JPH06101043A - Al alloy plated metallic material excellent in corrosion resistance in edge face and its production - Google Patents
Al alloy plated metallic material excellent in corrosion resistance in edge face and its productionInfo
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- JPH06101043A JPH06101043A JP25157692A JP25157692A JPH06101043A JP H06101043 A JPH06101043 A JP H06101043A JP 25157692 A JP25157692 A JP 25157692A JP 25157692 A JP25157692 A JP 25157692A JP H06101043 A JPH06101043 A JP H06101043A
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Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、Al合金めっき金属材、
即ち、鋼材、チタン材、アルミニウム材、ステンレス鋼
材、クロム鋼材などの基体金属の表面にAl合金めっき皮
膜を有する材料に関する。本発明のAl合金めっき金属材
は端面耐食性に優れ、自動車外装用、建材、家電製品な
どの用途に最適である。The present invention relates to an Al alloy plated metal material,
That is, the present invention relates to a material having an Al alloy plating film on the surface of a base metal such as a steel material, a titanium material, an aluminum material, a stainless steel material, and a chrome steel material. The Al alloy-plated metal material of the present invention has excellent end face corrosion resistance, and is most suitable for applications such as automobile exteriors, building materials, and home appliances.
【０００２】[0002]
【従来の技術】AlまたはAl合金めっき金属材は、優れた
裸耐食性、美麗さ、無毒性など、多くの利点を有してい
ることはよく知られている。その製造方法としては、溶
融金属浸漬法、真空蒸着法、有機溶媒浴もしくは溶融塩
電解浴による電気めっき法等がある。このうち、主とし
て溶融金属浸漬法が採用されている。しかしながら、こ
の方法は、その対象がほとんどAl単体のめっきであり、
しかも薄めっきが困難で、かつ処理温度が700 ℃を超え
るため、基体金属との合金層の生成、母材への悪影響と
いった問題を抱えている。2. Description of the Related Art It is well known that Al or Al alloy plated metal materials have many advantages such as excellent bare corrosion resistance, beauty, and nontoxicity. Examples of the manufacturing method include a molten metal dipping method, a vacuum vapor deposition method, an electroplating method using an organic solvent bath or a molten salt electrolytic bath, and the like. Of these, the molten metal immersion method is mainly used. However, in this method, the target is plating of Al alone,
Moreover, since thin plating is difficult and the processing temperature exceeds 700 ° C, there are problems such as formation of an alloy layer with the base metal and adverse effect on the base material.
【０００３】近年では、溶融塩浴や非水溶媒浴による電
気めっき法を用いて、種々のAl合金めっき金属材 (例、
Al−Mn、Al−Ti、Al−Cr、Al−Pbなどの２元系Al合金め
っき金属材) を製造する試みがなされている。これらの
方法を用いると、薄めっきが容易で、処理温度が低いた
め母材に及ぼす影響も少なく、各種の合金めっきも可能
である。また、Al合金は、Al単体と比較すると、より優
れた耐食性が期待できる。しかしながら、これらのAl合
金めっき皮膜は塩水中での腐食電位がFeより貴であり、
特に鋼材と組合わせて用いた場合、犠牲防食能が小さ
く、鋼材露出部での耐食性 (即ち、端面耐食性) が劣る
という問題を有している。In recent years, various Al alloy-plated metal materials (eg, electroplating methods using molten salt baths and non-aqueous solvent baths) have been used.
Attempts have been made to produce binary Al alloy plated metal materials such as Al-Mn, Al-Ti, Al-Cr, and Al-Pb. When these methods are used, thin plating is easy, the treatment temperature is low, the influence on the base material is small, and various alloy plating is possible. Further, the Al alloy can be expected to have better corrosion resistance as compared with Al alone. However, these Al alloy plating films have a corrosion potential in salt water that is nobler than that of Fe,
In particular, when used in combination with a steel material, there is a problem that the sacrificial anticorrosion ability is small and the corrosion resistance at the exposed steel material (that is, the end surface corrosion resistance) is poor.
【０００４】このような問題を改善するために、先に本
発明者らは、金属材の表面に、犠牲防食能に優れたZnま
たはZn合金めっきを施し、その上にさらにAl合金めっき
を施した２層めっき金属材を提案した (特開昭61−2614
96号公報) 。しかし、特に自動車外装用鋼板等に要求さ
れる高度の端面耐食性に関しては、これらの２層めっき
鋼板でも十分な性能が得られていないのが現状である。In order to improve such a problem, the present inventors previously applied Zn or Zn alloy plating excellent in sacrificial anticorrosion ability to the surface of a metal material, and further applied Al alloy plating thereon. Proposed a two-layer plated metal material (JP-A-61-2614).
No. 96). However, in particular, regarding the high end face corrosion resistance required for steel sheets for automobile exteriors, the present situation is that these two-layer plated steel sheets have not obtained sufficient performance.
【０００５】[0005]
【発明が解決しようとする課題】本発明の目的は、Al合
金めっきの端面耐食性を改善することである。具体的に
は、３元系以上の多元系Al合金層を形成することによ
り、耐食性と同時に端面耐食性も改善されたAl合金めっ
き金属材を提供することである。An object of the present invention is to improve the end face corrosion resistance of Al alloy plating. Specifically, it is to provide an Al alloy plated metal material having improved corrosion resistance and at the same time end face corrosion resistance by forming a ternary or higher multi-element Al alloy layer.
【０００６】[0006]
【課題を解決するための手段】本発明者らは、上記の如
き２元系Al合金めっき (Al−Ｘ合金めっきとする) に、
AlまたはAl合金の腐食電位を卑にし、犠牲防食能を付与
することのできる第三の金属元素 (Ｙとする) を混入す
ることにより、端面耐食性を向上させることに着目し
た。しかし、このような３元系Al合金 (Al−Ｘ−Ｙ) か
らなるめっき皮膜を真空蒸着法、電気めっき法などによ
り直接形成しても、めっき皮膜の組成制御が困難であっ
て、実用に耐えるような製品を容易に製造することがで
きない。Means for Solving the Problems The inventors of the present invention have applied the binary Al alloy plating (Al-X alloy plating) as described above to
We focused on improving the end face corrosion resistance by making the corrosion potential of Al or Al alloy base and incorporating a third metal element (denoted as Y) capable of imparting sacrificial anticorrosion ability. However, even if a plating film made of such a ternary Al alloy (Al-XY) is directly formed by a vacuum vapor deposition method, an electroplating method, etc., it is difficult to control the composition of the plating film and it is practically used. A product that can withstand cannot be easily manufactured.
【０００７】そこで検討した結果、基体金属表面にAl−
Ｘ合金めっきとＹ金属またはＹ合金めっきとを、この両
めっき層が互いに隣接するように設けた後、得られた多
層めっき金属材を熱処理すると、Ｙ金属がAl−Ｘ合金め
っき皮膜中に熱拡散して、Al−Ｘ−Ｙの３元系めっき層
をめっき皮膜中に形成することができ、端面耐食性に優
れたAl合金めっき金属材を得ることができること、およ
び、この時の熱処理条件によりＹ金属の拡散量を制御で
き、従って、Al−Ｘ−Ｙ合金層の組成制御が容易である
ことを知り、本発明に到達した。[0007] As a result of the study, Al-
After the X alloy plating and the Y metal or Y alloy plating are provided so that the both plating layers are adjacent to each other, when the obtained multilayer plated metal material is heat-treated, the Y metal is heated in the Al-X alloy plating film. By diffusing, an Al-XY ternary plating layer can be formed in the plating film, an Al alloy-plated metal material having excellent end face corrosion resistance can be obtained, and heat treatment conditions at this time The present invention has been reached, knowing that the amount of diffusion of Y metal can be controlled and therefore the composition of the Al—X—Y alloy layer can be controlled easily.
【０００８】ここに、本発明の要旨は、基体金属表面の
一部または全面にめっき皮膜を有する金属材であって、
該めっき皮膜中にAl−Ｘ−Ｙ (ただし、ＸはMn、Ti、
Ｗ、Mo、Fe、Ni、CoおよびCuよりなる群から選ばれた少
なくとも１種の金属、ＹはMg、Ca、Sr、Ba、Zn、Cd、I
n、Tl、Si、Ge、Sn、Pb、As、SbおよびBiよりなる群か
ら選ばれた少なくとも１種の金属であって、Ｘ：１〜50
重量％、Ｙ： 0.1〜20重量％、Al：残部) で表される、
少なくとも１層の熱拡散Al合金層が存在することを特徴
とする、端面耐食性に優れたAl合金めっき金属材にあ
る。Here, the gist of the present invention is a metal material having a plating film on a part or the whole surface of a base metal,
Al-XY (where X is Mn, Ti,
At least one metal selected from the group consisting of W, Mo, Fe, Ni, Co and Cu, Y is Mg, Ca, Sr, Ba, Zn, Cd, I
at least one metal selected from the group consisting of n, Tl, Si, Ge, Sn, Pb, As, Sb and Bi, and X: 1 to 50
%, Y: 0.1 to 20% by weight, Al: balance),
It is an Al alloy-plated metal material having excellent end face corrosion resistance, which is characterized by the presence of at least one heat diffusion Al alloy layer.
【０００９】このAl−Ｘ−Ｙで表される少なくとも１層
の熱拡散Al合金層は、互いに隣接したAl−Ｘ合金めっき
層 (ただし、Ｘは上記の少なくとも１種の金属であり、
Ｘ：１〜50重量％) とＹ金属めっき層またはＹ合金めっ
き層 (ただし、Ｙは上記のの少なくとも１種の金属) の
熱処理により形成できる。The at least one thermal diffusion Al alloy layer represented by Al-X-Y is an Al-X alloy plating layer adjacent to each other (where X is at least one of the above metals,
X: 1 to 50% by weight) and a Y metal plating layer or a Y alloy plating layer (where Y is at least one metal described above).
【００１０】本発明により、基体金属表面の一部または
全面に、Al−Ｘ合金めっき (ただし、Ｘは上記の少なく
とも１種の金属であり、Ｘ：１〜50重量％) とＹ金属め
っきまたはＹ合金めっき (ただし、Ｙは上記の少なくと
も１種の金属) とを、両めっき層が互いに隣接するよう
にそれぞれ少なくとも１回づつ施した後、得られた多層
めっき金属材を 100〜500 ℃の温度範囲で熱処理するこ
とにより、めっき皮膜中にAl−Ｘ−Ｙ（ただし、Ｘおよ
びＹは上記と同じ意味）で表される熱拡散Al合金層を形
成することを特徴とする、上記Al合金めっき金属材の製
造方法も提供される。According to the present invention, Al-X alloy plating (where X is at least one metal described above, X: 1 to 50% by weight) and Y metal plating are applied to a part or the whole surface of the base metal according to the present invention. Y alloy plating (where Y is at least one of the above metals) is applied at least once so that both plating layers are adjacent to each other, and then the resulting multi-layer plated metal material is applied at 100 to 500 ° C. A heat diffusion Al alloy layer represented by Al-XY (where X and Y have the same meanings as described above) is formed in the plating film by heat treatment in a temperature range, the above Al alloy. A method for manufacturing a plated metal material is also provided.
【００１１】[0011]
【作用】本発明のAl合金めっき金属材の基体金属は、鋼
材、チタンまたはチタン合金材、アルミニウムまたはア
ルミニウム合金材、ステンレス鋼材、クロム鋼材など任
意の金属材料でよく、形状も板材、パネル材、棒材、管
材、線材など任意の形状でよい。The base metal of the Al alloy plated metal material of the present invention may be any metal material such as steel material, titanium or titanium alloy material, aluminum or aluminum alloy material, stainless steel material, chrome steel material, and the shape is plate material, panel material, Any shape such as a rod material, a pipe material, or a wire material may be used.
【００１２】本発明のAl合金めっき金属材は、この基体
金属の表面の一部または全面に、Al−Ｘ−Ｙ (ただし、
ＸはMn、Ti、Ｗ、Mo、Fe、Ni、CoおよびCuよりなる群か
ら選ばれた少なくとも１種の金属、ＹはMg、Ca、Sr、B
a、Zn、Cd、In、Tl、Si、Ge、Sn、Pb、As、SbおよびBi
よりなる群から選ばれた少なくとも１種の金属であっ
て、Ｘ：１〜50重量％、Ｙ： 0.1〜20重量％、Al：残
部) で表される熱拡散Al合金層を含んだめっき皮膜を有
している。The Al alloy-plated metal material of the present invention has a structure in which Al-XY (however,
X is at least one metal selected from the group consisting of Mn, Ti, W, Mo, Fe, Ni, Co and Cu, and Y is Mg, Ca, Sr, B
a, Zn, Cd, In, Tl, Si, Ge, Sn, Pb, As, Sb and Bi
A plating film containing at least one metal selected from the group consisting of X: 1 to 50% by weight, Y: 0.1 to 20% by weight, and Al: the balance) have.
【００１３】合金元素Ｘとして選択したMn、Ti、Ｗ、M
o、Fe、Ni、CoおよびCuは、いずれもAl系めっきの密着
性、従って耐食性を改善すると共に、めっき外観を向上
させる作用を有する。熱拡散Al合金層中のＸ金属の含有
量 (２種以上のＸ金属を含む場合には合計含有量) を１
〜50重量％としたのは、１重量％未満ではめっき皮膜が
パウダー状またはデンドライト状になり、50重量％を超
えると、めっき皮膜が硬化して脆くなり、実用性を喪失
させるからである。好ましいＸ金属の含有量は、15〜40
重量％、より好ましくは20〜35重量％である。Mn, Ti, W, M selected as alloy element X
All of o, Fe, Ni, Co, and Cu have the function of improving the adhesion of the Al-based plating, and thus the corrosion resistance, and improving the plating appearance. The content of X metal in the thermal diffusion Al alloy layer (total content when two or more X metals are contained) is 1
The reason for setting the content to -50% by weight is that if it is less than 1% by weight, the plating film becomes powdery or dendrite-like, and if it exceeds 50% by weight, the plating film hardens and becomes brittle and loses practicality. The preferred X metal content is 15-40
%, More preferably 20 to 35% by weight.
【００１４】Ｙ金属として選択したMg、Ca、Sr、Ba、Z
n、Cd、In、Tl、Si、Ge、Sn、Pb、As、SbおよびBiは、
いずれもAlおよびAl合金の腐食電位を卑にし、犠牲防食
能を付与することができる。熱拡散Al合金層中のＹ金属
の含有量 (２種以上のＹ金属を含む場合には合計含有
量) を 0.1〜20重量％としたのは、 0.1重量％未満では
その効果が発揮できず、20重量％を超えると、めっき皮
膜の密着性が損なわれ、実用性を喪失させるからであ
る。好ましいＹ金属の含有量は 0.1〜15重量％、より好
ましくは 0.5〜10重量％である。Mg, Ca, Sr, Ba, Z selected as Y metal
n, Cd, In, Tl, Si, Ge, Sn, Pb, As, Sb and Bi are
Both can make the corrosion potentials of Al and Al alloys base and provide sacrificial anticorrosion ability. The content of Y metal in the thermal diffusion Al alloy layer (when 2 or more types of Y metals are included, the total content) is set to 0.1 to 20% by weight, because the effect cannot be exhibited at less than 0.1% by weight. If it exceeds 20% by weight, the adhesion of the plating film is impaired and the practicality is lost. The content of the Y metal is preferably 0.1 to 15% by weight, more preferably 0.5 to 10% by weight.
【００１５】後で述べるように、熱拡散合金層は傾斜組
成を有するので、Al−Ｘ−Ｙ合金層中の各金属の含有量
は連続的に変化する。従って、本発明におけるAl−Ｘ−
Ｙ合金層中のＸおよびＹ含有量とは、この合金層領域に
おける各金属の含有量の最高値を意味する。As will be described later, since the thermal diffusion alloy layer has a graded composition, the content of each metal in the Al-XY alloy layer changes continuously. Therefore, Al-X- in the present invention
The X and Y contents in the Y alloy layer mean the maximum values of the contents of each metal in this alloy layer region.
【００１６】このAl−Ｘ−Ｙ熱拡散合金層は、基体金属
の表面の一部または全面に、Al−Ｘ合金めっき (ただ
し、Ｘは上記の少なくとも１種の金属であり、Ｘ：１〜
50重量％) とＹ金属めっきまたはＹ合金めっき (ただ
し、Ｙは上記の少なくとも１種の金属) とを、両めっき
層が互いに隣接するようにそれぞれ少なくとも１回づつ
施した後、熱処理を行って、Ｙ金属をAl−Ｘ合金めっき
皮膜中に熱拡散させることにより形成できる。例えば、
基体金属が板材 (例、鋼板) である場合、用途に応じ
て、上記めっきは板の片面のみ (例、自動車外装用鋼
板) 、或いは両面に施すことができる。なお、Ｙ合金め
っきは、Ｙ金属間の合金およびＹ金属と他の金属との合
金のいずれであってもよい。This Al-XY thermal diffusion alloy layer is formed by Al-X alloy plating (where X is at least one of the above-mentioned metals, and X: 1 to 1) on a part or the whole surface of the base metal.
50% by weight) and Y metal plating or Y alloy plating (where Y is at least one metal described above) at least once so that both plating layers are adjacent to each other, and then heat treatment is performed. , Y metal can be formed by thermal diffusion in the Al—X alloy plating film. For example,
When the base metal is a plate material (eg, steel plate), the plating can be applied to only one surface of the plate (eg, steel sheet for automobile exterior) or both surfaces depending on the application. The Y alloy plating may be an alloy between Y metals or an alloy of Y metal and another metal.
【００１７】具体的には、まず、下記の表１の「熱処理
前の構造」の欄に示すように、 Al−Ｘ合金めっき層 (Al−Ｘと表記) の下層にＹまた
はＹ合金めっき層 (Ｙと表記) を有する多層めっき金属
材、 Al−Ｘ合金めっき層の上層にＹまたはＹ合金めっき層
を有する多層めっき金属材、または Al−Ｘ合金めっき層の上層と下層にＹまたはＹ合金め
っき層を有する多層めっき金属材、のいずれかを形成す
る。Specifically, first, as shown in the column "Structure before heat treatment" in Table 1 below, a Y or Y alloy plating layer is formed under the Al-X alloy plating layer (denoted as Al-X). (Denoted as Y), a multi-layer plated metal material, a multi-layer plated metal material having a Y or Y alloy plating layer above the Al-X alloy plating layer, or a Y or Y alloy layer above and below the Al-X alloy plating layer One of a multi-layer plated metal material having a plated layer is formed.
【００１８】この多層めっき金属材のめっき構造は、上
記〜のみに限定されるものではなく、互いに隣接し
たAl−Ｘ合金めっき層とＹまたはＹ合金めっき層とを少
なくとも１層づつ有する限り、任意のめっき構造とする
ことができる。例えば、ＹまたはＹ合金めっき層の上層
と下層にAl−Ｘ合金めっき層を有していてもよく、或い
は両めっき層を交互に２層づつ有する、一方のめっき層
３層と他方のめっき層２層とを交互に有するといった、
より複雑な多層めっき構造も可能である。さらには、上
記以外の他のめっき層を最上層または最下層に有してい
てもよい。しかし、通常は上記〜のいずれかのめっ
き構造で本発明の目的を十分に達成することができるの
で、これらのいずれかの構造の多層めっき金属材を形成
すればよい。The plating structure of the multi-layer plated metal material is not limited to the above-mentioned (1) to (3) and may be any structure as long as it has at least one Al--X alloy plating layer and at least one Y or Y alloy plating layer adjacent to each other. Can have a plated structure. For example, an Al-X alloy plating layer may be provided as an upper layer and a lower layer of the Y or Y alloy plating layer, or two plating layers are alternately provided, one plating layer having three layers and the other plating layer having two layers. Having two layers alternating,
More complex multilayer plating structures are possible. Further, a plating layer other than the above may be provided as the uppermost layer or the lowermost layer. However, since the object of the present invention can be sufficiently achieved with any of the plating structures described above in general, it is sufficient to form the multilayer plated metal material having any of these structures.
【００１９】各めっき層の形成方法は限定されず、従来
公知の適当なめっき方法を採用すればよい。例えば、Al
−Ｘ合金めっき層は、真空蒸着法や、有機溶媒浴もしく
は溶融塩浴からの電気めっき法により形成することがで
き、ＹまたはＹ合金めっきは、真空蒸着法や、水溶液
浴、有機溶媒浴もしくは溶融塩浴からの電気めっき法に
より形成することができる。熱処理前の各めっき層の付
着量または厚みも特に限定されないが、好ましい範囲は
Al−Ｘ合金めっき層とＹまたはＹ合金めっき層のいずれ
についても１〜30μｍの範囲内である。Al−Ｘ合金めっ
きは２元系めっきであるので、めっきの皮膜組成の制御
は比較的容易である。The method of forming each plating layer is not limited, and a conventionally known appropriate plating method may be adopted. For example, Al
The -X alloy plating layer can be formed by a vacuum deposition method or an electroplating method from an organic solvent bath or a molten salt bath, and the Y or Y alloy plating can be formed by a vacuum deposition method, an aqueous solution bath, an organic solvent bath or It can be formed by an electroplating method from a molten salt bath. The adhesion amount or thickness of each plating layer before heat treatment is not particularly limited, but a preferable range is
Both the Al-X alloy plated layer and the Y or Y alloy plated layer are in the range of 1 to 30 μm. Since Al-X alloy plating is a binary plating, it is relatively easy to control the coating composition of the plating.
【００２０】こうして得た多層めっき金属材を熱処理す
ると、Ｙ金属がAl−Ｘ合金めっき層中に熱拡散し、Al−
Ｘ−Ｙ合金層 (Al−Ｘ−Ｙと表記) が形成される。その
際、最初に形成した各めっき層の厚みや熱処理条件によ
って、少なくとも１つのめっき層が完全にAl−Ｘ−Ｙ合
金層に転換され、そのめっき層が消失する場合と、全て
のめっき層が一部は残存し、上記２種類のめっき層間に
Al−Ｘ−Ｙ合金層が形成される場合とがある。従って、
上記〜の多層めっき金属材を熱処理した場合に生成
するめっき構造は、表１の「熱処理後の構造」の欄に示
すように、幾通りかの可能性があるが、いずれもめっき
皮膜中にAl−Ｘ−Ｙ合金層を少なくとも１層有するとい
う共通点がある。そして、このAl−Ｘ−Ｙ合金層がめっ
き皮膜中に存在する限り、この合金層が示す犠牲防食能
により、めっきの端面耐食性が確保されるのである。ま
た、この合金層は、Ｘ金属の存在により耐食性にも優れ
ている。When the multi-layer plated metal material thus obtained is heat-treated, Y metal is thermally diffused in the Al-X alloy plated layer, and Al-
An XY alloy layer (denoted as Al-XY) is formed. At that time, at least one plating layer is completely converted into an Al—X—Y alloy layer depending on the thickness of each initially formed plating layer and heat treatment conditions, and the plating layer disappears and all plating layers are removed. Some remain, and between the above two types of plating layers
In some cases, an Al-XY alloy layer is formed. Therefore,
As shown in the column of "Structure after heat treatment" in Table 1, there are several possibilities for the plating structure generated when the above-mentioned multilayer plated metal materials are heat treated. They have a common point of having at least one Al-XY alloy layer. As long as the Al-XY alloy layer is present in the plating film, the sacrificial anticorrosive ability of the alloy layer ensures the end face corrosion resistance of the plating. Further, this alloy layer also has excellent corrosion resistance due to the presence of the X metal.
【００２１】[0021]
【表１】 [Table 1]
【００２２】表１には、各めっき層間の拡散により得ら
れる層構造しか示していないが、実際には、最下層のめ
っき層と気体金属間の熱拡散も考えられる。Although only the layer structure obtained by diffusion between the plating layers is shown in Table 1, in reality, thermal diffusion between the lowermost plating layer and the gas metal is also conceivable.
【００２３】Al−Ｘ合金めっき層 (Al−Ｘ層) とＹまた
はＹ合金めっき層 (Ｙ層) が隣接した多層めっき (Al−
Ｘ／Ｙ) を熱処理すると、Ｙ金属は比較的拡散し易いの
で、Al−Ｘ中にＹ金属が侵入し、Al−Ｘ／Ｙの境界から
Al−Ｘのバルク方向にＹの組成が徐々に減少する傾斜組
成を持ったAl−Ｘ−Ｙ合金層 (Al−Ｘ−Ｙ層) が形成さ
れる。図１に示すように、一般にAl−Ｘ／Ｙの境界で
は、Ｙの濃度が不連続的に、従って、AlとＸの濃度も不
連続的に変化するため、Ｙの侵入 (熱拡散) により生成
したAl−Ｘ−Ｙ層とＹ層との境界は、ＥＰＭＡ (Ｘ線マ
イクロアナライザー) 等の手段で直接、または適当なエ
ッチングによる金相学的手段で明確に判別される。この
Ｙの熱拡散により、Al−Ｘ−Ｙ／Ｙの境界 (もしくはAl
−Ｘ−Ｙ／基体の境界) には、過剰な厚みの新たな金属
間化合物が形成されない限り (この形成は熱処理条件の
制御により防止できる) 、各層間およびめっき層／基体
間の冶金的結合が改善され、めっき密着性が向上する。Multi-layer plating (Al-, where the Al-X alloy plating layer (Al-X layer) and the Y or Y alloy plating layer (Y layer) are adjacent to each other.
(X / Y) is heat-treated, the Y metal is relatively easy to diffuse, so the Y metal penetrates into Al-X, and from the boundary of Al-X / Y.
An Al-XY alloy layer (Al-XY layer) having a graded composition in which the Y composition gradually decreases in the Al-X bulk direction is formed. As shown in FIG. 1, generally, at the Al-X / Y boundary, the concentration of Y changes discontinuously, and therefore the concentrations of Al and X also change discontinuously. The boundary between the formed Al-XY layer and the Y layer is clearly discriminated directly by means such as EPMA (X-ray microanalyzer) or by metallurgical means by appropriate etching. Due to this thermal diffusion of Y, the boundary of Al-XY / Y (or Al
-X-Y / substrate boundary), unless a new intermetallic compound having an excessive thickness is formed (this formation can be prevented by controlling the heat treatment conditions), the metallurgical bond between each layer and between the plating layer / substrate is formed. Is improved and plating adhesion is improved.
【００２４】熱処理条件は、Ｙ金属のAl−Ｘ合金めっき
層中への熱拡散により所望の厚みのAl−Ｘ−Ｙ合金層が
形成されるように選択すればよい。熱処理温度は 100〜
500℃の範囲内が好ましい。100 ℃以下では熱拡散が起
こりにくく、500 ℃を超える高温は母材金属への悪影響
(例、耐食性に有害な粒界析出物の生成など) や層間で
の金属間化合物の生成を生ずる恐れがある。より好まし
い熱処理温度は 150〜300 ℃である。熱処理時間は温度
によっても異なるが、通常は５時間以内で十分であり、
好ましくは２時間以内とする。The heat treatment conditions may be selected so that the Al—X—Y alloy layer having a desired thickness is formed by thermal diffusion of Y metal into the Al—X alloy plating layer. Heat treatment temperature is 100 ~
It is preferably in the range of 500 ° C. Thermal diffusion is less likely to occur below 100 ° C, and high temperatures above 500 ° C have a negative effect on the base metal.
(Eg, formation of intergranular precipitates harmful to corrosion resistance) or formation of intermetallic compounds between layers may occur. A more preferable heat treatment temperature is 150 to 300 ° C. The heat treatment time varies depending on the temperature, but usually 5 hours or less is sufficient,
It is preferably within 2 hours.
【００２５】熱拡散により形成したAl−Ｘ−Ｙ合金層
は、少なくとも0.1 μｍの厚みとすることが望ましい。
それ以下の厚みでは、端面耐食性の向上効果が不十分に
なることがある。より好ましくは、Al−Ｘ−Ｙ熱拡散合
金層の厚みを１μｍ以上とする。なお、Al−Ｘ−Ｙ熱拡
散合金層の厚みとは、めっき皮膜中に形成された上記Al
−Ｘ−Ｙの定義に該当する部分の厚みを意味する (但
し、Ｙ含有量の下限は 0.1重量ではなく、図１に示すよ
うに、Ｙ含有量が0.05重量以上の部分をAl−Ｘ−Ｙ層の
厚みとする) 。The Al-XY alloy layer formed by thermal diffusion preferably has a thickness of at least 0.1 μm.
If the thickness is less than that, the effect of improving the end face corrosion resistance may be insufficient. More preferably, the thickness of the Al-XY thermal diffusion alloy layer is 1 μm or more. The thickness of the Al-XY thermal diffusion alloy layer means the Al formed in the plating film.
-X-Y means the thickness of the portion corresponding to the definition (however, the lower limit of the Y content is not 0.1 weight, but as shown in FIG. 1, the portion having a Y content of 0.05 weight or more is Al-X- Y layer thickness).
【００２６】Al−Ｘ−Ｙ熱拡散合金層におけるＸ含有量
は、最初に形成するAl−Ｘ合金めっき層のＸ含有量によ
り制御できる。この合金層のＹ含有量は、主に熱処理条
件により制御でき、場合によっては、最初に形成した２
種類のめっき層の相対的な厚みの比にも依存する。ま
た、この合金層の厚みも、熱処理条件や最初に形成した
めっき層の厚みにより制御できる。このようにして、Al
−Ｘ−Ｙ熱拡散合金層の合金組成と厚みを容易に制御で
き、それにより各種特性を調整できる点が、本発明の利
点の一つである。The X content in the Al-XY thermal diffusion alloy layer can be controlled by the X content in the Al-X alloy plating layer formed first. The Y content of this alloy layer can be controlled mainly by the heat treatment conditions.
It also depends on the relative thickness ratio of the type of plating layer. The thickness of this alloy layer can also be controlled by the heat treatment conditions and the thickness of the plating layer formed first. In this way, Al
One of the advantages of the present invention is that the alloy composition and thickness of the -XY thermal diffusion alloy layer can be easily controlled, and various characteristics can be adjusted accordingly.
【００２７】また、表１に示すように、最初に形成した
Al−Ｘ合金めっき層やＹまたはＹ合金めっき層が一部残
存している場合には、これらの残存めっき層により、裸
耐食性や端面耐食性の一層の向上が得られる。Further, as shown in Table 1, it was formed first.
When a part of the Al-X alloy plating layer or the Y or Y alloy plating layer remains, these residual plating layers can further improve bare corrosion resistance and end face corrosion resistance.
【００２８】本発明のAl合金めっき金属材は、Al合金め
っき金属材に固有の裸耐食性、美麗さに加えて、その弱
点であった端面耐食性が著しく改善されているので、建
材や家電製品はもとより、厳しい端面耐食性が要求され
る自動車外装用途にも適用可能である。The Al alloy-plated metal material of the present invention has not only the bare corrosion resistance and beauty peculiar to the Al alloy-plated metal material but also the end face corrosion resistance, which is its weak point, is remarkably improved. Of course, it can also be applied to automotive exterior applications where strict corrosion resistance on the end surface is required.
【００２９】次に実施例により本発明をさらに詳しく説
明する。実施例中、％は特に指定しない限り、重量％で
ある。Next, the present invention will be described in more detail with reference to examples. In the examples,% is% by weight unless otherwise specified.
【００３０】[0030]
【実施例】基体金属として板厚0.8 mm×幅100 mm×長さ
100 mmの冷延鋼板を使用し、この鋼板の片面にMg、Ca、
Sr、Ba、Zn、Cd、In、Tl、Si、Ge、Sn、Pb、As、Sbまた
はBiからなるＹ金属めっきと、ＸがMn、Ti、Ｗ、Mo、F
e、Ni、CoまたはCuであるAl−Ｘ合金めっきとを、種々
のめっき厚みで施して、次の〜に示す多層めっき鋼
板サンプルを作成した。[Example] As a base metal, plate thickness 0.8 mm x width 100 mm x length
Using 100 mm cold rolled steel sheet, Mg, Ca,
Y metal plating consisting of Sr, Ba, Zn, Cd, In, Tl, Si, Ge, Sn, Pb, As, Sb or Bi, and X is Mn, Ti, W, Mo, F
Al-X alloy plating which is e, Ni, Co or Cu was applied with various plating thicknesses to prepare multilayer plated steel sheet samples shown in to.
【００３１】Ｙ金属めっき→Al−Ｘ合金めっきの順に
めっきを施した冷延鋼板を、めっき後に230 ℃で５〜60
分間熱処理したサンプル。 Al−Ｘ合金めっき→Ｙ金属めっきの順にめっきを施し
た冷延鋼板を、めっき後に250 ℃で５〜60分間熱処理し
たサンプル。 Ｙ金属めっき→Al−Ｘ合金めっき→Ｙ金属めっきの順
にめっきを施した冷延鋼板を、めっき後に270 ℃で１〜
30分間熱処理したサンプル。A cold-rolled steel sheet plated in the order of Y metal plating → Al-X alloy plating is plated at 230 ° C. for 5 to 60
Sample heat treated for minutes. A sample in which a cold-rolled steel sheet plated in the order of Al-X alloy plating-> Y metal plating is heat-treated at 250 ° C for 5 to 60 minutes after plating. Cold-rolled steel sheet plated in the order of Y metal plating → Al-X alloy plating → Y metal plating is 1 to 270 ℃ after plating.
Sample heat treated for 30 minutes.
【００３２】Ｙ金属めっきは真空蒸着法により、Al−Ｘ
合金めっきは下記条件下で溶融塩浴電気めっき法により
行った。Al−Ｘ合金めっき条件 浴組成：AlCl3-NaCl-KCl (AlCl3: 62 mol%, NaCl: 20 mol%, KCl: 18 mol%) 浴温度：200 ℃ 添加Ｘ化合物：Ｘ金属の塩化物 電流密度：５〜70Ａ/dm2 液流速： 0.3 m/sec 熱処理後に得られたAl合金めっき鋼板サンプルのめっき
皮膜の構造 (層の数、最下層を第１層とする）と各層の
組成および層厚を、ＥＰＭＡを用いて次のように測定し
た。即ち、ＥＰＭＡにより、めっき表面から深さ方向に
断面の組成分析を行い、構成元素の違いによりAl−Ｘ−
Ｙ層、Al−Ｘ層、Ｙ層の分離を行った。次に、この断面
を写真にとり、ミクロンバーと対比することで、各層の
厚みを決定した。Y metal plating is performed by vacuum vapor deposition method using Al--X.
Alloy plating was performed by a molten salt bath electroplating method under the following conditions. Al-X alloy plating conditions Bath composition: AlCl 3 -NaCl-KCl (AlCl 3 : 62 mol%, NaCl: 20 mol%, KCl: 18 mol%) Bath temperature: 200 ℃ Addition X compound: X metal chloride current Density: 5 to 70 A / dm 2 Liquid flow rate: 0.3 m / sec Structure of plating film of Al alloy plated steel sheet sample obtained after heat treatment (number of layers, lowermost layer is the first layer), composition of each layer and layers The thickness was measured using EPMA as follows. That is, the composition of the cross section in the depth direction from the plating surface is analyzed by EPMA, and Al-X-
The Y layer, the Al-X layer, and the Y layer were separated. Next, this cross section was photographed, and the thickness of each layer was determined by comparing with a micron bar.
【００３３】また、各Al合金めっきサンプルのめっき外
観、端面耐食性、および加工性 (耐パウダリング性) を
次のようにして評価した。Further, the plating appearance, end surface corrosion resistance, and workability (powdering resistance) of each Al alloy plated sample were evaluated as follows.
【００３４】めっき外観は、目視観察により、色調、光
沢等を評価した。端面耐食性は、両面をシールし、端面
のみを露出させためっき鋼板の試験片を複合腐食サイク
ル試験 (35℃、５％塩水噴霧試験18時間→50℃乾燥３時
間→35℃５％塩水浸漬試験３時間を１サイクルとする)
に60サイクル供した後、端面近傍の最大腐食深さを測定
し、最大腐食深さの値により次の５段階で評価した。The plating appearance was evaluated by visual observation such as color tone and gloss. End face corrosion resistance is a compound corrosion cycle test (35 ° C, 5% salt spray test 18 hours → 50 ° C drying 3 hours → 35 ° C 5% salt water immersion test) (3 hours is one cycle)
After 60 cycles, the maximum corrosion depth in the vicinity of the end face was measured, and the maximum corrosion depth value was used to evaluate the following 5 levels.
【００３５】５：0.1 mm未満、 ４：0.1 mm以
上0.3 mm未満、３：0.3 mm以上0.5 mm未満、２：0.5 mm
以上1.0 mm未満１：1.0 mm以上。5: less than 0.1 mm, 4: 0.1 mm to less than 0.3 mm, 3: 0.3 mm to less than 0.5 mm, 2: 0.5 mm
More than 1.0 mm less than 1.0 mm.
【００３６】耐パウダリング性は、めっき鋼板から直径
90 mm のブランクを採取し、これを直径50 mm 、深さ28
mm の円筒状に深絞り成形して、その側壁面のめっき皮
膜を粘着テープで剥離させる試験を行い、その剥離量を
目視調査して、次の５段階で評価した。５：全く剥離な
し、４：テープの全面積に対して剥離片の付着している
テープ面積が１％未満、３：同じく１％以上５％未満、
２：同じく５％以上10％未満、１：同じく10％以上。The powdering resistance depends on the diameter from the plated steel plate.
Take a 90 mm blank, 50 mm in diameter and 28 mm deep.
A deep drawing was carried out in a cylindrical shape of mm 2 and a test for peeling the plating film on the side wall surface thereof with an adhesive tape was conducted. The peeling amount was visually inspected and evaluated in the following 5 grades. 5: no peeling at all, 4: less than 1% of tape area with peeling pieces adhered to the entire area of the tape, 3: same 1% or more and less than 5%,
2: Same 5% or more and less than 10%, 1: Same 10% or more.
【００３７】上記の測定および試験結果を、次の表２−
１〜表９−２にまとめて示す。The above measurement and test results are shown in Table 2 below.
1 to Table 9-2 collectively.
【００３８】[0038]
【表２−１】 [Table 2-1]
【００３９】[0039]
【表２−２】 [Table 2-2]
【００４０】[0040]
【表３−１】 [Table 3-1]
【００４１】[0041]
【表３−２】 [Table 3-2]
【００４２】[0042]
【表４−１】 [Table 4-1]
【００４３】[0043]
【表４−２】 [Table 4-2]
【００４４】[0044]
【表５−１】 [Table 5-1]
【００４５】[0045]
【表５−２】 [Table 5-2]
【００４６】[0046]
【表６−１】 [Table 6-1]
【００４７】[0047]
【表６−２】 [Table 6-2]
【００４８】[0048]
【表７−１】 [Table 7-1]
【００４９】[0049]
【表７−２】 [Table 7-2]
【００５０】[0050]
【表８−１】 [Table 8-1]
【００５１】[0051]
【表８−２】 [Table 8-2]
【００５２】[0052]
【表９−１】 [Table 9-1]
【００５３】[0053]
【表９−２】 [Table 9-2]
【００５４】以上の結果からわかるように、上記の方
法により３層めっきを施した場合でもあっても、熱処理
中に最上層と最下層のＹ金属が完全に中間のAl−Ｘ合金
層に熱拡散し、熱処理後に得られためっき皮膜はAl−Ｘ
−Ｙ熱拡散合金層１層のみとなることもある。また、上
記の方法により２層めっきを施した場合、熱処理条件
や最初の２層のめっき厚みにより、上層と下層の両方の
めっき層が残存する場合と、いずれか少なくとも一方の
めっき層が消失してAl−Ｘ−Ｙ熱拡散合金層に転換され
る場合とがある。即ち、めっき条件や熱処理条件によ
り、めっき構造を多様に変化させることができる。As can be seen from the above results, even when the three-layer plating is performed by the above method, the Y metal of the uppermost layer and the lowermost layer are completely heated to the intermediate Al-X alloy layer during the heat treatment. The plated film obtained after diffusion and heat treatment is Al-X
In some cases, there is only one -Y thermal diffusion alloy layer. When two-layer plating is performed by the above method, depending on the heat treatment conditions and the plating thickness of the first two layers, both the upper and lower plating layers may remain, and at least one of them may disappear. In some cases, it may be converted into an Al-XY thermal diffusion alloy layer. That is, the plating structure can be variously changed depending on the plating conditions and the heat treatment conditions.
【００５５】本発明により、熱処理後にAl−Ｘ−Ｙ（Ｘ
が１〜50％、Ｙが 0.1〜20％) で表される熱拡散合金層
が少なくとも１層形成されたAl合金めっき鋼板は、端面
耐食性と加工性のいずれにも優れ、めっき外観も良好で
あった。According to the present invention, after heat treatment, Al-XY (X
The Al alloy plated steel sheet on which at least one thermal diffusion alloy layer represented by 1 to 50% and Y from 0.1 to 20%) is formed is excellent in both end face corrosion resistance and workability and has a good plating appearance. there were.
【００５６】[0056]
【発明の効果】本発明のAl合金めっき金属材は、熱処理
により形成された、上記Al−Ｘ−Ｙで表される熱拡散合
金層をめっき皮膜中に少なくとも１層有していることか
ら、端面耐食性に優れている。しかも、Al合金めっきに
固有の優れた裸耐食性、めっき外観といった利点も失っ
ていない。また、２層以上のめっき層を有する場合で
も、組成が傾斜して連続変化しているため、加工性が向
上し、糸錆などの層状のAl系腐食が有効に防止される。The Al alloy plated metal material of the present invention has at least one thermal diffusion alloy layer represented by the above Al-XY formed in the plating film by heat treatment. Excellent end face corrosion resistance. Moreover, the advantages such as excellent bare corrosion resistance and plating appearance, which are unique to Al alloy plating, are not lost. Further, even when there are two or more plating layers, the composition is graded and continuously changed, so that the workability is improved and layered Al-based corrosion such as thread rust is effectively prevented.
【００５７】また、本発明のAl合金めっき金属材の製造
方法によれば、最初にAl−Ｘ合金層とＹまたはＹ合金め
っき層とを有する多層めっき金属材を製造し、その後で
熱処理を施すことにより、熱拡散により生成するAl−Ｘ
−Ｙ合金層の組成をめっき条件や熱処理条件によって容
易に制御することができ、製品の信頼性が高まる。ま
た、めっき条件や熱処理条件を変動させることにより、
多様な構造のめっき皮膜を得ることができる。According to the method for producing an Al alloy-plated metal material of the present invention, first, a multi-layer plated metal material having an Al-X alloy layer and a Y or Y alloy plating layer is produced, and then heat treatment is performed. Al-X generated by thermal diffusion
The composition of the —Y alloy layer can be easily controlled by the plating conditions and heat treatment conditions, and the reliability of the product is enhanced. Also, by changing the plating conditions and heat treatment conditions,
It is possible to obtain plating films with various structures.
【図１】Al−Ｘ−Ｙ層の傾斜組成を示す説明図である。FIG. 1 is an explanatory diagram showing a gradient composition of an Al-XY layer.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 瀬戸 宏久 大阪市中央区北浜４丁目５番33号 住友金 属工業株式会社内 ─────────────────────────────────────────────────── ─── Continued Front Page (72) Inventor Hirohisa Seto 4-53-3 Kitahama, Chuo-ku, Osaka Sumitomo Metal Industries, Ltd.
Claims (3)
皮膜を有する金属材であって、該めっき皮膜中にAl−Ｘ
−Ｙ (ただし、ＸはMn、Ti、Ｗ、Mo、Fe、Ni、Coおよび
Cuよりなる群から選ばれた少なくとも１種の金属、Ｙは
Mg、Ca、Sr、Ba、Zn、Cd、In、Tl、Si、Ge、Sn、Pb、A
s、SbおよびBiよりなる群から選ばれた少なくとも１種
の金属であって、Ｘ：１〜50重量％、Ｙ： 0.1〜20重量
％、Al：残部) で表される、少なくとも１層の熱拡散Al
合金層が存在することを特徴とする、端面耐食性に優れ
たAl合金めっき金属材。1. A metal material having a plating film on a part or the whole surface of a base metal, wherein Al-X is contained in the plating film.
-Y (where X is Mn, Ti, W, Mo, Fe, Ni, Co and
At least one metal selected from the group consisting of Cu, Y is
Mg, Ca, Sr, Ba, Zn, Cd, In, Tl, Si, Ge, Sn, Pb, A
at least one metal selected from the group consisting of s, Sb, and Bi, represented by X: 1 to 50% by weight, Y: 0.1 to 20% by weight, Al: balance) Thermal diffusion Al
An Al alloy-plated metal material excellent in end face corrosion resistance, characterized by the presence of an alloy layer.
層の熱拡散Al合金層が、互いに隣接したAl−Ｘ合金めっ
き層 (ただし、Ｘは請求項１記載の少なくとも１種の金
属であり、Ｘ：１〜50重量％) とＹ金属めっき層または
Ｙ合金めっき層 (ただし、Ｙは請求項１記載の少なくと
も１種の金属) の熱処理により形成されたものである、
請求項１記載のAl合金めっき金属材。2. At least one represented by Al—X—Y
The thermal diffusion Al alloy layers of the layers are adjacent Al-X alloy plating layers (where X is at least one metal according to claim 1, X: 1 to 50% by weight) and Y metal plating layers or A Y alloy plating layer (where Y is at least one metal according to claim 1) is formed by heat treatment.
The Al alloy plated metal material according to claim 1.
Ｘ合金めっき (ただし、Ｘは請求項１記載の少なくとも
１種の金属であり、Ｘ：１〜50重量％) とＹ金属めっき
またはＹ合金めっき (ただし、Ｙは請求項１記載の少な
くとも１種の金属) とを、両めっき層が互いに隣接する
ようにそれぞれ少なくとも１回づつ施した後、得られた
多層めっき金属材を 100〜500 ℃の温度範囲で熱処理す
ることにより、めっき皮膜中にAl−Ｘ−Ｙ (ただし、Ｘ
およびＹは上記と同じ意味であり、Ｘ：１〜50重量％、
Ｙ： 0.1〜20重量％、Al：残部である) で表される熱拡
散Al合金層を形成することを特徴とする、請求項１また
は２記載のAl合金めっき金属材の製造方法。3. Al-on all or part of the surface of the base metal.
X alloy plating (where X is at least one kind of metal according to claim 1, X: 1 to 50% by weight) and Y metal plating or Y alloy plating (where Y is at least one kind according to claim 1) Metal) and at least once so that both plating layers are adjacent to each other, and then heat-treating the obtained multi-layered metal material in the temperature range of 100 to 500 ° C to form Al in the plating film. -XY (however, X
And Y have the same meanings as above, and X: 1 to 50% by weight,
Y: 0.1 to 20% by weight, Al: the balance) The heat diffusion Al alloy layer is formed, and the method for producing an Al alloy plated metal material according to claim 1 or 2, characterized in that:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4251576A JP2924492B2 (en) | 1992-09-21 | 1992-09-21 | Al alloy plated metal sheet with excellent end face corrosion resistance and its manufacturing method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4251576A JP2924492B2 (en) | 1992-09-21 | 1992-09-21 | Al alloy plated metal sheet with excellent end face corrosion resistance and its manufacturing method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH06101043A true JPH06101043A (en) | 1994-04-12 |
| JP2924492B2 JP2924492B2 (en) | 1999-07-26 |
Family
ID=17224874
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4251576A Expired - Lifetime JP2924492B2 (en) | 1992-09-21 | 1992-09-21 | Al alloy plated metal sheet with excellent end face corrosion resistance and its manufacturing method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2924492B2 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01177358A (en) * | 1987-12-30 | 1989-07-13 | Nippon Aen Kogyo Kk | Highly anticorrosive metallic material and its production |
-
1992
- 1992-09-21 JP JP4251576A patent/JP2924492B2/en not_active Expired - Lifetime
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01177358A (en) * | 1987-12-30 | 1989-07-13 | Nippon Aen Kogyo Kk | Highly anticorrosive metallic material and its production |
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