JP2005154844A - Different metal-joined member having excellent corrosion resistance, and its production method - Google Patents

Different metal-joined member having excellent corrosion resistance, and its production method Download PDF

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JP2005154844A
JP2005154844A JP2003396050A JP2003396050A JP2005154844A JP 2005154844 A JP2005154844 A JP 2005154844A JP 2003396050 A JP2003396050 A JP 2003396050A JP 2003396050 A JP2003396050 A JP 2003396050A JP 2005154844 A JP2005154844 A JP 2005154844A
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metal
zinc
aluminum
corrosion resistance
ion
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JP4365667B2 (en
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Hidekazu Ido
秀和 井戸
Mikako Takeda
実佳子 武田
Wataru Urushibara
亘 漆原
Atsushi Kato
淳 加藤
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Kobe Steel Ltd
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Kobe Steel Ltd
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Abstract

<P>PROBLEM TO BE SOLVED: To secure excellent corrosion resistance in a member obtained by joining an iron based material and an aluminum or aluminum alloy material by a means suitable for practical use. <P>SOLUTION: In the method of producing a different metal-joined member having excellent corrosion resistance, a member obtained by joining an iron based material and an aluminum or aluminum alloy material is dipped into a solution comprising fluoro complex ions and zinc ions, and metal zinc is deposited near the joint. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

本発明は、自動車等に使用されるアルミ−鋼異種金属接合部位に使用される、耐異種金属接触腐食性に優れる部材とその製造方法に関する。     The present invention relates to a member excellent in the dissimilar metal contact corrosion resistance used in an aluminum-steel dissimilar metal joint site used for automobiles and the like, and a method for producing the same.

自動車等の部材の接合部位に異種金属を組み合わせて用いると、異種金属が互いに接触して電気的に導通するために腐食が促進されることが知られている。
この様な異種金属の接触による腐食は、金属のイオン化傾向の違いによってこの金属間に電位差が生じ腐食電流が流れることによって発生する。従来、異種金属接触による腐食を防止するために、以下のような対策が知られている。 It is known that when dissimilar metals are used in combination at a joint portion of a member such as an automobile, the dissimilar metals come into contact with each other and are electrically connected, thereby promoting corrosion.
Corrosion due to contact of such different metals occurs when a potential difference occurs between the metals due to a difference in ionization tendency of the metal and a corrosion current flows. Conventionally, the following countermeasures are known in order to prevent corrosion due to contact with different metals.

(1)従来技術１（特許文献１など）
卑電位を示す金属と貴電位を示す金属とが接触する場合、その中間電位を示す金属を卑電位を示す金属側に溶射する。溶射は卑貴両金属のいずれか一方又は両方に施してもよい。こうして両金属との電位差を小さくすることができ、卑電位を示す金属の電食を低減することができる。 (1) Prior art 1 (Patent Document 1 etc.)
When a metal showing a base potential and a metal showing a noble potential come into contact, the metal showing the intermediate potential is sprayed on the metal side showing the base potential. Thermal spraying may be applied to either or both of the base metals. Thus, the potential difference between the two metals can be reduced, and the electrolytic corrosion of the metal exhibiting a base potential can be reduced.

(2)従来技術２（特許文献２など）
水溶液中で接触させた２種の金属のうちアノードを形成する金属の表面に選択的アニオン透過作用を有する塗料を下塗りする。さらにその上に選択的カチオン透過作用を有する塗料を重ね塗りするか、カチオン交換膜を下塗り塗料で接着被覆するか、あるいはイオン交換複合膜を金属側にアニオン交換体側、溶液側にカチオン交換体側が向くように下塗り塗料で接着被膜する。またはカソードを形成する金属面上にカチオン透過作用を有する塗料を下塗りし、その上に選択的アニオン透過作用を有する塗料を重ね塗り、又はその他の方法で両金属間におけるイオンの電気泳動を遮断して、接触腐食を防止する。 (2) Prior art 2 (Patent Document 2 etc.)
A paint having a selective anion permeation effect is primed on the surface of the metal that forms the anode of the two metals contacted in an aqueous solution. Further, a coating having a selective cation permeating action is repeatedly applied thereon, or the cation exchange membrane is adhesively coated with a primer coating, or the ion exchange composite membrane is placed on the anion exchanger side on the metal side and the cation exchanger side on the solution side. Adhesive coat with undercoat so that it faces. Alternatively, a cation-permeating paint is primed on the metal surface that forms the cathode, and a selective anion-permeating paint is overcoated thereon, or otherwise the ion electrophoresis between the two metals is blocked. Prevent contact corrosion.

(3) 従来技術３（特許文献３など）
異なる金属材料に端子を設け、直流電圧を印加し、金属材料のイオン化を防ぎ、電食の発生を防止する。 (3) Prior art 3 (Patent Document 3 etc.)
Terminals are provided on different metal materials, DC voltage is applied, ionization of the metal material is prevented, and the occurrence of electrolytic corrosion is prevented.

(4)従来技術４（特許文献４など）
中継器筐体およびアンカーハウジングの金属表面にアルミニウムより卑な金属を多量に含有する導電性塗料を塗布する
(5)従来技術５（特許文献５など）
Cu、Cu−Zn合金およびNiなどの金属表面に、Crめっきを施すと、接触する異種金属材料の相手方金属材料であるZn合金、Fe、Alなどのより卑の方の金属材料の腐食量が減少する
(6)従来技術６（特許文献６など）
鉄よりイオン化傾向が大きい金属からなるシートの両面に異種金属をメッキ処理して、鋼板との自然電極電位差が０乃至−３００ｍＶの防錆シートを構成し、この防錆シートを２枚の鋼板の接合面間に挟持せしめることにより防錆層を形成する。 (4) Prior art 4 (Patent Document 4 etc.)
Apply conductive paint containing a larger amount of metal than aluminum to the metal surfaces of the relay housing and anchor housing.
(5) Prior art 5 (Patent Document 5 etc.)
When Cr plating is applied to a metal surface such as Cu, Cu-Zn alloy and Ni, the amount of corrosion of the base metal material such as Zn alloy, Fe, Al, etc., which is the opposite metal material of the dissimilar metal material that comes into contact, is reduced. Decrease
(6) Prior art 6 (Patent Document 6 etc.)
Dissimilar metals are plated on both sides of a sheet made of a metal that has a higher ionization tendency than iron to form a rust-proof sheet having a natural electrode potential difference of 0 to -300 mV with the steel sheet. A rust prevention layer is formed by sandwiching between the joining surfaces.

(7)従来技術７（特許文献７など）
アルミニウム合金と接触する異種金属物体に、合金めっきを基準として１〜５重量% のコバルト含有量の亜鉛・コバルト合金めっきを施す。 (7) Prior art 7 (Patent Document 7 etc.)
A dissimilar metal object in contact with the aluminum alloy is plated with a zinc / cobalt alloy having a cobalt content of 1 to 5% by weight based on the alloy plating.

(8)従来技術８（特許文献８など）
応力腐食感受性を有するアルミニウム合金鋳物と異種金属の鋼部材とが応力負荷下に接する構造物において、アルミニウム合金鋳物の応力腐食を防止する方法であり、これら鋳物と鋼部材との間における接触領域の少なくとも一部に、鋳物の自然電位より１００ｍＶｖｓＳＣＥ以上卑であるか、あるいは、混成電位で−１５００ｍＶｖｓＳＣＥ以上貴である金属部材又は金属層を介在させるアルミニウム合金鋳物の応力腐食防止方法である。
特開昭５５−６４１１号公報 特開昭６０−５８２７２号公報 特開昭６１−２３７７７号公報 特公昭５４−２８９４号公報 特公昭５９−３７７５３号公報 特開平５−２２２５５７号公報 特開平７−２５２６７９号公報 特開平９−１５７８７０号公報 上記のように、異種金属の接触腐食を防止する方法は種々あるが、実際の接合部材への適用を想定した場合、これらの従来技術は以下のような問題点を有している。従来技術１は溶射を用いるため複雑形状の部材には適用できない。従来技術２、４及び８は接合部の最近傍やすき間に塗装することは困難である。従来技術３は異なる金属材料に端子を設けて安定的に直流電圧を印加することは、輸送機や建材において実施困難である。従来技術５は貴な金属にCrめっきを施すことは、適用できる部材の大きさの点で限界がある。また、６価クロムを使用するため、環境上問題がある。従来技術６は異種金属をめっきしたシートを接合部に挟み込むことは、製造上大変困難であり、また、接合時の熱によってシートが消失する可能性がある。従来技術７は接合部材に適用する場合には、接合部のめっきが溶融除去されるため、効果が小さい。 (8) Prior art 8 (Patent Document 8 etc.)
This is a method for preventing stress corrosion of an aluminum alloy casting in a structure in which an aluminum alloy casting having stress corrosion sensitivity and a steel member of a dissimilar metal are in contact with each other under a stress load. This is a method for preventing stress corrosion of an aluminum alloy casting in which a metal member or a metal layer, which is at least partially lower than the natural potential of the casting by 100 mV vs SCE or lower than the hybrid potential by −1500 mV vs SCE, is interposed.
Japanese Patent Laid-Open No. 55-6411 JP 60-58272 A JP 61-23777 A Japanese Patent Publication No.54-2894 Japanese Examined Patent Publication No.59-37753 Japanese Patent Laid-Open No. 5-222557 Japanese Patent Laid-Open No. 7-252679 As described above, there are various methods for preventing contact corrosion of dissimilar metals. However, when the application to an actual joining member is assumed, these conventional techniques have the following problems. Have. Since prior art 1 uses thermal spraying, it cannot be applied to a member having a complicated shape. It is difficult for the prior arts 2, 4 and 8 to be applied in the vicinity of the joint and the gap. In the prior art 3, it is difficult to implement terminals in different metal materials and stably apply a DC voltage in transportation equipment and building materials. In the prior art 5, there is a limit in applying Cr plating to a noble metal in terms of the size of an applicable member. Moreover, since hexavalent chromium is used, there is an environmental problem. In the prior art 6, it is very difficult to manufacture a sheet that is plated with a dissimilar metal between the joints, and there is a possibility that the sheet may disappear due to heat at the time of joining. When the prior art 7 is applied to a joining member, the plating at the joint is melted and removed, so that the effect is small.

本発明は上記した従来技術の問題点を一挙に解消し、実用に適した手段により鉄系材料とアルミニウム又はアルミニウム合金材料接合された部材の優れた耐食性を確保することをその課題としたものである。   The object of the present invention is to solve the above-mentioned problems of the prior art at once, and to ensure excellent corrosion resistance of a member joined with an iron-based material and aluminum or aluminum alloy material by means suitable for practical use. is there.

上記の課題を達成するために、本発明者らが提案する発明の特徴は以下の通りである。
（１）鉄系材料とアルミニウム又はアルミニウム合金材料が接合された部材を、フルオロ錯イオンおよび亜鉛イオンを含有する溶液中に浸漬し、接合部近傍に金属亜鉛を析出させることを特徴とする耐食性に優れた異種金属接合部材の製造方法（請求項１）。
（２）前記フルオロ錯イオンがヘキサフルオロケイ酸イオン、又は、テトラフルオロホウ酸イオンである上記（１）に記載の製造方法（請求項２）。
（３）前記フルオロ錯イオン濃度、及び、前記亜鉛イオン濃度が2mmol/L以上である上記（１）又は（２）に記載の製造方法（請求項３）。
（４）鉄系材料とアルミニウム又はアルミニウム合金材料が接合された部材であって、鉄系材料の接合面側接合部近傍に、金属亜鉛を存在させたことを特徴とする耐食性に優れた異種金属接合部材（請求項４）。
（５）金属亜鉛が析出されたものである上記（４）に記載の耐食性に優れた異種金属接合部材（請求項５）。
（６）金属亜鉛がフルオロ錯イオンおよび亜鉛イオンを含有する溶液中に、接合された部材を浸漬して析出されたものである上記（４）に記載の耐食性に優れた異種金属接合部材（請求項６）。 In order to achieve the above object, the features of the invention proposed by the present inventors are as follows.
(1) Corrosion resistance characterized by immersing a member in which an iron-based material and aluminum or an aluminum alloy material are joined in a solution containing a fluoro complex ion and zinc ions to deposit metallic zinc in the vicinity of the joint. A method for producing an excellent dissimilar metal joining member (Claim 1).
(2) The production method according to (1), wherein the fluoro complex ion is a hexafluorosilicate ion or a tetrafluoroborate ion (claim 2).
(3) The production method according to (1) or (2), wherein the fluoro complex ion concentration and the zinc ion concentration are 2 mmol / L or more (Claim 3).
(4) A member in which an iron-based material and aluminum or an aluminum alloy material are joined, and is made of metal zinc in the vicinity of the joint portion on the joining surface side of the iron-based material. Joining member (Claim 4).
(5) The dissimilar metal joining member having excellent corrosion resistance according to (4), wherein metallic zinc is deposited (Claim 5).
(6) The dissimilar metal joint member having excellent corrosion resistance according to the above (4), wherein the metal zinc is deposited by immersing the joined member in a solution containing fluoro complex ions and zinc ions (claim) Item 6).

本発明によれば、アルミニウムより電気化学的に貴な金属である鉄系材料とアルミニウムとの接合部近傍に、金属亜鉛を析出状態で存在させたことによって、耐異種金属接触腐食性を確実に向上させることができる。   According to the present invention, the presence of metal zinc in a precipitated state in the vicinity of the junction between the iron-based material, which is an electrochemically noble metal than aluminum, and aluminum ensures the resistance to dissimilar metal contact corrosion. Can be improved.

アルミニウム又はアルミニウム合金材料（以下、アルミニウム系材料あるいは単にアルミニウムという）と鉄、鋼又は鉄合金（以下鉄系材料あるいは単に鉄という）を接合させた場合、図２に示すように、通常、鉄（Ｆｅ）より脾な金属であるアルミニウム（Ａｌ）がＡｌ3+イオンとなって溶出し、腐食が促進される。これはアルミニウムと鉄との電位差が大きいために、腐食電流が両材料間に流れるためである。
従って、こうした腐食の促進を防止するためには、この異種金属接合影響部に、アルミと鉄の中間的なイオン化傾向を有する金属を存在させることによりこの電位差を小さすれば良いことがわかる。先の従来技術もこのような原理を利用して接触腐食を抑制しようとしているのである。
しかしながら、従来技術では前述の通りの実用上の問題点を有し、特に接合部の最近傍や小さなすき間に中間的なイオン化傾向を有する金属を十分に存在させることが困難であり、このため実際の技術として採用するまでには至っていないのが現状である。
本発明者らはかかる実情に鑑みて、鋭意、実験と研究を積み重ねた結果、アルミと鉄の接合部材を、フルオロ錯イオンおよび亜鉛イオンを含有する溶液中に浸漬することによって、接合部近傍に緻密且つ強固な密着性の高い金属亜鉛を短時間で確実に存在させることができ、そしてこの金属亜鉛がアルミと鉄の中間的なイオン化傾向を有するために上記接合部材の優れた異種金属接触耐食性が発揮されることを確認した。
このフルオロ錯イオンおよび亜鉛イオンを含有する溶液中に接合体を浸漬する方法によれば、両材料の電位差があることを利用して、下記反応
２Ａｌ + ３Ｚｎ2+ → ２Ａｌ3+ + ３Ｚｎ
を接合部近傍の異種金属接合による電位差の影響がある部位で進行させ、図１に示すように、金属亜鉛をこの部位の鉄の表面に析出させて、付着、存在させることができる。そして、この亜鉛は析出によって形成されるため非常に狭い接合部近傍であっても鉄の表面に確実且つ十分に付着させることができ、しかも亜鉛の析出層は緻密で密着性が高く、剥離や破壊によって消失し難く長期に亘って付着状態を維持することができる。この結果、電位差の影響が緩和され、腐食を効果的に抑制することができるのである。 When aluminum or an aluminum alloy material (hereinafter referred to as an aluminum-based material or simply aluminum) and iron, steel or an iron alloy (hereinafter referred to as an iron-based material or simply iron) are joined, as shown in FIG. Aluminum (Al), which is a spleen metal of Fe), elutes as Al 3+ ions and promotes corrosion. This is because the corrosion current flows between both materials because the potential difference between aluminum and iron is large.
Therefore, in order to prevent the promotion of such corrosion, it can be understood that this potential difference should be reduced by allowing a metal having an ionization tendency intermediate between aluminum and iron to be present in the dissimilar metal joint influence part. The prior art also attempts to suppress contact corrosion using this principle.
However, the prior art has practical problems as described above, and in particular, it is difficult to have a metal having an intermediate ionization tendency in the vicinity of a joint or a small gap. The current situation is that the technology has not yet been adopted.
In view of such circumstances, the present inventors have earnestly conducted experiments and research, and as a result, the aluminum and iron joint members are immersed in a solution containing a fluoro complex ion and zinc ions, so that the vicinity of the joint is obtained. Dense and strong metallic zinc with high adhesion can be surely present in a short time, and since this metallic zinc has an intermediate ionization tendency between aluminum and iron, the excellent dissimilar metal contact corrosion resistance of the above joining member It was confirmed that
According to the method of immersing the joined body in the solution containing this fluoro complex ion and zinc ion, the following reaction 2Al + 3Zn 2+ → 2Al 3+ + 3Zn is made possible by utilizing the potential difference between the two materials.
Can be made to proceed at a site affected by the potential difference due to the dissimilar metal bonding in the vicinity of the bonded portion, and as shown in FIG. And since this zinc is formed by precipitation, it can be reliably and sufficiently adhered to the surface of iron even in the vicinity of a very narrow joint, and the deposited layer of zinc is dense and has high adhesiveness. It is difficult to disappear due to destruction, and the adhesion state can be maintained for a long time. As a result, the influence of the potential difference is alleviated and corrosion can be effectively suppressed.

さらに、フルオロ錯イオンはアルミニウム表面の酸化皮膜を溶解し、上記反応を円滑にする働きがある。フルオロ錯イオンを含む塩としては、たとえば、ヘキサフルオロケイ酸塩、テトラフルオロホウ酸塩、ヘキサフルオロりん酸塩、フルオロ硫酸塩があるが、安定性、反応性からヘキサフルオロケイ酸塩、テトラフルオロホウ酸塩を用いることが好ましい。   Furthermore, the fluoro complex ion has a function of dissolving the oxide film on the aluminum surface and smoothing the reaction. Examples of the salt containing a fluoro complex ion include hexafluorosilicate, tetrafluoroborate, hexafluorophosphate, and fluorosulfate. From the viewpoint of stability and reactivity, hexafluorosilicate, tetrafluoro It is preferable to use a borate.

処理時間としては接合部材の耐食性確保と生産性から３０秒〜３分が望ましく、処理温度は反応性と温度制御の容易さから４０℃以上、処理液の蒸発抑制から８０℃以下であることが望ましい。
なお、接合部近傍は通常部材に挟まれた部分であるため、電気めっきや溶射等他の方法では処理不能である。 The treatment time is preferably 30 seconds to 3 minutes from the viewpoint of ensuring corrosion resistance and productivity of the joining member, and the treatment temperature is 40 ° C. or more from the viewpoint of reactivity and ease of temperature control, and 80 ° C. or less from the suppression of evaporation of the treatment liquid. desirable.
Since the vicinity of the joint is a portion sandwiched between ordinary members, it cannot be processed by other methods such as electroplating or thermal spraying.

１.実験方法
(1)スポット溶接
軟鋼板(30×100×0.8mm)とアルミ板(6022および5023、30×100×0.8mm)を12kV、200msの条件でスポット溶接した。
(2)亜鉛塩処理
表１に示す溶液に60℃で30〜120s浸漬した。
(3)化成処理
処理工程： (a)脱脂→ (b)水洗→ (c)表面調整→ (d)化成処理（ディップ処理）→ (e)化成後乾き→ (f)水洗→ (g)純水洗→ (h)水切り乾燥→ (i)塗装の順に処理を行った。
(a)脱脂：アルカリ脱脂処理剤（日本ペイント（株）社製、商品名「サーフクリーナーＳＤ２５０」）のＡ剤：１．５ｗｔ％、Ｂ剤：０．９ｗｔ％水溶液を用い、４３℃で２分間、浸漬処理した。
(b)水洗：室温で水道水中に１５秒間浸漬した。
(c)表面調整：表面調整剤（日本ペイント（株）社製、商品名「サーフファイン５Ｎ−１０」建浴用）の０．１ｗｔ％水溶液を用い、室温で３０秒間、処理対象金属を浸漬処理した。
(d)化成処理：下記リン酸亜鉛処理剤を処理浴として被処理材を50℃、2min浸漬して化成処理を行った。
亜鉛イオン：１．０ｇ／ｌ、ニッケルイオン：１．０ｇ／ｌ、マンガンイオン：０．８ｇ／ｌ、リン酸イオン：１５．０ｇ／ｌ、硝酸イオン：６．０ｇ／ｌ、亜硝酸イオン：０．１２ｇ／ｌ
トーナー値：２．５ｐｔ、全酸度：２２ｐｔ、遊離酸度：０．３〜０．５ ｐｔ
(4)電着塗装
カチオン電着塗料（日本ペイント（株）社製、商品名「パワートップＶ５０グレー」）をカチオン電着塗装により塗装し、温度１７０℃で２５分間焼き付けし、膜厚３０μｍの塗装皮膜を形成した。 1. Experimental method
(1) Spot weld mild steel plate (30 × 100 × 0.8 mm) and aluminum plate (6022 and 5023, 30 × 100 × 0.8 mm) were spot welded under conditions of 12 kV and 200 ms.
(2) Zinc salt treatment It was immersed in the solution shown in Table 1 at 60 ° C for 30 to 120 seconds.
(3) Chemical conversion treatment process: (a) Degreasing → (b) Water washing → (c) Surface adjustment → (d) Chemical conversion treatment (dip treatment) → (e) Drying after chemical conversion → (f) Water washing → (g) Pure The treatment was performed in the order of washing with water → (h) draining / drying → (i) painting.
(a) Degreasing: Alkaline degreasing agent (trade name “Surf Cleaner SD250”, manufactured by Nippon Paint Co., Ltd.) A agent: 1.5 wt%, B agent: 0.9 wt% aqueous solution at 43 ° C. 2 Immersion treatment was performed for a minute.
(b) Washing with water: Dipped in tap water at room temperature for 15 seconds.
(c) Surface adjustment: The metal to be treated is dipped for 30 seconds at room temperature using a 0.1 wt% aqueous solution of a surface conditioner (made by Nippon Paint Co., Ltd., trade name “Surffine 5N-10” for building bath). did.
(d) Chemical conversion treatment: The chemical treatment was performed by immersing the material to be treated in the following zinc phosphate treatment agent as a treatment bath at 50 ° C. for 2 minutes.
Zinc ion: 1.0 g / l, nickel ion: 1.0 g / l, manganese ion: 0.8 g / l, phosphate ion: 15.0 g / l, nitrate ion: 6.0 g / l, nitrite ion: 0.12 g / l
Toner value: 2.5 pt, total acidity: 22 pt, free acidity: 0.3 to 0.5 pt
(4) Electrodeposition coating Cationic electrodeposition paint (manufactured by Nippon Paint Co., Ltd., trade name “Power Top V50 Gray”) was applied by cationic electrodeposition coating and baked at a temperature of 170 ° C. for 25 minutes. A paint film was formed.

(5)耐食性試験(CCT)
上述(1)〜(4)で作製した試験片を用いて、複合腐食試験を行い異種金属接触腐食防止性の評価を行った。腐食試験は、塩水噴霧２時間、乾燥２時間、湿潤２時間を１サイクルとする試験をくり返し１００回行なった。接合部を剥離させて観察し、耐食性(Alの最大腐食深さ)を評価した。
２.結果
耐食性、化成処理性の評価結果を表１に示す。ここで耐食性はＡｌの最大腐食深さ（mm）を測定し、○：０〜０.０１（mm）、△：０.０１〜０.１（mm）、×：０.１（mm）以上の３段階にランク分けして評価した。また、化成処理性は塗膜の付着量を測定し、○：１〜２（ｇ／m2）、△：０.５〜１（ｇ／m2）、×：０〜０.５（ｇ／m2）の３段階にランク分けして評価した。
同表から発明例1〜9では化成処理性、耐食性共に優れていることが分かる。一方、比較例10ではフルオロ錯イオンの反応性が低いため、効果が不十分である。
なお、以上の説明では、異種金属接合部材としてアルミニウムと鉄について述べたが、本発明はそのイオン化傾向が亜鉛より貴な金属と脾な金属を接合した部材の耐食性向上策にも応用することが可能である。 (5) Corrosion resistance test (CCT)
Using the test pieces prepared in the above (1) to (4), a composite corrosion test was performed to evaluate the corrosion resistance against dissimilar metals. The corrosion test was repeated 100 times with a cycle of 2 hours of salt spray, 2 hours of drying and 2 hours of wetting. The joint was peeled and observed to evaluate the corrosion resistance (maximum corrosion depth of Al).
2. Results Table 1 shows the evaluation results of corrosion resistance and chemical conversion treatment. Here, the corrosion resistance is measured by measuring the maximum corrosion depth (mm) of Al, ○: 0 to 0.01 (mm), Δ: 0.01 to 0.1 (mm), ×: 0.1 (mm) or more Evaluation was performed by classifying into three stages. Further, the chemical conversion treatment was performed by measuring the adhesion amount of the coating film, ○: 1-2 (g / m 2 ), Δ: 0.5-1 (g / m 2 ), x: 0-0.5 (g / M 2 ) and graded into three stages.
It can be seen from Table 1 that Invention Examples 1 to 9 are excellent in chemical conversion treatment properties and corrosion resistance. On the other hand, in Comparative Example 10, the reactivity of the fluoro complex ion is low, so the effect is insufficient.
In the above description, aluminum and iron are described as the dissimilar metal joining members. However, the present invention can be applied to a measure for improving the corrosion resistance of a member obtained by joining a metal having a higher ionization tendency than a zinc and a spleen metal. Is possible.

本発明によるアルミニウム−鉄接合部材の接合部近傍（接合影響部）における金属亜鉛の析出状態並びに腐食の抑制メカニズムを示す模式図である。It is a schematic diagram which shows the precipitation suppression state of metal zinc in the joint part vicinity (joining influence part) of the aluminum-iron joining member by this invention, and the suppression mechanism of corrosion. アルミニウム−鉄接合部材の接合部近傍（接合影響部）における腐食の促進メカニズムを示す模式図である。It is a schematic diagram which shows the acceleration | stimulation mechanism of corrosion in the junction part vicinity (joining influence part) of an aluminum-iron joining member.

Claims (6)

鉄系材料とアルミニウム又はアルミニウム合金材料が接合された部材を、フルオロ錯イオンおよび亜鉛イオンを含有する溶液中に浸漬し、接合部近傍に金属亜鉛を析出させることを特徴とする耐食性に優れた異種金属接合部材の製造方法。 A member in which an iron-based material and aluminum or an aluminum alloy material are bonded is immersed in a solution containing a fluoro complex ion and zinc ion, and metallic zinc is precipitated in the vicinity of the bonded portion. Manufacturing method of metal joining member. 前記フルオロ錯イオンがヘキサフルオロケイ酸イオン、又は、テトラフルオロホウ酸イオンである請求項１に記載の製造方法。 The production method according to claim 1, wherein the fluoro complex ion is a hexafluorosilicate ion or a tetrafluoroborate ion. 前記フルオロ錯イオン濃度、及び、前記亜鉛イオン濃度が2mmol/L以上である請求項１又は２に記載の製造方法。 The production method according to claim 1, wherein the fluoro complex ion concentration and the zinc ion concentration are 2 mmol / L or more. 鉄系材料とアルミニウム又はアルミニウム合金材料が接合された部材であって、鉄系材料の接合面側接合部近傍に、金属亜鉛を存在させたことを特徴とする耐食性に優れた異種金属接合部材。 A member in which an iron-based material and aluminum or an aluminum alloy material are bonded, wherein a metal zinc is present in the vicinity of a bonding surface side bonded portion of the iron-based material, and the dissimilar metal bonded member having excellent corrosion resistance. 金属亜鉛が析出されたものである請求項４に記載の耐食性に優れた異種金属接合部材。 5. The dissimilar metal joining member having excellent corrosion resistance according to claim 4, wherein metallic zinc is deposited. 金属亜鉛がフルオロ錯イオンおよび亜鉛イオンを含有する溶液中に、接合された部材を浸漬して析出されたものである請求項４に記載の耐食性に優れた異種金属接合部材。


5. The dissimilar metal bonded member with excellent corrosion resistance according to claim 4, wherein the metal zinc is deposited by immersing the bonded member in a solution containing fluoro complex ions and zinc ions.


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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1882542A1 (en) 2006-07-25 2008-01-30 Nissan Motor Co., Ltd. Method and apparatus for bonding dissimilar metals materials using a seal material interposed therebetween ; Bonding structure formed by such method
KR20190138021A (en) 2018-06-04 2019-12-12 동국대학교 경주캠퍼스 산학협력단 Adhering member of hetero materials and method for preparing the same
JP2020040101A (en) * 2018-09-12 2020-03-19 太平洋工業株式会社 Aluminum alloy casting and method for manufacturing the same
JP6923099B1 (en) * 2021-03-23 2021-08-18 秋田県 Dissimilar metal joints and their manufacturing methods
JP7079436B1 (en) * 2021-07-12 2022-06-02 秋田県 Plating method

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1882542A1 (en) 2006-07-25 2008-01-30 Nissan Motor Co., Ltd. Method and apparatus for bonding dissimilar metals materials using a seal material interposed therebetween ; Bonding structure formed by such method
US8476549B2 (en) 2006-07-25 2013-07-02 Nissan Motor Co., Ltd. Method for bonding a seal member and dissimilar materials made from metals
KR20190138021A (en) 2018-06-04 2019-12-12 동국대학교 경주캠퍼스 산학협력단 Adhering member of hetero materials and method for preparing the same
JP2020040101A (en) * 2018-09-12 2020-03-19 太平洋工業株式会社 Aluminum alloy casting and method for manufacturing the same
JP6923099B1 (en) * 2021-03-23 2021-08-18 秋田県 Dissimilar metal joints and their manufacturing methods
WO2022202221A1 (en) * 2021-03-23 2022-09-29 秋田県 Dissimilar metal joined body and method for manufacturing same
JP7079436B1 (en) * 2021-07-12 2022-06-02 秋田県 Plating method

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