JP2009161801A - Stainless steel sheet having composite plated layer for soldering, and product manufactured by using the same - Google Patents
Stainless steel sheet having composite plated layer for soldering, and product manufactured by using the same Download PDFInfo
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Abstract
Description
本発明は、ろう付け用多層めっき層を有するステンレス鋼板及びこれを用いて製造された物品に関する。本発明のステンレス鋼板は、複数のプレートとフィンを積層し、互いにろう付けすることで製造される積層型熱交換器の製造に使用するプレートの材料として特に適している。 The present invention relates to a stainless steel plate having a multilayer plating layer for brazing and an article produced using the same. The stainless steel plate of the present invention is particularly suitable as a material for a plate used in the production of a laminated heat exchanger produced by laminating a plurality of plates and fins and brazing them together.
従来、熱交換器において、高い伝熱面密度と熱流速とが要求される場合には、積層型のプレート・フィン熱交換器が使用されてきた。ＥＧＲ(Exhaust Gas Recirculation)（排気ガス再循環装置）は、排気ガスの一部を吸気系に戻し、混合気が燃焼する時の最高温度を低くしてNOxの生成量を抑える装置であり、ＥＧＲクーラは、排気の一部を吸気系に戻す途中に装着され、排気を冷やしてエンジンに送り込む働きをする熱交換器である。このような熱交換器は例えば、ステンレス鋼板製の薄板状のプレートと矩形フィンとを多数積層し、複数の構成部品を互いにろう付けすることで一体構造体として製造される。ろう付けに使用されるろう材としては、高温特性と耐食性が要求され、ＪＩＳ Ｚ ３２６５−１９９８に規定されるＮｉろう ＢＮｉ−５などが使用されてきた。市販のニッケルろう材には、粉末状、粉末を有機系のバインダで混合したペースト状、さらにアモルファス箔状のものがあり、粉末、ペーストは必要箇所に塗布、介入して、アモルファス箔の場合は、置きろうとして使用される。 Conventionally, in a heat exchanger, when a high heat transfer surface density and a heat flow rate are required, a laminated plate-fin heat exchanger has been used. EGR (Exhaust Gas Recirculation) is a device that returns a part of the exhaust gas to the intake system, lowers the maximum temperature when the air-fuel mixture burns, and reduces the amount of NOx produced. The cooler is a heat exchanger that is mounted in the middle of returning a part of the exhaust gas to the intake system and functions to cool the exhaust gas and send it to the engine. Such a heat exchanger is manufactured, for example, as a monolithic structure by laminating a large number of thin plate plates and rectangular fins made of stainless steel plates and brazing a plurality of components to each other. As a brazing material used for brazing, high temperature characteristics and corrosion resistance are required, and Ni brazing BNi-5 defined in JIS Z 3265-1998 has been used. Commercially available nickel brazing materials include powders, pastes in which powders are mixed with organic binders, and amorphous foils. Powders and pastes are applied and intervened where necessary, and in the case of amorphous foils , Used to put.
ペースト状、粉末状のろう材をプレートとフィンの接合部間に塗布、介入させようとすると、その接合個所が非常に多いため、ろう付け作業に多大な労力を要し、製品の生産性は著しく低くなり、その結果、製造コストの上昇を招くという問題がある。近年、熱交換器の高効率化、小型化が加速したため、この問題はさらに顕在化してきた。 Applying and interposing paste-like or powder-like brazing material between the joints of the plate and fins requires a lot of labor for brazing because there are so many joints, and product productivity is low. There is a problem that the cost is significantly lowered, resulting in an increase in manufacturing cost. In recent years, this problem has become more apparent as the efficiency and miniaturization of heat exchangers have accelerated.
また、ＢＮｉ−５ Ｎｉろうは耐食性や耐熱性が良好であるが、液相線温度が約１１６０℃と高いため、ろう付け温度は１２００℃以上の高温を必要とする。このため、接合しようとするステンレス鋼板の耐熱強度が低い場合には、反りなどの熱変形が生じる。 BNi-5 Ni brazing has good corrosion resistance and heat resistance. However, since the liquidus temperature is as high as about 1160 ° C., the brazing temperature requires a high temperature of 1200 ° C. or higher. For this reason, when the heat resistant strength of the stainless steel plate to be joined is low, thermal deformation such as warpage occurs.
さらに、ペースト状のろう材では、有機系のバインダを使用するため、バインダの蒸発工程（真空中５００℃で２０分程度）が必要となるほか、バインダの蒸発にともなう悪臭の発生やろう付け炉内が汚染されるといった問題が生じる。また、アモルファス箔材の場合は、ろう材自体が非常に脆いため、ろう付け製品の組み立て時の取り扱いが難しく、製造コストが高くなるという問題がある。 Furthermore, since the paste-like brazing material uses an organic binder, a binder evaporation step (approximately 20 minutes at 500 ° C. in a vacuum) is required, and the generation of bad odors due to the evaporation of the binder and brazing furnace The problem that the inside becomes polluted arises. In the case of an amorphous foil material, since the brazing material itself is very brittle, there is a problem that handling at the time of assembling the brazed product is difficult and the manufacturing cost increases.
特許文献１〜４においては、めっき皮膜にろう材の機能を持たせる方法が記載されている。これらの方法では、ステンレス鋼板製のプレート材の表面にＮｉ−Ｐ（Ｐ％＝８〜１１質量％）の合金めっきを施した後、加熱処理によってＮｉ−Ｐ皮膜を溶融させ、フィンとの接合箇所において、ろう材としての機能を持たせている。 Patent Documents 1 to 4 describe a method of giving a plating film the function of a brazing material. In these methods, after Ni-P (P% = 8 to 11% by mass) alloy plating is applied to the surface of a plate made of stainless steel plate, the Ni-P film is melted by heat treatment and bonded to the fins. In some places, it has a function as a brazing material.
しかしながら、このＮｉ−Ｐろうはろう付け温度が低いという利点はあるが、ＪＩＳ Ｚ ３２６５−１９９８に規定されるＮｉろう ＢＮｉ−５など、Ｃｒ入りのろう材に比べて耐食性が著しく劣るという欠点がある。このため、窒素酸化物や硫酸成分が含まれる排気ガスが流入する厳しい腐食環境のＥＧＲクーラには適応できない。 However, although this Ni-P brazing has the advantage that the brazing temperature is low, there is a disadvantage that the corrosion resistance is remarkably inferior compared with a brazing material containing Cr such as Ni brazing BNi-5 defined in JIS Z 3265-1998. is there. For this reason, it cannot be applied to an EGR cooler in a severe corrosive environment into which exhaust gas containing nitrogen oxides and sulfuric acid components flows.
さらに特許文献５には、板厚方向に複数交互に積層されるステンレス鋼板よりなる第１、第２成形プレートの両端面にＣｒ鍍金してクロム系ろう材層を形成し、そのクロム系ろう材層上にＮｉ−Ｐ鍍金を施してニッケル系ろう材層を形成し、第１、第２成形プレート間にクロム系ろう材層およびニッケル系ろう材層を介在した状態で一体ろう付け接合することにより、第１、第２成形プレートの両端面にＮｉ−Ｃｒ２８−Ｐ８−他の合金組成を含有する高耐食ろう材を含む高耐腐食性熱交換器の製造方法が記載されている。しかし、この方法は、ステンレス鋼板とクロム系ろう材層との密着性が充分でないという問題がある。 Further, in Patent Document 5, a chromium brazing material layer is formed by plating Cr on both end faces of first and second forming plates made of stainless steel plates alternately laminated in the thickness direction. Ni-P plating is formed on the layer to form a nickel brazing filler metal layer, and brazing is integrally performed with the chromium brazing filler metal layer and the nickel brazing filler metal layer interposed between the first and second molding plates. Describes a method of manufacturing a highly corrosion-resistant heat exchanger that includes a highly corrosion-resistant brazing material containing Ni—Cr28—P8—other alloy composition on both end faces of the first and second molded plates. However, this method has a problem that the adhesion between the stainless steel plate and the chromium brazing material layer is not sufficient.
本発明の目的は、ろう付け用多層めっき層を有するステンレス鋼板を提供することである。
本発明の他の目的は、上記ステンレス鋼板を用いて製造された物品を提供することである。
本発明のさらに他の目的は、複数のプレートとフィンを積層し、互いにろう付けすることで製造される積層型熱交換器の製造に使用するプレートの材料として特に適しているステンレス鋼板を提供することである。
本発明のさらに他の目的は、積層型熱交換器を製造する方法を提供することである。
An object of the present invention is to provide a stainless steel plate having a multilayer plating layer for brazing.
Another object of the present invention is to provide an article manufactured using the stainless steel plate.
Still another object of the present invention is to provide a stainless steel plate that is particularly suitable as a material for a plate used for manufacturing a laminated heat exchanger manufactured by stacking a plurality of plates and fins and brazing them together. That is.
Still another object of the present invention is to provide a method of manufacturing a stacked heat exchanger.
本発明は以下に示すろう付け用多層めっき層を有するステンレス鋼板、これを用いた物品、その製造方法を提供するものである。
１．ステンレス鋼板の少なくとも一方の面に、ストライクＮｉめっき層、Ｎｉ−Ｐめっき層及びＣｒめっき層をこの順に設けたことを特徴とするろう付け用多層めっき層を有するステンレス鋼板。
２．ステンレス鋼板の両面に、ストライクＮｉめっき層、Ｎｉ−Ｐめっき層及びＣｒめっき層をこの順に設けたことを特徴とするろう付け用多層めっき層を有するステンレス鋼板。
３．Ｎｉ−Ｐめっき層中のＰ含量が５〜１５質量％である上記１又は２記載のステンレス鋼板。
４．Ｎｉ−Ｐめっき層の厚みが４〜１００μｍである上記１〜３のいずれか１項記載のステンレス鋼板。
５．Ｃｒめっき層の厚みが２〜５０μｍである上記１〜４のいずれか１項記載のステンレス鋼板。
６．Ｎｉ−Ｐめっき層の厚みとＣｒめっき層の厚みの比が１０：１〜１：１０である上記１〜５のいずれか１項記載のステンレス鋼板。
７．Ｎｉ−Ｐめっき層とＣｒめっき層の全厚が６〜１５０μｍである上記１〜６のいずれか１項記載のステンレス鋼板。
８．上記１〜７のいずれか１項記載のステンレス鋼板を使用して製造された物品。
９．積層型熱交換器である上記８記載の物品。
１０．ＥＧＲクーラである上記８記載の物品。
１１．複数のプレートとフィンを積層し、互いにろう付けして積層型熱交換器を製造する方法において、該プレートの材料が、ステンレス鋼板の両面に、ストライクＮｉめっき層、Ｎｉ−Ｐめっき層及びＣｒめっき層をこの順に設けたろう付け用多層めっき層を有するステンレス鋼板であることを特徴とする積層型熱交換器を製造する方法。
１２．積層型熱交換器が、ＥＧＲクーラである上記１１記載の方法。
The present invention provides a stainless steel plate having a multilayer plating layer for brazing shown below, an article using the same, and a method for producing the same.
1. A stainless steel plate having a brazing multilayer plating layer, wherein a strike Ni plating layer, a Ni-P plating layer, and a Cr plating layer are provided in this order on at least one surface of the stainless steel plate.
2. A stainless steel plate having a multilayer plating layer for brazing, wherein a strike Ni plating layer, a Ni-P plating layer, and a Cr plating layer are provided in this order on both surfaces of the stainless steel plate.
3. The stainless steel plate according to 1 or 2 above, wherein the P content in the Ni-P plating layer is 5 to 15% by mass.
4). The stainless steel plate according to any one of the above items 1 to 3, wherein the Ni-P plating layer has a thickness of 4 to 100 µm.
5. The stainless steel plate according to any one of the above 1 to 4, wherein the Cr plating layer has a thickness of 2 to 50 µm.
6). The stainless steel plate according to any one of 1 to 5 above, wherein the ratio of the thickness of the Ni-P plating layer to the thickness of the Cr plating layer is 10: 1 to 1:10.
7). The stainless steel plate according to any one of 1 to 6 above, wherein the total thickness of the Ni-P plating layer and the Cr plating layer is 6 to 150 µm.
8). Articles manufactured using the stainless steel plate according to any one of 1 to 7 above.
9. 9. The article according to 8 above, which is a laminated heat exchanger.
10. 9. The article according to 8 above, which is an EGR cooler.
11. In a method of manufacturing a laminated heat exchanger by laminating a plurality of plates and fins and brazing each other, the material of the plate is a strike Ni plating layer, a Ni-P plating layer and a Cr plating on both surfaces of a stainless steel plate A method for producing a laminated heat exchanger, characterized in that it is a stainless steel plate having a brazing multilayer plating layer in which layers are provided in this order.
12 12. The method according to 11 above, wherein the stacked heat exchanger is an EGR cooler.
本発明の多層めっき層を有するステンレス鋼板は、コイル材として多層めっき処理が可能であり、製造コストを大幅に低くすることが可能である。この多層めっき層をろう材として用いることにより、作業性が優れ、安価で、耐食性、ぬれ性が優れ、さらに低融点（１０５０℃程度）のろう接合を行うことができる。このため、耐食性に優れたろう接合物品、例えば、ＥＧＲクーラをはじめとする熱交換器等の物品を安価に製造することができる。 The stainless steel plate having the multilayer plating layer of the present invention can be subjected to multilayer plating as a coil material, and can greatly reduce the manufacturing cost. By using this multilayer plating layer as a brazing material, it is possible to perform brazing with excellent workability, low cost, excellent corrosion resistance and wettability, and a low melting point (about 1050 ° C.). For this reason, brazing joint articles excellent in corrosion resistance, for example, articles such as heat exchangers including EGR coolers can be manufactured at low cost.
ステンレス鋼板の表面上へのＮｉ−Ｐめっきには、その下地処理として脱脂、酸による活性化処理、塩酸＋塩化ニッケル浴によるストライクＮｉめっき処理が必要である。このストライクＮｉめっき皮膜の存在によって、ステンレス鋼板製プレートとＮｉ−Ｐめっき層とは強固に密着する。脱脂、酸による活性化処理、塩酸＋塩化ニッケル浴によるストライクＮｉめっき処理はいずれも公知の方法を適用できる。例えば、脱脂は、ＮａＯＨ等の苛性アルカリの濃度５〜１００ｇ／Ｌのアルカリ電解脱脂剤を用いて、１０〜９０℃、０．１〜１００Ａ／ｄｍ2の電流密度で１０秒間〜１０分間のアノード電解脱脂処理を行えば良い。 Ni-P plating on the surface of a stainless steel plate requires degreasing, activation treatment with an acid, and strike Ni plating treatment with a hydrochloric acid + nickel chloride bath as a base treatment. Due to the presence of the strike Ni plating film, the stainless steel plate and the Ni-P plating layer are firmly adhered. Any known method can be applied to degreasing, activation treatment with acid, and strike Ni plating treatment using hydrochloric acid + nickel chloride bath. For example, degreasing is performed by using an alkaline electrolytic degreasing agent having a caustic concentration of 5 to 100 g / L such as NaOH at 10 to 90 ° C. and a current density of 0.1 to 100 A / dm 2 for 10 seconds to 10 minutes. An electrolytic degreasing process may be performed.
酸による活性化処理は、上記脱脂処理したものを水洗後、５０〜２００ｇ／Ｌ濃度、例えば、１００ｇ／Ｌ濃度、３０〜８０℃、例えば、６０℃の塩酸水溶液に１〜１０分間、例えば、３分間浸漬して、試料表面を活性化させ、試料を水洗することなく、直ちに、５０〜２００ｇ／Ｌ濃度、例えば、１００ｇ／Ｌ濃度、５〜５０℃、例えば、室温の塩酸水溶液に浸漬後、０．１〜５０Ａ／ｄｍ2、例えば、５Ａ／ｄｍ2の電流密度で０．１〜１０分間、例えば、１分間のカソード電解を施し、表面調製を行う。 In the activation treatment with an acid, after washing the above-mentioned degreased treatment, it is washed with a hydrochloric acid aqueous solution having a concentration of 50 to 200 g / L, for example, 100 g / L, 30 to 80 ° C., for example, 60 ° C. for 1 to 10 minutes. Immediately after immersion in an aqueous hydrochloric acid solution at a concentration of 50 to 200 g / L, for example, 100 g / L, 5 to 50 ° C., for example, room temperature without rinsing the sample surface by immersing for 3 minutes and washing the sample with water 0.1 to 50 A / dm 2 , for example, 5 A / dm 2 at a current density of 0.1 to 10 minutes, for example, for 1 minute, cathode electrolysis is performed to prepare the surface.
その後、試料を水洗することなく、直ちに、５０〜２００ｇ／Ｌ濃度、例えば、１００ｇ／Ｌ濃度の塩酸と５０〜５００ｇ／Ｌ濃度、例えば、２５０ｇ／Ｌ濃度の塩化ニッケル（６水和物）の溶液中で、０．１〜３０Ａ／ｄｍ2、例えば、５Ａ／ｄｍ2の電流密度で０．１〜１０分間、例えば、１分間のカソード電解を施し、試料表面に０．０１〜１μｍ、例えば、約０．３μｍ厚さのＮｉめっき（ストライクＮｉめっき）を生成させる。このストライクＮｉめっき処理は、上層となるＮｉ−Ｐめっきとの密着性を確保する上で欠かせない処理である。 Thereafter, without washing the sample with water, immediately, hydrochloric acid having a concentration of 50 to 200 g / L, for example, 100 g / L concentration and nickel chloride (hexahydrate) having a concentration of 50 to 500 g / L, for example, 250 g / L. In the solution, cathodic electrolysis is performed at a current density of 0.1 to 30 A / dm 2 , for example, 5 A / dm 2 for 0.1 to 10 minutes, for example, 1 minute, and 0.01 to 1 μm, for example, on the sample surface. Then, Ni plating (strike Ni plating) having a thickness of about 0.3 μm is generated. This strike Ni plating process is an indispensable process for ensuring the adhesion with the Ni-P plating as an upper layer.
Ｎｉ−Ｐめっき方法は、還元剤として次亜リン酸塩、例えば、次亜リン酸ナトリウム等を１０〜３０ｇ／Ｌ濃度で含む浴（ｐＨは好ましくは４〜１０）で、７０〜１００℃、３０〜６０分間の無電解めっきを行う方法、硫酸ニッケル、塩化ニッケル等のニッケル塩を１００〜５００ｇ／Ｌ濃度で含む水溶液にホスホン酸、リン酸等を５〜２００ｇ／Ｌ加えた浴（ｐＨは好ましくは０．１〜７）で、２０〜８０℃、０．１〜５０Ａ／ｄｍ2、例えば、６０℃、５Ａ／ｄｍ2の電流密度で５〜３０分間の電気めっきを行う方法のいずれでもよい。 The Ni-P plating method is a bath (pH is preferably 4 to 10) containing hypophosphite as a reducing agent, for example, sodium hypophosphite and the like at a concentration of 10 to 30 g / L. A method of performing electroless plating for 30 to 60 minutes, a bath in which 5-200 g / L of phosphonic acid, phosphoric acid or the like is added to an aqueous solution containing nickel salts such as nickel sulfate and nickel chloride at a concentration of 100 to 500 g / L (pH is Any of the methods in which electroplating is preferably performed at a current density of 20 to 80 ° C. and 0.1 to 50 A / dm 2 , for example, 60 ° C. and 5 A / dm 2 for 5 to 30 minutes. Good.
ただし、無電解めっきに比べて、電気めっきは、短時間で目標厚さまで皮膜を成長させることができるが、電流密度の分布に不均一が生じた場合には、皮膜厚さ、およびＰ含有量にばらつきが生じる。一方、無電解めっきでは、めっき層の厚さ、Ｐ含有量は一定であるが、浴の寿命が短いという欠点がある。
Ｎｉ−Ｐめっき層のＰ含有量は好ましくは５〜１５質量％、さらに好ましくは８〜１３質量％である。Ｎｉ−Ｐめっき皮膜中のＰ含有量が高くなるとともに、液相線温度が低下し、融点が低下するが、１５質量％を越えると、過共晶傾向が強くなり、液相線温度が上昇する。
Ｎｉ−Ｐめっき層の厚みは好ましくは４〜１００μｍ、さらに好ましくは４〜５０μｍ、最も好ましくは１０〜５０μｍである。
However, compared with electroless plating, electroplating can grow a film to the target thickness in a short time. However, if the current density distribution is uneven, the film thickness and the P content Variation occurs. On the other hand, in electroless plating, the thickness of the plating layer and the P content are constant, but there is a drawback that the bath life is short.
The P content of the Ni-P plating layer is preferably 5 to 15% by mass, more preferably 8 to 13% by mass. While the P content in the Ni-P plating film increases, the liquidus temperature decreases and the melting point decreases. However, when the content exceeds 15% by mass, the hypereutectic tendency increases and the liquidus temperature increases. To do.
The thickness of the Ni—P plating layer is preferably 4 to 100 μm, more preferably 4 to 50 μm, and most preferably 10 to 50 μm.
上層のＣｒめっき層は、一般的に使用されているサージャント浴（三酸化クロム：硫酸＝１００：１）や、またはこれに電流（析出）効率を上昇させる市販の添加剤や、フッ化物、ケイフッ化物、例えば、ケイフッ化ナトリウム等を１〜１０ｇ／Ｌ程度加えてもよい。
具体的には、三酸化クロム（２００〜５００ｇ／Ｌ、例えば、３２０ｇ／Ｌ）と硫酸（２〜５ｇ／Ｌ、例えば、４ｇ／Ｌ）に市販の添加剤（例えば、カニングジャパン（株）製ＭＭ−４１）を１００〜１４０ｍｌ／Ｌ加えた浴において、３５〜６５℃、例えば、５５℃、電流密度１０〜５０Ａ／ｄｍ2、例えば、４０Ａ／ｄｍ2一定で、５〜３０分間処理することによりＣｒめっきを施す。
The upper Cr plating layer may be a commonly used sergeant bath (chromium trioxide: sulfuric acid = 100: 1), or a commercially available additive, fluoride, or silica fluoride that increases current (precipitation) efficiency. A compound such as sodium silicofluoride may be added in an amount of about 1 to 10 g / L.
Specifically, chromium trioxide (200 to 500 g / L, for example, 320 g / L) and sulfuric acid (2 to 5 g / L, for example, 4 g / L) are commercially available additives (for example, manufactured by Canning Japan Co., Ltd.). MM-41) in a bath containing 100 to 140 ml / L, treated at 35 to 65 ° C., for example, 55 ° C., current density of 10 to 50 A / dm 2 , for example, 40 A / dm 2 constant for 5 to 30 minutes. Apply Cr plating.
Ｃｒめっき層の厚みは好ましくは２〜５０μｍ、さらに好ましくは３〜３０μｍ、最も好ましくは４〜３０μｍである。
こうして形成された多層めっき皮膜は、下層Ｎｉ−Ｐめっきの融点以上の温度で溶融する。例えばＮｉ−１１％Ｐの融点は８８０℃であり、これ以上の温度で溶融する。溶融したＮｉ−Ｐは上層のＣｒめっき層及び下層のストライクＮｉ層と反応して、これを融解させ、その結果、Ｎｉ−Ｃｒ−Ｐの合金組成を有するろうが生成する。
The thickness of the Cr plating layer is preferably 2 to 50 μm, more preferably 3 to 30 μm, and most preferably 4 to 30 μm.
The multilayer plating film thus formed melts at a temperature equal to or higher than the melting point of the lower layer Ni—P plating. For example, the melting point of Ni-11% P is 880 ° C. and melts at a temperature higher than this. The molten Ni—P reacts with the upper Cr plating layer and the lower strike Ni layer to melt it, resulting in the formation of a braze having an alloy composition of Ni—Cr—P.
本発明において、Ｎｉ−Ｐめっき層の厚みとＣｒめっき層の厚みの比は、好ましくは１０：１〜１：１０、さらに好ましくは５：１〜１：５、最も好ましくは３：１〜１：３である。
またＮｉ−Ｐめっき層とＣｒめっき層の全厚は好ましくは６〜１５０μｍ、さらに好ましくは７〜８０μｍ、最も好ましくは１０〜６０μｍである。
In the present invention, the ratio of the Ni-P plating layer thickness to the Cr plating layer thickness is preferably 10: 1 to 1:10, more preferably 5: 1 to 1: 5, and most preferably 3: 1 to 1. : 3.
The total thickness of the Ni—P plating layer and the Cr plating layer is preferably 6 to 150 μm, more preferably 7 to 80 μm, and most preferably 10 to 60 μm.
上記ステンレス鋼板を使用し、各種の物品を製造することができる。
例えば、ステンレス鋼製の薄板状のプレートと矩形フィンとを複数積層し、該複数の構成部品を加熱して互いにろう付けし、熱交換器を製造する方法において、該プレートとして本発明の上記ステンレス鋼板を使用し、該ステンレス鋼板のＮｉ−Ｐめっき層の融点より高温、例えば、９００〜１２００℃で１〜２０分間加熱処理することにより積層型熱交換器を製造することができる。この際、ステンレス鋼板の多層めっき層がろう材として機能し、構成部品が互いにろう付けされ、熱交換器が形成される。この方法は、作業性が優れ、安価で、ろう付けされた部分の耐食性、ぬれ性が優れ、さらに低融点（1050℃程度）でろう接合が可能である。この方法によりＥＧＲクーラ等の熱交換器を安価で製造できる。
Various articles can be manufactured using the stainless steel sheet.
For example, in a method of laminating a plurality of thin plate plates made of stainless steel and rectangular fins, heating the plurality of components and brazing each other, and manufacturing a heat exchanger, the stainless steel of the present invention is used as the plate. A laminated heat exchanger can be manufactured by using a steel plate and heat-treating it at a temperature higher than the melting point of the Ni—P plating layer of the stainless steel plate, for example, at 900 to 1200 ° C. for 1 to 20 minutes. At this time, the multilayer plating layer of the stainless steel plate functions as a brazing material, and the components are brazed together to form a heat exchanger. This method has excellent workability, is inexpensive, has excellent corrosion resistance and wettability at the brazed portion, and can be brazed with a low melting point (about 1050 ° C.). By this method, a heat exchanger such as an EGR cooler can be manufactured at low cost.
以下、本発明の代表的な実施例を示す。
実施例
板厚０．４ｍｍのフェライト系ステンレス鋼板のＳＵＳ４３０Ｊ１Ｌを供試材として用いた。この供試材の化学組成は、質量％で０．０１％Ｃ−０．４７％Ｓｉ−０．１３％Ｍｎ−０．０２５％Ｐ−０．００４％Ｓ−０．２８％Ｎｉ−１９．３０％Ｃｒ−０．４５％Ｃｕ−０．６０％Ｎｂである。この供試材を適当な大きさ（２０ｍｍ×２０ｍｍ）に切断して、プレート試料とした。
Hereinafter, typical examples of the present invention will be described.
Example SUS430J1L, a ferritic stainless steel plate having a thickness of 0.4 mm, was used as a test material. The chemical composition of this test material is 0.01% C-0.47% Si-0.13% Mn-0.025% P-0.004% S-0.28% Ni-19. 30% Cr-0.45% Cu-0.60% Nb. This sample material was cut into an appropriate size (20 mm × 20 mm) to obtain a plate sample.
試料を、ＮａＯＨ濃度が４０ｇ／Ｌの市販アルカリ電解脱脂剤を用いて、６０℃、５Ａ／ｄｍ2の電流密度で１分間のアノード電解脱脂処理した。水洗後に１００ｇ／Ｌ濃度、６０℃の塩酸水溶液に３分間浸漬して、試料表面を活性化させた。 The sample was subjected to anodic electrolytic degreasing treatment at 60 ° C. and a current density of 5 A / dm 2 for 1 minute using a commercially available alkaline electrolytic degreasing agent having a NaOH concentration of 40 g / L. After washing with water, the sample surface was activated by immersing in an aqueous hydrochloric acid solution having a concentration of 100 g / L and 60 ° C. for 3 minutes.
試料を水洗することなく、直ちに、１００ｇ／Ｌ濃度、室温の塩酸水溶液に浸漬後、５Ａ／ｄｍ2の電流密度で１分間のカソード電解を施し、表面調製を行った。 Without rinsing the sample, the sample was immediately immersed in an aqueous hydrochloric acid solution having a concentration of 100 g / L and room temperature, followed by cathodic electrolysis for 1 minute at a current density of 5 A / dm 2 to prepare the surface.
その後、試料を水洗することなく、直ちに、１００ｇ／Ｌ濃度の塩酸と２５０ｇ／Ｌ濃度の塩化ニッケル（６水和物）の溶液中で、５Ａ／ｄｍ2の電流密度で１分間のカソード電解を施した。これによって、試料表面には約０．３μｍ厚さのＮｉめっき（ストライクＮｉめっき）が生成した。このストライクＮｉめっきは、上層となるＮｉ−Ｐめっきとの密着性を確保する上で欠かせない処理である。 Then, without washing the sample with water, immediately, cathodic electrolysis for 1 minute at a current density of 5 A / dm 2 in a solution of 100 g / L hydrochloric acid and 250 g / L nickel chloride (hexahydrate) was performed. gave. As a result, Ni plating (strike Ni plating) having a thickness of about 0.3 μm was formed on the sample surface. This strike Ni plating is a process indispensable for ensuring adhesion with the Ni-P plating as an upper layer.
試料を水洗後、硫酸ニッケル６水和物（１７０ｇ／Ｌ）、８５質量％リン酸（５０ｍＬ／Ｌ）、塩化ニッケル６水和物（５０ｇ／Ｌ）、ホスホン酸（亜リン酸：１０ｇ／Ｌ）の水溶液中、６０℃で電流密度１５Ａ／ｄｍ2一定で電解時間を変化させながらＮｉ−Ｐめっきを施した。なお、処理後にＮｉ−Ｐめっき皮膜のＰ濃度をＥＰＭＡ分析した結果、Ｐ濃度は１２質量％であることが分かった。 After washing the sample with water, nickel sulfate hexahydrate (170 g / L), 85 mass% phosphoric acid (50 mL / L), nickel chloride hexahydrate (50 g / L), phosphonic acid (phosphorous acid: 10 g / L) Ni-P plating was carried out at 60 ° C. in a constant current density of 15 A / dm 2 while varying the electrolysis time. As a result of EPMA analysis of the P concentration of the Ni—P plating film after the treatment, it was found that the P concentration was 12% by mass.
試料を水洗後、三酸化クロム（３２０ｇ／Ｌ）と硫酸（４ｇ／Ｌ）に市販の添加剤（カニングジャパン（株）製ＭＭ−４１）（１２０ｍｌ／Ｌ）を加えた浴において、５５℃、電流密度４０Ａ／ｄｍ2一定で、電解時間を変化させながらＣｒめっきを施した。 After washing the sample with water, in a bath in which a commercially available additive (MM-41 manufactured by Canning Japan Co., Ltd.) (120 ml / L) was added to chromium trioxide (320 g / L) and sulfuric acid (4 g / L), Cr plating was performed while changing the electrolysis time at a constant current density of 40 A / dm 2 .
このように、ステンレス鋼板製のプレート表面にＮｉ−Ｐめっきを施した後、上層にＣｒめっきを施し、これらめっき層をろう材とするプレート試料を調製した（Ｎｉ−Ｐめっき厚さおよびＣｒめっき厚さの異なる９水準）。この多層めっきプレート試料表面にＳＵＳ３０４鋼（質量％で０．０６％Ｃ−０．４６％Ｓｉ−０．８３％Ｍｎ−０．０２９％Ｐ−０．００４％Ｓ−８．６５％Ｎｉ−１８．２０％Ｃｒ）製のパイプ（外径１．２ｍｍφ、内径０．９ｍｍφ）を載置し、真空炉内にセットした後、真空度３×１０-5ｔｏｒｒにおいて１０５０℃まで昇温させ、５分間の保持後、冷却した。 Thus, after Ni-P plating was performed on the surface of a stainless steel plate, Cr plating was applied to the upper layer, and a plate sample using these plating layers as a brazing material was prepared (Ni-P plating thickness and Cr plating). 9 levels with different thickness). SUS304 steel (0.06% C-0.46% Si-0.83% Mn-0.029% P-0.004% S-8.65% Ni-18 on the surface of this multilayer plating plate sample. .20% Cr) pipe (outer diameter 1.2 mmφ, inner diameter 0.9 mmφ) was placed and set in a vacuum furnace, and then the temperature was raised to 1050 ° C. at a vacuum degree of 3 × 10 −5 torr. After holding for a minute, it was cooled.
ろう付け前の多層めっき層の密着性、ろう材のろう付け性、耐食性を評価した。
（１）めっき皮膜の密着試験：
ろう付け前のめっき皮膜の密着性は、試料をＲ＝０．４ｍｍでＶブロック法の９０度曲げして、皮膜の剥離程度を評価した。
○：剥離なし、
×：剥離あり
（２）ろう付け性：
パイプおよびＳＵＳ４３０Ｊ１Ｌ製プレート材の断面組織が観察できるように試料を切断した。この切断試料を樹脂に埋め込んだ後、湿式およびバフ研磨によって鏡面に仕上げ、レーザー顕微鏡によってろう材の状態を観察して評価した。
○：ろうのはじき無し（ぬれ広がり性良好）
△：ろうのはじき僅かに有り
×：ろうのはじき有り
（３）耐食性：
上記（２）の試料を５質量％塩酸水溶液、３０℃に試料を１時間浸漬し、ＳＵＳ４３０Ｊ１Ｌプレートとろう材の侵食程度を比較した。
○：ろう材の耐食性がＳＵＳ４３０Ｊ１Ｌプレート材より優れる
△：ろう材の耐食性がＳＵＳ４３０Ｊ１Ｌプレート材と同等
×：ろう材の耐食性がＳＵＳ４３０Ｊ１Ｌプレート材より劣る
The adhesion of the multilayer plating layer before brazing, the brazing property of the brazing material, and the corrosion resistance were evaluated.
(1) Plating film adhesion test:
For the adhesion of the plating film before brazing, the sample was bent at 90 ° by the V-block method with R = 0.4 mm, and the degree of peeling of the film was evaluated.
○: No peeling
X: Peeling (2) Brazing property:
The sample was cut so that the cross-sectional structure of the pipe and the plate material made of SUS430J1L could be observed. After this cut sample was embedded in the resin, it was finished to a mirror surface by wet and buffing, and evaluated by observing the state of the brazing material with a laser microscope.
○: No wax repellency (good wettability)
△: There is a slight amount of wax repellency ×: There is a wax repellency (3) Corrosion resistance:
The sample (2) was immersed in a 5% by mass hydrochloric acid aqueous solution at 30 ° C. for 1 hour, and the degree of erosion between the SUS430J1L plate and the brazing material was compared.
○: Corrosion resistance of brazing material is superior to SUS430J1L plate material. Δ: Corrosion resistance of brazing material is equivalent to SUS430J1L plate material. ×: Corrosion resistance of brazing material is inferior to SUS430J1L plate material.
表１に試料の詳細および評価結果を示す。「−」は試験しなかったことを示す。
ろう付け前のめっき皮膜は、９０度曲げ（曲げＲ＝０．４ｍｍ）することにより、すべての試料（試料Ｎｏ．１〜９）で軽微な割れが発生したが、皮膜の剥離は認められず、密着性は十分あると考えられる。なお、めっき皮膜の密着性が不完全ならば、高温においてめっき皮膜にフクレ、剥離が発生し、多層めっきの合金化が不完全になるものと推定されるが、ろう付け後にはＣｒ−Ｎｉ−Ｐが合金化されており、めっき皮膜の密着性は優れたものであると判断できる。
Table 1 shows the details of the samples and the evaluation results. “-” Indicates not tested.
The plating film before brazing was bent at 90 degrees (bending R = 0.4 mm), and minor cracks occurred in all samples (sample Nos. 1 to 9), but no peeling of the film was observed. It is considered that there is sufficient adhesion. In addition, if the adhesion of the plating film is incomplete, it is estimated that blistering and peeling occur in the plating film at a high temperature, and the alloying of the multilayer plating becomes incomplete, but after brazing, Cr—Ni— It can be judged that P is alloyed and the adhesion of the plating film is excellent.
また、多層めっき層がＶブロック法の９０度曲げ試験で剥離しなかったことから、ろう付け前の多層めっき皮膜は軽微なプレス加工にも耐え得ると考えられる。さらに、コイル材として多層めっき処理は可能であり、製造コストを大幅に小さくすることが可能と考えられる。 Moreover, since the multilayer plating layer did not peel in the 90-degree bending test of the V block method, it is considered that the multilayer plating film before brazing can withstand a slight press work. Furthermore, multilayer plating can be performed as the coil material, and the manufacturing cost can be significantly reduced.
ろう付け性の評価結果から、Ｎｉ−Ｐ皮膜の厚さは４μｍ以上、好ましくは１０μｍ以上が望ましいことがわかる。
ろう材の耐食性に関しては、Ｃｒめっき厚さが、２μｍ以上、好ましくは４μｍ以上が望ましいことがわかる。
From the evaluation results of the brazeability, it can be seen that the thickness of the Ni-P coating is preferably 4 μm or more, and more preferably 10 μm or more.
With respect to the corrosion resistance of the brazing material, it can be seen that the Cr plating thickness is desirably 2 μm or more, preferably 4 μm or more.
図１に、試料Ｎｏ．８の条件でろう付けした後のレーザー顕微鏡による断面観察結果を示す。１０５０℃で５分間の短時間ろう付けにもかかわらず、ぬれ広がり性も十分であることがわかる。 In FIG. The cross-sectional observation result by the laser microscope after brazing on condition of 8 is shown. It can be seen that, despite the short brazing at 1050 ° C. for 5 minutes, the wetting and spreading properties are sufficient.
Claims (12)
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2013036338A (en) * | 2011-08-03 | 2013-02-21 | Toyota Motor Corp | Egr system of internal combustion engine |
| US20140093419A1 (en) * | 2012-10-02 | 2014-04-03 | Hon Hai Precision Industry Co., Ltd. | Mold made of nickel-phosphorus alloy |
| JP2020050928A (en) * | 2018-09-28 | 2020-04-02 | 国立大学法人群馬大学 | Method of manufacturing brazing sheet |
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| JP2000061627A (en) * | 1998-08-20 | 2000-02-29 | Nisshin Steel Co Ltd | Brazing method for ferritic stainless steel plate |
| JP2002028775A (en) * | 2000-05-10 | 2002-01-29 | Denso Corp | Method for manufacturing corrosion resistant heat exchanger |
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| JPS61204392A (en) * | 1985-03-07 | 1986-09-10 | Nisshin Steel Co Ltd | Production of chromium coated stainless steel strip |
| JP2000061627A (en) * | 1998-08-20 | 2000-02-29 | Nisshin Steel Co Ltd | Brazing method for ferritic stainless steel plate |
| JP2002028775A (en) * | 2000-05-10 | 2002-01-29 | Denso Corp | Method for manufacturing corrosion resistant heat exchanger |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2013036338A (en) * | 2011-08-03 | 2013-02-21 | Toyota Motor Corp | Egr system of internal combustion engine |
| US20140093419A1 (en) * | 2012-10-02 | 2014-04-03 | Hon Hai Precision Industry Co., Ltd. | Mold made of nickel-phosphorus alloy |
| JP2020050928A (en) * | 2018-09-28 | 2020-04-02 | 国立大学法人群馬大学 | Method of manufacturing brazing sheet |
| JP7209276B2 (en) | 2018-09-28 | 2023-01-20 | 国立大学法人群馬大学 | Brazing sheet manufacturing method |
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