view (schematic diagram) of a brazing composite material according to a first embodiment of the present invention. As shown in FIG. 1, in the brazing composite material 1A of the present embodiment, each metal layer of the brazing material formed on the surface of the base material 2 made of stainless steel contains chromium in order from the base material 2 side. The first layer 3 of the contained nickel alloy, the second layer 4 of aluminum or aluminum alloy, and the third layer 5 of nickel alloy containing chromium are laminated.
前記ろう付け加工用複合材１Ａを用いて、ろう付け製品である例えば熱交換器の構成部材であるステンレス鋼とのろう付けを行う。ろう付けを行う熱処理炉の炉内の熱処理雰囲気は、７×１０−２Ｐａ以下の真空であり、ろう付け温度は１１００℃程度である。ろう付け加工用複合材１Ａは、基材およびろう材を構成する各金属同士の相互拡散により合金化し、ろう材全体が溶融、凝固し、ろう付けが完了する。 The brazing composite material 1A is used for brazing with a brazing product, for example, stainless steel, which is a constituent member of a heat exchanger. The heat treatment atmosphere in the heat treatment furnace for brazing is a vacuum of 7 × 10 −2 Pa or less, and the brazing temperature is about 1100 ° C. The brazing composite material 1A is alloyed by mutual diffusion between the base metal and each metal constituting the brazing material, and the entire brazing material is melted and solidified to complete the brazing.
ろう付け後のろう付け部を高温例えば６００℃で大気中に晒すと、ろう付け部の表面酸化が開始する。その際、ろう付け部の合金成分のうち、クロム成分およびアルミニウム成分は酸素と結合しやすく、優先的に酸化し、ろう付け部表面に酸化層を形成する。特に、アルミニウム酸化物は、高温下では安定であるため、ろう付け部表面には安定な酸化膜が形成され、ろう付け部内部への酸化進行を抑制することができ、ろう材全体の酸化速度を遅くすることができ、ろう材全体の強度の低下および腐食を低減することができる。これにより、ろう付け材をろう付けした後、高温酸化雰囲気中に晒した際のろう付け部の酸化進行を抑制することができる。 When the brazed part after brazing is exposed to the atmosphere at a high temperature, for example, 600 ° C., surface oxidation of the brazed part starts. At that time, among the alloy components of the brazing portion, the chromium component and the aluminum component are easily combined with oxygen, and are preferentially oxidized to form an oxide layer on the surface of the brazing portion. In particular, since aluminum oxide is stable at high temperatures, a stable oxide film is formed on the surface of the brazed part, and the progress of oxidation into the brazed part can be suppressed. Can reduce the strength of the brazing material and corrosion. Thereby, after brazing a brazing material, it is possible to suppress the progress of oxidation of the brazed portion when exposed to a high-temperature oxidizing atmosphere.
また、ろう付け加工用複合材１Ａのろう材の融点は低く、ろう付け温度は低くて良い（１１００℃以下）ため、炉体および周辺部品に与える熱ダメージが少なく、熱処理炉の耐久性の向上（長寿命化）が図れる。さらに、ろう材中のクロム成分は、湿潤環境でのＳＯｘガスおよびＮＯｘガスに対する耐食性の向上に寄与し、ろう材全体の高い湿式耐食性を維持することが可能となる。 In addition, since the melting point of the brazing material of the brazing composite material 1A is low and the brazing temperature may be low (1100 ° C. or less), there is little thermal damage to the furnace body and peripheral parts, and the durability of the heat treatment furnace is improved. (Long life) can be achieved. Further, the chromium component in the brazing material contributes to the improvement of the corrosion resistance against SOx gas and NOx gas in a wet environment, and the high wet corrosion resistance of the entire brazing material can be maintained.
図２は本発明の第２実施形態に係るろう付け加工用複合材の横断面図（模式図）である。図２に示すように、本実施形態のろう付け加工用複合材１Ｂは、ステンレス鋼からなる基材２の表面に形成されたろう材の各金属層が、基材２側から順に、クロムを含んだニッケル合金の第１の層３と、アルミニウムまたはアルミニウム合金の第２の層４とを積層して構成されている。本実施形態のような構成の複合材１Ｂを用いた場合にも、前記同様の効果が得られる。 FIG. 2 is a cross-sectional view (schematic diagram) of a brazing composite material according to a second embodiment of the present invention. As shown in FIG. 2, in the brazing composite material 1B of the present embodiment, each metal layer of the brazing material formed on the surface of the base material 2 made of stainless steel contains chromium sequentially from the base material 2 side. The first layer 3 made of nickel alloy and the second layer 4 made of aluminum or aluminum alloy are laminated. Even when the composite material 1B having the configuration as in the present embodiment is used, the same effect as described above can be obtained.
第１実施形態、第２実施形態における、ろう材中のアルミニウム成分は、４０質量％以上かつ７０質量％以下であることが望ましい。４０質量％以下ではろう材全体が合金化した際の融点が高くなり、ろう付け温度が高くなるからである。ろう付け温度が高くなると、ろう付け熱処理炉に与える熱ダメージが大きくなり、炉の寿命を短くする。また、７０質量％以上であると、ろう材全体の湿潤環境下での耐食性が低下してしまうからである。組成範囲は、好ましくは４５質量％〜６５質量％、さらに好ましくは５０質量％〜６０質量％が望ましい。 In the first embodiment and the second embodiment, the aluminum component in the brazing material is desirably 40% by mass or more and 70% by mass or less. This is because when the amount is 40% by mass or less, the melting point when the entire brazing material is alloyed becomes high, and the brazing temperature becomes high. When the brazing temperature is increased, thermal damage to the brazing heat treatment furnace is increased and the life of the furnace is shortened. Moreover, it is because the corrosion resistance in the moist environment of the whole brazing material will fall that it is 70 mass% or more. The composition range is preferably 45 mass% to 65 mass%, more preferably 50 mass% to 60 mass%.
ろう材中のクロム成分は、５質量％以上かつ２０質量％以下であることが望ましい。５質量％以下では、ろう材の湿潤環境での耐食性が低下するからである。また、２０質量％以上であると、ろう材全体の融点が上昇し、ろう付け温度を高くする必要があるからである。ろう付け温度が高いと、ろう付け熱処理炉への熱ダメージが大きくなり、且つ蒸発金属量も増加するため、ろう付け熱処理炉の寿命が短くなってしまう。組成範囲は、好ましくは６質量％〜１８質量％、さらに好ましくは７質量％〜１５質量％が望ましい。 The chromium component in the brazing material is preferably 5% by mass or more and 20% by mass or less. This is because if the content is 5% by mass or less, the corrosion resistance of the brazing material in a wet environment decreases. Moreover, it is because it is necessary to make brazing temperature high that melting | fusing point of the whole brazing material rises that it is 20 mass% or more. When the brazing temperature is high, thermal damage to the brazing heat treatment furnace increases, and the amount of evaporated metal also increases, so the life of the brazing heat treatment furnace is shortened. The composition range is preferably 6% by mass to 18% by mass, and more preferably 7% by mass to 15% by mass.
また、ろう材を構成するアルミニウムまたはアルミニウム合金の第１の層３は、基材２と接触しない箇所へ配置するのが望ましく、かつろう材表面への配置を避けるのが望ましい。ステンレス鋼の基材２とアルミニウムが接触していると、ろう材を構成する金属層同士および金属層と基材間の接合強化のための拡散熱処理の際に、金属間化合物を形成するため、クラッド板の接合強度を保つことができないからである。 Moreover, it is desirable to arrange | position the 1st layer 3 of the aluminum or aluminum alloy which comprises a brazing material in the location which does not contact the base material 2, and it is desirable to avoid the arrangement | positioning on the brazing material surface. When the stainless steel base material 2 and aluminum are in contact with each other, in order to form an intermetallic compound during diffusion heat treatment for strengthening the bonding between the metal layers constituting the brazing material and between the metal layer and the base material, This is because the bonding strength of the clad plate cannot be maintained.
ろう材表面側にアルミニウムを配置すると、アルミニウムは他のろう材構成金属より融点が低いため、ろう付け時に表面のアルミニウム層が先行して溶融し、このため、ろう材全体の均一な合金化および溶融が困難となる。したがって、アルミニウムまたはアルミニウム合金層はろう材を構成する２種以上の層に挟まれる図１の構成（第１実施形態）がもっとも望ましい。ろう付け時の拡散反応がアルミニウムまたはアルミニウム合金層の両面側に同時に生じるため、ろう材全体の合金化が円滑になる。 When aluminum is arranged on the brazing material surface side, aluminum has a lower melting point than other brazing metal constituent metals, so the aluminum layer on the surface is melted first during brazing, and thus uniform alloying of the entire brazing material and Melting becomes difficult. Therefore, the configuration of FIG. 1 (first embodiment) in which the aluminum or aluminum alloy layer is sandwiched between two or more layers constituting the brazing material is most desirable. Since the diffusion reaction during brazing occurs simultaneously on both sides of the aluminum or aluminum alloy layer, alloying of the entire brazing material becomes smooth.
実施例１
板厚１．０ｍｍのコイル状クロム入りニッケル板（Ｎｉ−２０質量％Ｃｒ）、板厚５．０ｍｍのコイル状アルミニウム板、板厚１．０ｍｍのコイル状クロム入りニッケル板（Ｎｉ−２０質量％Ｃｒ）を重ね合わせ、合計３層の構造にし、熱間圧延を行い板厚１．４ｍｍのクラッド板を得た。引き続き冷間圧延により板厚１．０ｍｍのクラッド板を仕上げた。
Example 1
Coiled chromium-containing nickel plate (Ni-20 mass% Cr) with a plate thickness of 1.0 mm, coil-shaped aluminum plate with a plate thickness of 5.0 mm, coil-shaped chromium-containing nickel plate with a thickness of 1.0 mm (Ni-20 mass%) Cr) was superposed to form a total of three layers, and hot rolled to obtain a clad plate having a thickness of 1.4 mm. Subsequently, a clad plate having a thickness of 1.0 mm was finished by cold rolling.
前記クラッド板とステンレス条（ＳＵＳ３０４、厚さ２．５ｍｍ）に冷間圧延法によりクラッド、冷間圧延を行い、厚さ０．５ｍｍの複合基材を作製した。 The clad plate and stainless steel strip (SUS304, thickness 2.5 mm) were clad and cold-rolled by a cold rolling method to produce a composite substrate having a thickness of 0.5 mm.
実施例２
板厚１．０ｍｍのコイル状クロム入りニッケル板（Ｎｉ−２０質量％Ｃｒ）、板厚３．７３ｍｍのコイル状アルミニウム板、板厚１．０ｍｍのコイル状クロム入りニッケル板（Ｎｉ−２０質量％Ｃｒ）を重ね合わせ、合計３層の構造にし、熱間圧延を行い板厚１．４ｍｍのクラッド板を得た。引き続き冷間圧延により板厚１．０ｍｍのクラッド板を仕上げた。
Example 2
Coiled chromium-plated nickel plate with a thickness of 1.0 mm (Ni-20% by mass Cr), coiled aluminum plate with a thickness of 3.73 mm, coiled chromium-containing nickel plate with a thickness of 1.0 mm (Ni-20% by mass) Cr) was superposed to form a total of three layers, and hot rolled to obtain a clad plate having a thickness of 1.4 mm. Subsequently, a clad plate having a thickness of 1.0 mm was finished by cold rolling.
前記クラッド板とステンレス条（ＳＵＳ３０４、厚さ２．５ｍｍ）に冷間圧延法によりクラッド、冷間圧延を行い、厚さ０．５ｍｍの複合基材を作製した。 The clad plate and stainless steel strip (SUS304, thickness 2.5 mm) were clad and cold-rolled by a cold rolling method to produce a composite substrate having a thickness of 0.5 mm.
実施例３
板厚１．０ｍｍのコイル状クロム入りニッケル板（Ｎｉ−９質量％Ｃｒ）、板厚５．０ｍｍのコイル状アルミニウム板、板厚１．０ｍｍのコイル状クロム入りニッケル板（Ｎｉ−２０質量％Ｃｒ）を重ね合わせ、合計３層の構造にし、熱間圧延を行い板厚１．４ｍｍのクラッド板を得た。引き続き冷間圧延により板厚１．０ｍｍのクラッド板を仕上げた。
Example 3
Coiled chromium-plated nickel plate (Ni-9 mass% Cr) with a plate thickness of 1.0 mm, coil-shaped aluminum plate with a plate thickness of 5.0 mm, coil-shaped chromium-containing nickel plate with a thickness of 1.0 mm (Ni-20 mass%) Cr) was superposed to form a total of three layers, and hot rolled to obtain a clad plate having a thickness of 1.4 mm. Subsequently, a clad plate having a thickness of 1.0 mm was finished by cold rolling.
前記クラッド板とステンレス条（ＳＵＳ３０４、厚さ２．５ｍｍ）に冷間圧延法によりクラッド、冷間圧延を行い、厚さ０．５ｍｍの複合基材を作製した。 The clad plate and stainless steel strip (SUS304, thickness 2.5 mm) were clad and cold-rolled by a cold rolling method to produce a composite substrate having a thickness of 0.5 mm.
実施例４
板厚０．９５ｍｍのコイル状クロム入りニッケル板（Ｎｉ−２０質量％Ｃｒ）、板厚３．９ｍｍのコイル状アルミニウム板、板厚０．９５ｍｍのコイル状クロム入りニッケル板（Ｎｉ−２０質量％Ｃｒ）を重ね合わせ、合計３層の構造にし、熱間圧延を行い板厚１．４ｍｍのクラッド板を得た。引き続き冷間圧延により板厚１．０ｍｍのクラッド板を仕上げた。
Example 4
Coiled chromium-containing nickel plate with a thickness of 0.95 mm (Ni-20% by mass Cr), coiled aluminum plate with a thickness of 3.9 mm, coiled chromium-containing nickel plate with a thickness of 0.95 mm (Ni-20% by mass) Cr) was superposed to form a total of three layers, and hot rolled to obtain a clad plate having a thickness of 1.4 mm. Subsequently, a clad plate having a thickness of 1.0 mm was finished by cold rolling.
前記クラッド板とステンレス条（ＳＵＳ３０４、厚さ２．５ｍｍ）に冷間圧延法によりクラッド、冷間圧延を行い、厚さ０．５ｍｍの複合基材を作製した。 The clad plate and stainless steel strip (SUS304, thickness 2.5 mm) were clad and cold-rolled by a cold rolling method to produce a composite substrate having a thickness of 0.5 mm.
実施例５
板厚１．０ｍｍのコイル状クロム入りニッケル板（Ｎｉ−２０質量％Ｃｒ）、板厚１４．２５ｍｍのコイル状アルミニウム板、板厚１．０ｍｍのコイル状クロム入りニッケル板（Ｎｉ−２０質量％Ｃｒ）を重ね合わせ、合計３層の構造にし、熱間圧延を行い板厚１．４ｍｍのクラッド板を得た。引き続き冷間圧延により板厚１．０ｍｍのクラッド板を仕上げた。
Example 5
Coiled chromium-containing nickel plate (Ni-20 mass% Cr) with a plate thickness of 1.0 mm, coil-shaped aluminum plate with a plate thickness of 14.25 mm, coil-shaped chromium-containing nickel plate with a thickness of 1.0 mm (Ni-20 mass%) Cr) was superposed to form a total of three layers, and hot rolled to obtain a clad plate having a thickness of 1.4 mm. Subsequently, a clad plate having a thickness of 1.0 mm was finished by cold rolling.
前記クラッド板とステンレス条（ＳＵＳ３０４、厚さ２．５ｍｍ）に冷間圧延法によりクラッド、冷間圧延を行い、厚さ０．５ｍｍの複合基材を作製した。 The clad plate and stainless steel strip (SUS304, thickness 2.5 mm) were clad and cold-rolled by a cold rolling method to produce a composite substrate having a thickness of 0.5 mm.
実施例６
板厚０．９ｍｍのコイル状クロム入りニッケル板（Ｎｉ−２０質量％Ｃｒ）、板厚４．６２ｍｍのコイル状アルミニウム合金板（Ａｌ-１．５質量％Ｍｎ）、板厚０．９ｍｍのコイル状クロム入りニッケル板（Ｎｉ−２０質量％Ｃｒ）を重ね合わせ、合計３層の構造にし、熱間圧延を行い板厚１．４ｍｍのクラッド板を得た。引き続き冷間圧延により板厚１．０ｍｍのクラッド板を仕上げた。
Example 6
Coiled chromium-plated nickel plate with a thickness of 0.9 mm (Ni-20 mass% Cr), coil-shaped aluminum alloy plate with a thickness of 4.62 mm (Al-1.5 mass% Mn), coil with a thickness of 0.9 mm Chromium-containing nickel plates (Ni-20 mass% Cr) were superposed to form a total of three layers, and hot rolled to obtain a clad plate having a thickness of 1.4 mm. Subsequently, a clad plate having a thickness of 1.0 mm was finished by cold rolling.
前記クラッド板とステンレス条（ＳＵＳ３０４、厚さ２．５ｍｍ）に冷間圧延法によりクラッド、冷間圧延を行い、厚さ０．５ｍｍの複合基材を作製した。 The clad plate and stainless steel strip (SUS304, thickness 2.5 mm) were clad and cold-rolled by a cold rolling method to produce a composite substrate having a thickness of 0.5 mm.
比較例１
板厚１．０ｍｍのコイル状クロム入りニッケル板（Ｎｉ−２０質量％Ｃｒ）、板厚２．６２ｍｍのコイル状アルミニウム板、板厚１．０ｍｍのコイル状クロム入りニッケル板（Ｎｉ−２０質量％Ｃｒ）を重ね合わせ、合計３層の構造にし、熱間圧延を行い板厚１．４ｍｍのクラッド板を得た。引き続き冷間圧延により板厚１．０ｍｍのクラッド板を仕上げた。
Comparative Example 1
Coiled chromium-containing nickel plate with a thickness of 1.0 mm (Ni-20% by mass Cr), Coiled aluminum plate with a thickness of 2.62 mm, Coiled chromium-containing nickel plate with a thickness of 1.0 mm (Ni-20% by mass) Cr) was superposed to form a total of three layers, and hot rolled to obtain a clad plate having a thickness of 1.4 mm. Subsequently, a clad plate having a thickness of 1.0 mm was finished by cold rolling.
前記クラッド板とステンレス条（ＳＵＳ３０４、厚さ２．５ｍｍ）に冷間圧延法によりクラッド、冷間圧延を行い、厚さ０．５ｍｍの複合基材を作製した。 The clad plate and stainless steel strip (SUS304, thickness 2.5 mm) were clad and cold-rolled by a cold rolling method to produce a composite substrate having a thickness of 0.5 mm.
比較例２
板厚１．０ｍｍのコイル状クロム入りニッケル板（Ｎｉ−２０質量％Ｃｒ）、板厚１２．２ｍｍのコイル状アルミニウム板、板厚１．０ｍｍのコイル状クロム入りニッケル板（Ｎｉ−２０質量％Ｃｒ）を重ね合わせ、合計３層の構造にし、熱間圧延を行い板厚１．４ｍｍのクラッド板を得た。引き続き冷間圧延により板厚１．０ｍｍのクラッド板を仕上げた。
Comparative Example 2
Coiled chromium-plated nickel plate (Ni-20 mass% Cr) with a plate thickness of 1.0 mm, coil-shaped aluminum plate with a plate thickness of 12.2 mm, coil-shaped chromium-containing nickel plate with a thickness of 1.0 mm (Ni-20 mass%) Cr) was superposed to form a total of three layers, and hot rolled to obtain a clad plate having a thickness of 1.4 mm. Subsequently, a clad plate having a thickness of 1.0 mm was finished by cold rolling.
前記クラッド板とステンレス条（ＳＵＳ３０４、厚さ２．５ｍｍ）に冷間圧延法によりクラッド、冷間圧延を行い、厚さ０．５ｍｍの複合基材を作製した。 The clad plate and stainless steel strip (SUS304, thickness 2.5 mm) were clad and cold-rolled by a cold rolling method to produce a composite substrate having a thickness of 0.5 mm.
比較例３
板厚１．０ｍｍのコイル状クロム入りニッケル板（Ｎｉ−６質量％Ｃｒ）、板厚２．６２ｍｍのコイル状アルミニウム板、板厚１．０ｍｍのコイル状クロム入りニッケル板（Ｎｉ−６質量％Ｃｒ）を重ね合わせ、合計３層の構造にし、熱間圧延を行い板厚１．４ｍｍのクラッド板を得た。引き続き冷間圧延により板厚１．０ｍｍのクラッド板を仕上げた。
Comparative Example 3
Coiled chromium-containing nickel plate with a thickness of 1.0 mm (Ni-6% by mass Cr), Coiled aluminum plate with a thickness of 2.62 mm, Coiled chromium-containing nickel plate with a thickness of 1.0 mm (Ni-6% by mass) Cr) was superposed to form a total of three layers, and hot rolled to obtain a clad plate having a thickness of 1.4 mm. Subsequently, a clad plate having a thickness of 1.0 mm was finished by cold rolling.
前記クラッド板とステンレス条（ＳＵＳ３０４、厚さ２．５ｍｍ）に冷間圧延法によりクラッド、冷間圧延を行い、厚さ０．５ｍｍの複合基材を作製した。 The clad plate and stainless steel strip (SUS304, thickness 2.5 mm) were clad and cold-rolled by a cold rolling method to produce a composite substrate having a thickness of 0.5 mm.
比較例４
板厚１．０ｍｍのコイル状クロム入りニッケル板（Ｎｉ−３５質量％Ｃｒ）、板厚４．１ｍｍのコイル状アルミニウム板、板厚１．０ｍｍのコイル状クロム入りニッケル板（Ｎｉ−３５質量％Ｃｒ）を重ね合わせ、合計３層の構造にし、熱間圧延を行い板厚１．４ｍｍのクラッド板を得た。引き続き冷間圧延により板厚１．０ｍｍのクラッド板を仕上げた。
Comparative Example 4
Coiled chromium-containing nickel plate with a thickness of 1.0 mm (Ni-35% by mass Cr), Coiled aluminum plate with a thickness of 4.1 mm, Coiled chromium-containing nickel plate with a thickness of 1.0 mm (Ni-35% by mass) Cr) was superposed to form a total of three layers, and hot rolled to obtain a clad plate having a thickness of 1.4 mm. Subsequently, a clad plate having a thickness of 1.0 mm was finished by cold rolling.
前記クラッド板とステンレス条（ＳＵＳ３０４、厚さ２．５ｍｍ）に冷間圧延法によりクラッド、冷間圧延を行い、厚さ０．５ｍｍの複合基材を作製した。 The clad plate and stainless steel strip (SUS304, thickness 2.5 mm) were clad and cold-rolled by a cold rolling method to produce a composite substrate having a thickness of 0.5 mm.
従来例１
板厚１．７ｍｍのコイル状純ニッケル板、板厚４．１ｍｍのコイル状純チタン板、板厚１．７ｍｍのコイル状純ニッケル板を重ね合わせ、合計３層の構造にし、熱間圧延を行い板厚１．４ｍｍのクラッド板を得た。引き続き冷間圧延により板厚１．０ｍｍのクラッド板を仕上げた。
Conventional Example 1
A coiled pure nickel plate with a plate thickness of 1.7 mm, a coiled pure titanium plate with a plate thickness of 4.1 mm, and a coiled pure nickel plate with a plate thickness of 1.7 mm are stacked to form a total of three layers, and hot rolling is performed. A clad plate having a thickness of 1.4 mm was obtained. Subsequently, a clad plate having a thickness of 1.0 mm was finished by cold rolling.
前記クラッド板とＳＵＳ３０４条（銅成分０％、厚さ２．５ｍｍ）に冷間圧延法によりクラッド、冷間圧延を行い、厚さ０．５ｍｍの複合基材を作製した。 The clad plate and SUS304 strip (copper component 0%, thickness 2.5 mm) were clad and cold-rolled by a cold rolling method to prepare a composite substrate having a thickness of 0.5 mm.
以上の実施例で作製したクラッド板を２０ｍｍ×２５ｍｍに切り出し、その中央にステンレス製パイプ（ＳＵＳ３０４、Φ６ｍｍ×１５ｍｍ）をワイヤなどで固定し、ろう付け熱処理を行った。ろう付け条件は、ろう付け温度１１００℃×１５ｍｉｎで、真空度は８．０×１０−２Ｐａであった。 The clad plate produced in the above example was cut out to 20 mm × 25 mm, a stainless steel pipe (SUS304, Φ6 mm × 15 mm) was fixed to the center with a wire, and brazing heat treatment was performed. The brazing conditions were a brazing temperature of 1100 ° C. × 15 min and a degree of vacuum of 8.0 × 10 −2 Pa.
前記条件にて作製したろう付け材について、大気中にて８００℃×１００ｈの高温酸化試験を行い、中央断面におけるパイプ接合部のろう付けフィレット表面の酸化層形成状況について調べた。また、硝酸系の凝縮水試験により、ろう付け部の湿式耐食性の評価を行った。 About the brazing material produced on the said conditions, the high temperature oxidation test of 800 degreeC x 100 h was performed in air | atmosphere, and the oxidation layer formation condition of the brazing fillet surface of the pipe junction part in a center cross section was investigated. The wet corrosion resistance of the brazed part was evaluated by a nitric acid-based condensed water test.
腐食発生の有無は、腐食試験前後のろう付け部の断面観察を行い、最大侵食深さにより評価した。最大侵食深さが２０μｍ未満を○、２０μｍ以上１００μｍ未満を△、１００μｍ以上を×とした。腐食による溶出物の量については、ろう材中に含まれる元素で試験溶液を溶出した量が１ｍｇ／Ｌを超えるものがある場合を×、０．５ｍｇ／Ｌ以上１ｍｇ／Ｌ未満を△、いずれの元素の溶出量も０．５ｍｇ／Ｌ未満である場合を○とした。これらの結果は最大侵食深さによる評価と一致し、総合的に判断した。試験液としては、塩素イオン２００ｐｐｍ、硝酸イオン８０ｐｐｍ、硫酸イオン１０００ｐｐｍ、を含む水溶液を用いた。試料は、２５ｍｍ×２５ｍｍのろう材を備えた基材の上にΦ６ｍｍのステンレス鋼パイプを設置し、基材とＳＵＳパイプの間で接合フィレットを生成させたものを使用した。 The presence or absence of corrosion was evaluated by observing the cross section of the brazed part before and after the corrosion test and evaluating the maximum erosion depth. The maximum erosion depth was less than 20 μm, ◯, 20 μm or more and less than 100 μm, and 100 μm or more as x. As for the amount of the eluate due to corrosion, the case where the amount of the element contained in the brazing material eluted from the test solution exceeds 1 mg / L, x is 0.5 mg / L or more and less than 1 mg / L, either The case where the elution amount of the element was less than 0.5 mg / L was evaluated as ◯. These results were consistent with the evaluation by the maximum erosion depth, and were judged comprehensively. As the test solution, an aqueous solution containing 200 ppm chlorine ions, 80 ppm nitrate ions, and 1000 ppm sulfate ions was used. As a sample, a stainless steel pipe having a diameter of 6 mm was installed on a base material provided with a brazing material of 25 mm × 25 mm, and a joining fillet was generated between the base material and the SUS pipe was used.
表１は、実施例および比較例および従来例の複合材の構成、ろう材中のアルミニウムおよびクロムの含有比率、フィレット表面の酸化層厚さ、湿式耐食性評価、１１００℃でのろう付け可否および総合評価を示したものである。酸化層の厚さは、フィレットの曲面の断面写真に基づいて最大である箇所を計測した。 Table 1 shows the composition of the composite materials of Examples, Comparative Examples, and Conventional Examples, the content ratio of aluminum and chromium in the brazing material, the thickness of the oxide layer on the fillet surface, the evaluation of wet corrosion resistance, and whether or not brazing at 1100 ° C. The evaluation is shown. The maximum thickness of the oxide layer was measured based on a cross-sectional photograph of the fillet curved surface.
表１によれば、本発明の実施例１〜６および比較例１〜４は、従来例と比べてフィレット表面の酸化層厚さが薄く、耐高温酸化性に優れているといえる。 According to Table 1, it can be said that Examples 1 to 6 and Comparative Examples 1 to 4 of the present invention have a thinner oxide layer on the fillet surface than the conventional example, and are excellent in high temperature oxidation resistance.
しかし、比較例１、３および４は、ろう材中のＡｌ含有比率が低いため、ろう材全体の融点が上昇し、１１００℃でのろう付けが不可となり、総合評価は×となった。また、比較例２はＣｒ濃度が低いため、湿潤下での耐食性が悪化し、総合評価は×となった。 However, in Comparative Examples 1, 3 and 4, since the Al content ratio in the brazing material was low, the melting point of the brazing material as a whole increased, brazing at 1100 ° C. was impossible, and the overall evaluation was x. Moreover, since the comparative example 2 had low Cr density | concentration, the corrosion resistance under wet condition deteriorated, and the comprehensive evaluation became x.
これに対し、実施例は比較例および従来例と比べて、耐高温酸化性、湿式耐食性、ろう付け温度すべての点において、比較例および従来例と比べて優れたろう付け材（ろう付け加工用複合材）であるといえる。 On the other hand, compared with the comparative example and the conventional example, the examples are superior to the comparative example and the conventional example in terms of high-temperature oxidation resistance, wet corrosion resistance, and brazing temperature. Material).
以上、本発明の実施の形態を図面により詳述してきたが、本発明は前記実施の形態に限定されるものではなく、本発明の要旨を逸脱しない範囲での種々の設計変更が可能である。 The embodiments of the present invention have been described in detail with reference to the drawings. However, the present invention is not limited to the above-described embodiments, and various design changes can be made without departing from the gist of the present invention. .
１Ａ ろう付け加工用複合材
１Ｂ ろう付け加工用複合材
２ 基材
３ 第１の層
４ 第２の層
５ 第３の層
DESCRIPTION OF SYMBOLS 1A Composite material for brazing process 1B Composite material for brazing process 2 Base material 3 1st layer 4 2nd layer 5 3rd layer
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