JP2727598B2 - Alloyed hot-dip galvanized steel sheet excellent in workability and paintability and method for producing the same - Google Patents

Alloyed hot-dip galvanized steel sheet excellent in workability and paintability and method for producing the same

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Publication number
JP2727598B2
JP2727598B2 JP27043688A JP27043688A JP2727598B2 JP 2727598 B2 JP2727598 B2 JP 2727598B2 JP 27043688 A JP27043688 A JP 27043688A JP 27043688 A JP27043688 A JP 27043688A JP 2727598 B2 JP2727598 B2 JP 2727598B2
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Japan
Prior art keywords
steel sheet
less
plating
layer
hot
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JPH02118087A (en
Inventor
泰久 田尻
聰一 島田
理孝 櫻井
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JFE Engineering Corp
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Nippon Kokan Ltd
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Description

【発明の詳細な説明】 [産業上の利用分野] この発明は、自動車や家電機器或は建材等に使用され
るFe−Zn合金めっき鋼板に関するものである。
Description: TECHNICAL FIELD The present invention relates to a Fe—Zn alloy plated steel sheet used for automobiles, home electric appliances, building materials, and the like.

[従来技術] 亜鉛めっき鋼板は安価で耐食性や強度に優れた材料と
して広く使われており、なかでも自動車の内外板には耐
食性に加えて、加工性や塗装性を考慮したものが多量に
使われている。亜鉛めっき鋼板の量産法として一般には
電気めっき法と溶融めっき法とがあるが、電気めっき法
では、低温で処理するので熱影響による相変化が無くめ
っき被膜の成分コントロールも容易であるが、めっき付
着量を多くするには処理時間を増さねばならない。これ
に対して、溶融めっき法では処理時間を増すことなく簡
単に付着量を増すことが出来、めっき後熱処理を施すこ
とにより容易にFe−Zn合金を作ることが出来る。しか
し、めっき皮膜組成と生成される相のコントロールに工
夫を要する。近年自動車用の鋼板では、塩害への対処等
もあってより高度の耐食性が要求され、これに呼応し
て、付着量が容易に確保出来、且つ経済的な溶融亜鉛め
っきを主体に、めっき組成や相コントロールを上手に行
い、高い耐食性を確保しながらその上で加工性や塗装性
を合わせ持っためっき鋼板の開発に力が注がれている。
[Prior art] Galvanized steel sheets are widely used as materials that are inexpensive and have excellent corrosion resistance and strength. Among them, the inner and outer plates of automobiles are made of a large amount of materials that take into account not only corrosion resistance but also workability and paintability. Have been done. Generally, there are two methods of mass production of galvanized steel sheet: electroplating and hot-dip galvanizing.Electroplating is a low-temperature treatment, so there is no phase change due to thermal effects and component control of the plating film is easy. To increase the amount of deposition, the processing time must be increased. On the other hand, in the hot-dip plating method, the amount of adhesion can be easily increased without increasing the processing time, and a Fe—Zn alloy can be easily produced by performing a heat treatment after plating. However, some contrivance is required to control the composition of the plating film and the phase generated. In recent years, steel sheets for automobiles have been required to have a higher level of corrosion resistance due to measures against salt damage, etc., and in response to this, the coating composition can be easily secured and the economical hot-dip galvanizing is mainly used. The focus is on the development of plated steel sheets that have good workability and paintability, while maintaining high corrosion resistance by performing well and phase control.

加工性で最も問題になるのが耐パウダリング性であ
り、塗装性で問題になるのが耐クレータリング性であ
る。パウダリングとは、プレス成形の際にめっき皮膜が
粉状になって脱落する現象であり、クレータリングと
は、めっき皮膜に化成処理を施した後行う電着塗装処理
において塗膜に目視できる凹凸(クレータ)が発生する
現象である。前者はめっき皮膜中に鉄含有率の高いΓ相
(Fe3Zn10,Fe20〜28wt%)が生成され、これが硬くて脆
いために起こり、後者はめっき皮膜表面の不均一さ(表
面形状、酸化膜、めっき皮膜相構造等)に起因して発生
する。
The most problematic in workability is powdering resistance, and the problem in paintability is cratering resistance. Powdering is a phenomenon in which a plating film becomes powdery and falls off during press molding, and cratering is a phenomenon that can be visually observed on a coating film in an electrodeposition coating process performed after a chemical conversion treatment is performed on the plating film. (Craters). In the former, a Γ phase (Fe 3 Zn 10 , Fe 20 to 28 wt%) with a high iron content is generated in the plating film, which is caused by the hardness and brittleness, and the latter is caused by unevenness of the plating film surface (surface shape, oxidation Film, plating film phase structure, etc.).

従来、自動車用に使用されている合金化溶融亜鉛めっ
き鋼板は、溶融めっき後全めっき皮膜平均の鉄含有率が
10wt%前後に達するまで合金化処理を施し、めっき表面
までFeを拡散させて耐食性、特に塗装後耐食性を向上さ
せたものである。即ち、鋼板に連続的に前処理(熱処理
を含む)を施して素材を調整した後、亜鉛を溶融しため
っき浴に浸漬してめっきし、後続してこのめっき鋼板を
合金化炉内で500℃から700℃の温度に急速に昇温させ短
時間(10〜30秒)保持して、めっき皮膜の鉄含有率を10
%前後に合金化させたものである。しかし、このように
して作られる合金化溶融亜鉛めっき鋼板は急速な昇温に
よって高温に加熱されるので、めっき皮膜中の鉄含有量
が場所により異なりがちで、めっき皮膜の面方向及び深
さ方向共に合金化が不均一になること、これに加えてめ
っき被膜内での鉄濃度勾配が大きくなり、表層の鉄含有
量を確保するため鋼素地との界面の鉄含有率が高まりΓ
相の生成が避けられないこと、更に高温処理と急速冷却
によりめっき皮膜に熱応力が発生すること等の問題を抱
えている。
Conventionally, alloyed hot-dip galvanized steel sheets used for automobiles have an average iron content of all coating films after hot-dip coating.
Alloying treatment is performed until it reaches about 10 wt%, and Fe is diffused to the plating surface to improve corrosion resistance, especially after coating. That is, the steel sheet is continuously subjected to pretreatment (including heat treatment) to adjust the material, and then immersed in a plating bath in which zinc is melted to perform plating. Subsequently, the plated steel sheet is heated to 500 ° C. in an alloying furnace. To 700 ° C and hold for a short time (10 to 30 seconds) to reduce the iron content of the plating film to 10
% Alloyed. However, the alloyed hot-dip galvanized steel sheet produced in this way is heated to a high temperature by rapid temperature rise, so that the iron content in the plating film tends to vary depending on the location, and the surface direction and depth direction of the plating film In both cases, the alloying becomes non-uniform, and in addition to this, the iron concentration gradient in the plating film increases, and the iron content at the interface with the steel substrate increases to secure the iron content in the surface layer.
There is a problem that generation of a phase is unavoidable, and that thermal stress is generated in the plating film by high-temperature treatment and rapid cooling.

一方、合金化処理を一次二次の二工程に分けて処理す
る方法が提案されている。例えば、特公昭59−14541号
では、一次加熱において、めっき皮膜の平滑性を得るた
めにZnめっき皮膜を再溶融させる急速昇温高温加熱を行
う。この加熱では鉄含有率を2.2〜5.5wt%の低い範囲に
留めるので、この一次加熱の結果に応じて、二次加熱を
亜鉛の融点以下の低温で時間をかけて行い、鉄含有率を
6〜13wt%の範囲に納めるものである。そしてこの方法
によって、表面が平滑で外観が優れ、且つ加工の際に剥
離やパウダリングのない合金化溶融亜鉛めっき皮膜が得
られることを開示している。
On the other hand, a method has been proposed in which the alloying treatment is divided into two steps, primary and secondary. For example, in Japanese Patent Publication No. 59-14541, in the primary heating, rapid heating and high temperature heating for remelting a Zn plating film is performed in order to obtain smoothness of the plating film. In this heating, the iron content is kept in a low range of 2.2 to 5.5 wt%, and accordingly, according to the result of the primary heating, the secondary heating is performed at a low temperature equal to or lower than the melting point of zinc, and the iron content is reduced to 6%. It should be within the range of ~ 13wt%. It discloses that this method provides an alloyed hot-dip galvanized film having a smooth surface, excellent appearance, and no peeling or powdering during processing.

他方、めっき皮膜表層のみの鉄含有率を高めて耐クレ
ータリング性を改善したものも提案されている。例え
ば、特公昭58−15554号の提案は、耐食性金属層を内層
とし、その上に鉄含有率の高いFe−Zn合金被覆層を付し
てカチオン電着塗装性を向上させためっき鋼板である。
この提案では、内層である前記耐食性金属層として溶融
亜鉛めっき後に熱処理によりFe−Zn合金化した合金化溶
融亜鉛めっき層が開示されている。
On the other hand, there has also been proposed one in which the iron content of only the surface layer of the plating film is increased to improve the cratering resistance. For example, Japanese Patent Publication No. 58-15554 proposes a plated steel sheet in which a corrosion-resistant metal layer is used as an inner layer, and a Fe-Zn alloy coating layer having a high iron content is applied thereon to improve the cationic electrodeposition coating property. .
In this proposal, an alloyed hot-dip galvanized layer in which an Fe—Zn alloy is formed by heat treatment after hot-dip galvanizing is disclosed as the inner corrosion-resistant metal layer.

[発明が解決しようとする課題] しかしながら上述した特公昭59−14541号では、耐ク
レータリング性を満足するものではない。耐クレータリ
ング性に関しては、表面の鉄含有率は不十分である。
又、耐パウダリング性に関しても、溶融亜鉛めっき後急
速昇温高温加熱によって合金化処理を行うので合金化反
応が不均一に進むことが避けられず、その結果、加工性
に劣るΓ層が成長してしまう。又、場合によっては、合
金化されない部分と合金化の進んだ部分とが混在してい
わゆる焼けむらの現象を呈したりする。このように、一
次加熱が不均一になり易いので、一次加熱の結果を基に
した二次加熱条件が極めて複雑になり実操業ではその実
施に大きな困難を伴う。
[Problem to be Solved by the Invention] However, Japanese Patent Publication No. 59-14541 does not satisfy the cratering resistance. Regarding cratering resistance, the iron content of the surface is insufficient.
Also, regarding the powdering resistance, the alloying treatment is performed by rapid temperature rise and high temperature heating after hot-dip galvanizing, so that the alloying reaction inevitably proceeds in a non-uniform manner, resulting in poor workability. Resulting in. Further, in some cases, a portion that is not alloyed and a portion where alloying has progressed are mixed, and a phenomenon of so-called uneven burning is exhibited. As described above, since the primary heating is likely to be non-uniform, the secondary heating conditions based on the result of the primary heating become extremely complicated, and there are great difficulties in carrying out the actual operation.

特公昭58−15554号では、めっき表面の鉄濃度を飛躍
的に高めたので、耐クレータリング性は改善されるが、
溶融亜鉛めっき後の熱処理によって合金化を完結させて
いるので、特公昭59−14541号と同様に合金化の不均一
さの問題があり、加えてめっき皮膜内での鉄濃度勾配が
大きくなり、鉄濃度の高くなる鋼素地との界面ではΓ相
が成長してしまう。又、急熱急冷による熱歪みも耐パウ
ダリング性にとっては好ましくない。
In Japanese Patent Publication No. 58-15554, the iron concentration on the plating surface is dramatically increased, so that the cratering resistance is improved.
Since the alloying is completed by heat treatment after hot-dip galvanizing, there is a problem of non-uniformity of alloying as in Japanese Patent Publication No. 59-14541, and in addition, the iron concentration gradient in the plating film increases, The Γ phase grows at the interface with the steel substrate where the iron concentration is high. In addition, thermal distortion due to rapid thermal quenching is not preferable for powdering resistance.

このように、耐パウダリング性、耐クレータリング性
を満たすべく工夫がなされてきたが、未だ両特性を共に
満足させる溶融亜鉛めっき鋼板は得られていない。
As described above, efforts have been made to satisfy the powdering resistance and the cratering resistance, but a hot-dip galvanized steel sheet satisfying both properties has not yet been obtained.

この問題を解決するために、この発明はなされたもの
で、耐食性に加えて耐パウダリング性と耐クレータリン
グ性とを共に満たすめっき鋼板とその製造法を提供する
ことを目的とするものである。
In order to solve this problem, the present invention has been made, and an object of the present invention is to provide a plated steel sheet that satisfies both powdering resistance and cratering resistance in addition to corrosion resistance and a method for producing the same. .

[課題を解決するための手段及び作用] この目的を達成するための手段は、鋼板の少なくとも
片面に、溶融亜鉛めっきによる第一層とその上のFe95.0
wt%以上100wt%未満で残りがCu,Co,Mo,Ni,Sn,V,Wから
選ばれた一種または二種以上を合計0.001wt%以上5wt%
以下含有するFe基合金めっきによる第二層とを熱処理し
て形成しためっき皮膜を有し、該めっき皮膜は、表層が
前記第二層のFe含有率であるFe基合金めっきで内層が厚
さ0.5μmの鋼素地との境界層を除いてδ相とζ相か
らなる合金化亜鉛めっきであって、面方向に鉄含有率が
均一に分布していることを特徴とする加工性、塗装性に
優れた合金化溶融亜鉛めっき鋼板である。
[Means and Actions for Solving the Problems] A means for achieving this object is to provide at least one surface of a steel sheet with a first layer by hot-dip galvanizing and a Fe95.0 layer thereon.
One or more selected from the group consisting of Cu, Co, Mo, Ni, Sn, V, and W, with the balance being 0.001 wt% or more and 5 wt% or less.
A plating layer formed by heat-treating a second layer formed by Fe-based alloy plating containing the following, and the plating layer is formed of a Fe-based alloy plating in which the surface layer has the Fe content of the second layer and the inner layer has a thickness. Workability and coating characterized by alloyed galvanizing consisting of δ 1 phase and ζ phase except for the boundary layer with a 0.5 μm steel substrate, wherein the iron content is uniformly distributed in the plane direction. This is a galvannealed steel sheet with excellent heat resistance.

上記合金化溶融亜鉛めっき鋼板を製造する方法として
は、次のものがある。
The following are methods for producing the alloyed hot-dip galvanized steel sheet.

一つの方法は、 (イ)通常の前処理を施した鋼板をAl0.05wt%以上0.3w
t%以下且つPb0.2wt%以下を含有する溶融亜鉛めっき浴
に浸漬して30g/m2以上90g/m2以下の第一層のめっきを施
す工程、 (ロ)めっき皮膜が溶融状態であるうちにスパングルの
微細化処理を施す工程、 (ハ)めっき皮膜が固化した後スキンパス処理を行い、
溶融亜鉛めっき皮膜の表面を平滑化する工程、 (ニ)この溶融亜鉛めっき鋼板の片面又は両面に0.5g/m
2以上10g/m2以下のFe95.0wt%以上100wt%未満で残りが
Cu,Co,Mo,Ni,Sn,V,Wから選ばれた一種または二種以上を
合計0.001wt%以上5wt%以下含有する第二層のFe基合金
めっきを施す工程、 (ホ)前記工程でめっきを施した鋼板を非酸化性又は還
元性雰囲気に維持したバッチ式焼鈍炉内でオープンコイ
ルの状態で320℃以上亜鉛の融点以下の温度範囲で10分
から50時間加熱する工程を含む方法である。
One method is as follows.
a step of immersing in a hot-dip galvanizing bath containing t% or less and Pb 0.2 wt% or less to apply a first layer of 30 g / m 2 or more and 90 g / m 2 or less, (b) the plating film is in a molten state (C) performing a skin pass treatment after the plating film is solidified,
Step of smoothing the surface of the hot-dip galvanized film, (d) 0.5 g / m on one or both sides of this hot-dip galvanized steel sheet
2 to 10 g / m 2 Fe95.0 wt% to less than 100 wt%
Applying a second layer Fe-based alloy plating containing a total of 0.001 wt% or more and 5 wt% or less of one or more selected from Cu, Co, Mo, Ni, Sn, V and W; In a method including a step of heating from 10 minutes to 50 hours in a temperature range of 320 ° C or more and the melting point of zinc or less in a state of an open coil in a batch type annealing furnace maintained in a non-oxidizing or reducing atmosphere of a steel sheet plated with is there.

他の方法は、 前記(イ)の溶融亜鉛めっき工程の後、めっき皮膜が
溶融状態であるうちに鋼板の片面又は両面にFe95.0wt%
以上100wt%未満で残りがCu,Co,Mo,Ni,Sn,V,Wから選ば
れた一種または二種以上を合計0.001wt%以上5wt%以下
含有するFe基合金パウダーを吹き付けて0.5g/m2以上10g
/m2以下の第二層のめっきを施す工程を含み,その後前
記(ハ)、(ニ)、(ホ)の工程を含む方法である。
Another method is that after the hot dip galvanizing step (a), while the plating film is in a molten state, one side or both sides of the steel sheet has Fe95.0 wt%
More than less than 100 wt%, and the remainder is sprayed with an Fe-based alloy powder containing at least 0.001 wt% and not more than 5 wt% of one or more selected from Cu, Co, Mo, Ni, Sn, V, and W at 0.5 g / m 2 or more 10 g
/ m 2 or less, followed by steps (c), (d) and (e).

以上の手段について、以下にその作用も含め、詳しく
述べる。
The above means, including its operation, will be described in detail below.

先ず、めっき用の鋼板は冷延鋼板でも熱延鋼板でもよ
く、通常の前処理として表面調整とともに焼鈍処理を施
してもよい。
First, the steel sheet for plating may be a cold-rolled steel sheet or a hot-rolled steel sheet, and may be subjected to an annealing treatment together with a surface adjustment as a normal pretreatment.

めっき皮膜表層の鉄含有率を95wt%以上とすると、電
着塗装時のクレータ発生が防止される。即ち、合金化溶
融亜鉛めっき鋼板は、めっき面に燐酸塩処理を施した後
カチオン電着塗装が施されるが、この化成処理によって
生成される燐酸塩結晶に、Feを含むホスホフィライト
[Zn2Fe(PO4・4H2O]と称する粒状で緻密な結晶と
Feを含まないホパイト[Zn3(PO4・4H2O]と称する
粗大な針状結晶とがある。
When the iron content in the surface layer of the plating film is 95 wt% or more, craters are prevented from being generated during electrodeposition coating. That is, the alloyed hot-dip galvanized steel sheet is subjected to cationic electrodeposition coating after subjecting the plated surface to phosphate treatment. Phosphitelite [Zn] containing Fe is added to phosphate crystals generated by this chemical conversion treatment. 2 Fe (PO 4 ) 2 · 4H 2 O]
There is a coarse needle-like crystal called Fe-free Hopite [Zn 3 (PO 4 ) 2 .4H 2 O].

クレータ発生原因の一つに化成処理皮膜欠陥部への局
所的な電流集中が考えられるが、ホスホフィライトで形
成さる皮膜はホパイトのそれより緻密で欠陥部が少な
い。したがって、ホスホフィライトが生成し易いように
めっき面上で十分なFeを供給してやれば、クレータは生
じにくくなる。また、めっき皮膜表層にCu,Co,Mo,Ni,S
n,V,Wから選ばれた一種または二種以上を合計0.001wt%
以上5wt%以下が含まれていると、化成処理時のFeの溶
解が促進され、前記ホスボフィライトの生成がしやすく
なる。この際、めっき皮膜中のCu,Co,Mo,Ni,Sn,V,Wから
選ばれた一種または二種以上の合計の含有量が0.001wt
%未満ではFeの溶解を促進する作用を発揮するに至ら
ず、5wt%を超えるとその溶解促進効果は飽和する。こ
の発明の合金化溶融亜鉛めっき鋼板のめっき皮膜表層は
鉄含有率がFe95.0wt%以上100wt%未満、Cu,Co,Mo,Ni,S
n,V,Wから選ばれた一種または二種以上の合計の含有量
が0.001wt%以上5wt%以下であるので、Feの供給が順調
に行われ、緻密で均一な化成処理皮膜が形成される。こ
のため、クレータの発生は著しく減少する。
One of the causes of crater generation is considered to be local current concentration on the chemical conversion film defect, but the film formed of phosphophyllite is denser and less defective than that of Hopite. Therefore, if sufficient Fe is supplied on the plating surface so that phosphophyllite is easily generated, craters are less likely to occur. In addition, Cu, Co, Mo, Ni, S
0.001wt% of one or more selected from n, V, W
When the content is at least 5 wt% or less, the dissolution of Fe during the chemical conversion treatment is promoted, and the formation of the phosphofilite is facilitated. At this time, the total content of one or more selected from Cu, Co, Mo, Ni, Sn, V, W in the plating film is 0.001 wt.
When the amount is less than 5% by weight, the effect of promoting the dissolution of Fe is not exhibited. When the amount exceeds 5% by weight, the effect of promoting the dissolution is saturated. The surface layer of the coating film of the galvannealed steel sheet according to the present invention has an iron content of 95.0 wt% or more and less than 100 wt% of Fe, Cu, Co, Mo, Ni, S
Since the total content of one or more selected from n, V, and W is 0.001 wt% or more and 5 wt% or less, the supply of Fe is performed smoothly, and a dense and uniform chemical conversion coating is formed. You. Therefore, the occurrence of craters is significantly reduced.

合金化溶融亜鉛めっき鋼板の場合、めっき付着量と皮
膜中の鉄含有率によって耐食性の殆どが決定される。し
たがって、内層においても合金化されている必要がある
が、表層のように高い鉄含有率は必要でなく、5wt%か
ら20wt%程度で充分である。また、この内層の加工特性
は極めて重要である。Γ相は内層と鋼素地との境界に生
成し易いが、このΓ相が検出されないめっき皮膜は耐パ
ウダリング性が良好である。そしてΓ相が0.5μm以上
の暑さに成長していないと検出することは困難である。
この発明の合金化溶融亜鉛めっき鋼板のめっき皮膜の大
半を占める内層は、厚さ0.5μmの鋼素地との境界層を
除いて、硬くて脆いΓ相を含まずδ相とζ相とからな
っており、加工に際して、欠陥部がなく、パウダリング
を非常に起こしにくい。また、鉄含有率の分布が面方向
に均一であることも加工性向上に非常によい影響をもた
らしている。そして、内層と鋼素地との境界が相互に熱
拡散されて一体構造に形成されており、熱拡散されて一
体構造となっためっき皮膜は鉄濃度が連続して変化した
状態となっている。このような内層の構造によって、め
っき皮膜は機械的性質や電気化学的性質が隣接した部分
で極端に異なることが無く、加工性及び耐食性において
優れたものとなる。
In the case of an alloyed hot-dip galvanized steel sheet, most of the corrosion resistance is determined by the coating weight and the iron content in the film. Therefore, it is necessary that the inner layer be alloyed, but a high iron content is not required as in the surface layer, and about 5 wt% to 20 wt% is sufficient. Further, the processing characteristics of the inner layer are extremely important. The Γ phase is easily formed at the boundary between the inner layer and the steel substrate, but the plating film in which this Γ phase is not detected has good powdering resistance. And it is difficult to detect that the Γ phase has not grown to a heat of 0.5 μm or more.
The inner layer occupying most of the coating film of the galvannealed steel sheet of the present invention, except for the boundary layer with the 0.5 μm-thick steel substrate, does not include the hard and brittle Γ phase and is composed of δ 1 phase and ζ phase. In processing, there is no defective portion and powdering is extremely unlikely to occur. In addition, the fact that the distribution of the iron content is uniform in the plane direction also has a very good effect on the improvement of workability. The boundary between the inner layer and the steel base is thermally diffused with each other to form an integral structure, and the plated film that has been thermally diffused into the integral structure has a state in which the iron concentration has continuously changed. Due to such a structure of the inner layer, the plating film does not have extremely different mechanical properties and electrochemical properties at adjacent portions, and is excellent in workability and corrosion resistance.

この発明の合金化溶融亜鉛めっき鋼板は用途によって
は耐食性、加工性、塗装性、外観、平滑性等を同時に両
面に要求されないこともあり、このような場合、他面に
はめっき皮膜がなくても或は他のめっき皮膜を付しても
よい。
Depending on the application, the galvannealed steel sheet of the present invention may not require corrosion resistance, workability, paintability, appearance, smoothness, etc. on both sides at the same time, and in such a case, there is no plating film on the other side. Alternatively, another plating film may be provided.

以下に、この発明による合金化溶融亜鉛めっき鋼板の
製造方法について述べる。
Hereinafter, a method for producing an alloyed hot-dip galvanized steel sheet according to the present invention will be described.

溶融亜鉛めっき浴には通常、Fe−Zn合金反応の抑制や
めっき面の平滑化等のためAlが0.2%前後添加されてお
り、スパングル調整のためPbが含まれている。このうち
Alは合金化抑制効果を持つので、0.05wt%以上添加し、
溶融亜鉛めっき浴浸漬後のFe−Zn合金が部分的且つ不均
一に生成することを防ぐ。この工程で不均一にFe−Zn合
金を生成させないことは重要なことであり、一旦不均一
化すると後の工程で修正することが出来ない。Alの添加
量が多過ぎて0.3wt%を超えると合金化の抑制効果が過
剰となり、後の合金化処理に時間が掛かり過ぎ工業的に
は不適切になる。Pbは合金化反応には直接関与しない
が、多量のPbは耐パウダリング性を低下させるので、0.
2wt%以下に制限しなければならない。
Usually, about 0.2% of Al is added to the hot-dip galvanizing bath for suppressing the reaction of the Fe-Zn alloy and smoothing the plated surface, and contains Pb for adjusting the spangle. this house
Al has an alloying suppression effect, so add 0.05 wt% or more,
It prevents the Fe-Zn alloy after immersion in the hot-dip galvanizing bath from being partially and non-uniformly formed. It is important not to generate the Fe-Zn alloy non-uniformly in this step, and once it is made non-uniform, it cannot be corrected in a later step. If the addition amount of Al is too large and exceeds 0.3% by weight, the effect of suppressing alloying becomes excessive, and the subsequent alloying process takes too much time, which is industrially unsuitable. Pb does not directly participate in the alloying reaction, but a large amount of Pb lowers the powdering resistance.
Must be limited to 2 wt% or less.

第一層は30g/m2から90g/m2の付着量が高耐食化のため
に適当である。この第一層はめっき皮膜の大半を占め、
耐食性や加工性に大きく影響するもので、高耐食性を確
保する為に30g/m2以上の付着量を必要とする。然し90g/
m2を超えた場合には過剰品質となるばかりか、後の工程
の低温で行う合金化処理において長時間を要し生産性を
低下させる。又、一般にめっき皮膜が厚くなると加工時
に皮膜の破壊や剥離が起こることがあり、合金化溶融亜
鉛めっき鋼板の場合ではパウダリングが起こり易くな
る。
In the first layer, a coating weight of 30 g / m 2 to 90 g / m 2 is appropriate for high corrosion resistance. This first layer occupies most of the plating film,
It has a significant effect on corrosion resistance and workability, and requires an adhesion amount of 30 g / m 2 or more to ensure high corrosion resistance. But 90g /
If it exceeds m 2 , not only the quality becomes excessive, but also the alloying treatment performed at a low temperature in a later step requires a long time and lowers the productivity. In general, when the plating film is thick, the film may be broken or peeled off during processing, and powdering is likely to occur in the case of an alloyed hot-dip galvanized steel sheet.

この第一層の溶融亜鉛めっき皮膜が溶融状態であるう
ちにスパングルを微細化し、更にめっき皮膜が固化した
後スキンパス処理を行うことによって平滑なめっき面が
得られ、この後に施す第二層のFe基合金めっきの被覆率
が向上する。その結果、耐クレータリング性を効率的に
向上させることができると共に、塗装後の鮮映度を向上
させることもできる。スキンパスは伸長率0.3%以上で
行うとめっき面は平滑となるが、伸長率が大き過ぎて5
%を超えると、一般的薄板用鋼板では加工性に影響する
おそれがある。
While the hot-dip galvanized film of the first layer is in a molten state, the spangles are refined, and a smooth-plated surface is obtained by performing a skin pass treatment after the plated film is solidified. The coverage of the base alloy plating is improved. As a result, the cratering resistance can be efficiently improved, and the sharpness after painting can also be improved. When the skin pass is performed at an elongation ratio of 0.3% or more, the plated surface becomes smooth, but the elongation ratio is too large and 5%.
%, The workability may be affected in a general steel sheet for thin sheets.

第二層の鉄含有率95wt%以上のFe−Cu,Co,Mo,Ni,Sn,
V,W合金めっきは、耐クレータリング性を確保すると共
に、この後の加熱処理において、先に施した第一層の溶
融亜鉛めっき層へ鋼素地とは反対面からFeを拡散させそ
の結果めっき皮膜内層部の鉄濃度勾配を小さく押さえる
ことになる。この際、第二層中のCu,Co,Mo,Ni,Sn,V,Wは
Feの拡散を促進するので、第一層の合金化は第二層中の
側から活発に行なわれる。これらの拡散促進元素は微量
でその効果を発揮し、0.001wt%存在すればよく、また5
wt%を超えても添加効果が飽和するので必要が無くな
る。上記合金めっきの処理方法は、亜鉛の融点より低い
温度で処理する方法であれば、電気めっき、蒸着めっ
き、溶射等、どのような方法でもよい。この合金めっき
処理を合金パウダー吹き付けで行うときは、先の溶融亜
鉛めっき層が溶融状態のうちに行うとスパングルの微細
化も同時に行われ、工程を一つ省くことが出来る。
Fe-Cu, Co, Mo, Ni, Sn, with an iron content of 95 wt% or more in the second layer
The V and W alloy plating ensures cratering resistance and, in the subsequent heat treatment, diffuses Fe from the surface opposite to the steel base into the first hot-dip galvanized layer, resulting in plating. The gradient of iron concentration in the inner layer of the film is kept small. At this time, Cu, Co, Mo, Ni, Sn, V, W in the second layer are
Since the diffusion of Fe is promoted, alloying of the first layer is actively performed from the side in the second layer. These diffusion-promoting elements exert their effects in a very small amount, and may be present in an amount of 0.001 wt%.
If it exceeds wt%, the effect of addition is saturated, so that it becomes unnecessary. The alloy plating treatment method may be any method such as electroplating, vapor deposition plating, or thermal spraying, as long as the treatment is performed at a temperature lower than the melting point of zinc. When this alloy plating process is performed by spraying alloy powder, if the preceding hot-dip galvanized layer is performed while it is in a molten state, the spangles can be miniaturized at the same time, and one step can be omitted.

第二層は付着量が0.5g/m2から10g/m2であることが必
要である。0.5g/m2未満ではめっき面全体にわたって十
分にFeを供給することが出来ない。また10g/m2を超えて
付着した場合にはその効果が飽和し、コスト的に不利に
なるばかりでなく、塗装後耐食性においても赤錆が発生
し易くなる。
The second layer needs to have a coating weight of 0.5 g / m 2 to 10 g / m 2 . If it is less than 0.5 g / m 2 , it is not possible to sufficiently supply Fe over the entire plating surface. In addition, when the amount exceeds 10 g / m 2 , the effect is saturated, and not only is the cost disadvantageous, but also red rust is easily generated in the corrosion resistance after coating.

上記した二度のめっき工程を経ためっき鋼板を加熱処
理するが、これは第一層の亜鉛をFe合金化することによ
って塗装後の高耐食性を実現するものであって、この加
熱処理によって形成される内層の鉄含有率は表層のよう
に高くする必要はなく5wt%〜20wt%の範囲で良好な塗
装後耐食性が得られる。
Heat treatment is performed on the coated steel sheet that has undergone the two plating steps described above.This is to realize high corrosion resistance after painting by alloying the first layer of zinc with Fe, and is formed by this heat treatment. The iron content of the inner layer does not need to be as high as the surface layer, and good corrosion resistance after coating can be obtained in the range of 5 wt% to 20 wt%.

非酸化性又は還元性雰囲気で行うのは表面の酸化を防
ぎ,塗装前の化成処理において化成皮膜結晶が不均一に
なることを避けるためであり、バッチ式焼鈍炉内で行う
のは低温で時間を掛けて処理するからである。オープン
コイルの状態で加熱するのは、均一に加熱することによ
って合金化にむらが生ずることを防止すると同時にめっ
き面同士が付着して欠陥が発生することを防ぐためであ
る。タイトコイルの状態では、温度分布が不均一とな
り、部分的に合金化速度の大きい部分と小さい部分とが
できてしまう。特に、鋼板長手方向にこの不均一が生
じ、高品質製品は得られ難い。加熱は低温で行うが、32
0℃以上の温度は必要である。320℃未満では塗装後耐食
性を確保するに足る合金化度を得るのに時間が掛かり過
ぎる。温度を亜鉛の融点(419.5℃)よりも高くする
と、合金化が急速に進む箇所が現れ又Γ相の生成も無視
できなくなる。更にオープンコイルの鋼板間に挿入する
スペーサーがめっき面に痕跡を残すおそれも出てくる。
第1図は上記の温度範囲で、パウダリングとクレータの
両者が共に発生しない条件を調べたもので、横軸は加熱
時間縦軸は加熱温度である。図で、点a,b,c,dを結ぶ線
で囲まれた範囲が、パウダリング及びクレータを発生さ
せない実操業上好ましい条件範囲で、加熱時間について
は、a点の時間座標からc点の時間座標まで、即ち10分
以上50時間以下となる。以上の加熱条件で熱処理を行う
と、Feは鋼素地側からと第二層のめっき側とから拡散す
るので、鋼素地側に大きなFe濃度勾配が出来ずに適正な
合金化が達成される。このため、Γ相は実質的に生成せ
ずδ相とζ相とのみからなるめっき皮膜が得られる。
そして、このめっき皮膜は、急速の高温加熱を避けてい
るので、面に沿っても均一となる。又、鉄含有率も5wt
%から20wt%の範囲に収まる。しかし、実操業時に起こ
りがちな条件のバラツキ等を考えると特に好ましいの
は、加熱温度が320℃から380℃まで、加熱時間が30分か
ら10時間までである。この場合めっき皮膜の鉄含有率は
5wt%から14wt%の範囲に収まる。更に、この熱処理に
よって、第一層と第二層はFeの熱拡散によって一体構造
となり、熱歪も除かれる。
Performing in a non-oxidizing or reducing atmosphere is to prevent oxidation of the surface and to prevent non-uniformity of the conversion film crystals during the chemical conversion treatment before coating. Is applied. The reason why the heating is performed in the state of the open coil is to prevent unevenness in the alloying due to the uniform heating and also to prevent the plating surfaces from adhering to each other and generating defects. In the state of the tight coil, the temperature distribution becomes non-uniform, and a part having a high alloying rate and a part having a small alloying rate are partially formed. In particular, this unevenness occurs in the longitudinal direction of the steel sheet, and it is difficult to obtain a high quality product. Heating is performed at low temperature, but 32
Temperatures above 0 ° C are required. If the temperature is lower than 320 ° C., it takes too much time to obtain a degree of alloying sufficient to secure corrosion resistance after painting. When the temperature is higher than the melting point of zinc (419.5 ° C.), a portion where alloying proceeds rapidly appears and the formation of a Γ phase cannot be ignored. Furthermore, the spacer inserted between the steel plates of the open coil may leave traces on the plating surface.
FIG. 1 shows the conditions under which neither powdering nor craters occur in the above temperature range. The horizontal axis represents the heating time and the vertical axis represents the heating temperature. In the figure, a range surrounded by a line connecting points a, b, c, and d is a preferable condition range for practical operation in which powdering and craters do not occur. The time is up to the time coordinate, that is, 10 minutes or more and 50 hours or less. When heat treatment is performed under the above heating conditions, Fe diffuses from the steel substrate side and from the plating side of the second layer, so that a proper alloying is achieved without a large Fe concentration gradient on the steel substrate side. For this reason, a plating film consisting of only the δ 1 phase and the ζ phase is obtained without substantially generating the Γ phase.
And since this plating film avoids rapid high-temperature heating, it becomes uniform even along the surface. Also, iron content is 5wt
% To 20 wt%. However, in consideration of the variation in conditions that are likely to occur during actual operation, it is particularly preferable that the heating temperature be from 320 ° C. to 380 ° C. and the heating time be from 30 minutes to 10 hours. In this case, the iron content of the plating film is
It falls in the range of 5 wt% to 14 wt%. Further, by this heat treatment, the first layer and the second layer become an integral structure due to the thermal diffusion of Fe, and thermal strain is also eliminated.

[実施例] 二種類の鋼板を使用し、溶融亜鉛めっき条件、上層め
っき条件及び合金化処理条件を変えて処理した25例(実
施例)の合金化溶融亜鉛めっき鋼板について、めっき皮
膜中の鉄含有率を調べ、パウダリング試験及びクレータ
リング試験を行って評価した。なお比較のために、この
発明の範囲外の条件で処理した6例(比較例)及び従来
技術による3例(従来例)についても同様に調べた。条
件の詳細は以下の通りである。
[Examples] 25 kinds of alloyed hot-dip galvanized steel sheets were processed by using two types of steel sheets and changing the hot-dip galvanizing conditions, upper layer plating conditions, and alloying treatment conditions. The content was examined and evaluated by performing a powdering test and a cratering test. For comparison, six cases (comparative example) and three cases (conventional example) according to the prior art, which were processed under conditions outside the scope of the present invention, were similarly examined. Details of the conditions are as follows.

用いた鋼鈑は板厚0.8mmの冷延鋼板で、汎用されてい
る薄板用低炭素Alキルド(素材A)で及び高加工用でパ
ウダリングを起こし易いと言われている超低炭チタン含
有鋼(素材B)とである。各々の成分を第1表に示す。
The steel plate used is a cold-rolled steel plate with a thickness of 0.8 mm. It is a commonly used low-carbon Al-killed sheet (material A) for thin sheets and contains ultra-low-carbon titanium, which is said to be prone to powdering for high processing. Steel (material B). Each component is shown in Table 1.

溶融亜鉛めっきは、無酸化炉、還元加熱炉を備えた連
続式めっき設備で行い、めっき浴直後に設けられた気体
絞り装置によって付着量の調整を行い、つづいてミスト
スプレイによりスパングルを微細化し、めっき層が冷却
後伸長率1.5%でスキンパスを行い表面を平滑にした。
Hot-dip galvanizing is performed in a continuous plating facility equipped with a non-oxidizing furnace and a reduction heating furnace, the amount of coating is adjusted by a gas throttle device provided immediately after the plating bath, and then spangles are refined by mist spraying. After cooling, the plating layer was skin-passed at an elongation of 1.5% to smooth the surface.

Fe基合金めっきには、電気めっき、プラズマ溶射又は
パウダースプレイの方法を用いたが、各々次の条件で処
理した。パウダースプレーめっきの場合はスプレーめっ
きによってスパングルの微細化を行ないミストスプレー
はおこなはなかった。
Electroplating, plasma spraying, or powder spraying was used for the Fe-based alloy plating, and each was processed under the following conditions. In the case of powder spray plating, the spangles were miniaturized by spray plating, and no mist spray was performed.

(1)電気めっき Fe2SO4・(NH4)SO4・6H2O 350g/ MeSO4・7H2O 0.5〜5g/ (MeはCu,Co,Mo,Ni,Sn,V,Wから選ばれた一種又は二種以
上の金属) CH3COONH4 20g/ PH 2.2, 浴温 50℃ 陰極電流密度 50A/dm2 (2)プラズマ溶射 プラズマガス Ar 溶射入熱 20KW 溶射距離 100mm 平均粉末粒径 約5μm 粉末供給速度 5g/min・dm2 (3)パウダースプレイ 平均粉末粒径 約5μm 粉末供給速度 3g/min・dm2 めっき皮膜表層中及びめっき内層中の鉄含有率は、そ
れぞれオージェ電子スペクトロメトリー及びグリムグロ
ー放電発光分光分析によって調べた。
(1) Electroplating Fe 2 SO 4. (NH 4 ) SO 4 .6H 2 O 350 g / MeSO 4 .7H 2 O 0.5 to 5 g / (Me is selected from Cu, Co, Mo, Ni, Sn, V, W One or more metals) CH 3 COONH 4 20g / PH 2.2, bath temperature 50 ° C Cathode current density 50A / dm 2 (2) Plasma spray Plasma gas Ar spray input heat 20KW Spray distance 100mm Average powder particle size 5 µm powder supply rate 5 g / min · dm 2 (3) Powder spray Average powder particle size about 5 µm Powder supply rate 3 g / min · dm 2 The iron content in the surface of the plating film and in the inner layer of the plating are determined by Auger electron spectrometry and It was examined by Grimm-glow discharge emission spectroscopy.

耐パウダリング性は、曲率半径2mmで90度に曲げた
後、曲げの内側に粘着テープを貼り付け、これを剥し
て、パウダーがこの粘着テープに付着した状況を目視観
察し、点数付けて評価した。評点の基準は、1;全く付着
無し、2;極くわずかに付着、3;わずかに付着、4;少し付
着、5;かなり付着、の五段階である。
Powdering resistance is evaluated after bending to 90 degrees with a radius of curvature of 2 mm, then sticking an adhesive tape inside the bend, peeling it off, visually observing the situation where powder adhered to this adhesive tape, scoring and evaluating did. The evaluation criteria are 1; no adhesion, 2; extremely slight adhesion, 3; slight adhesion, 4; slight adhesion, 5; considerable adhesion.

耐クレータリング性は、めっき面に化成処理を施し、
次いで電着塗装を行い、このとき発生したクレータの数
で評価した。化成処理には市販されている浸漬型の燐酸
塩系処理剤を用いた。電着塗装にはやはり市販されてい
るカチオン電着塗料を用いたが、調合後一週間撹拌し、
極間距離4cmで電着電圧300vを瞬時に印加して電着し
た。
Cratering resistance is achieved by subjecting the plated surface to a chemical conversion treatment,
Next, electrodeposition coating was performed, and the number of craters generated at this time was evaluated. For the chemical conversion treatment, a commercially available immersion type phosphate treatment agent was used. For the electrodeposition coating, a commercially available cationic electrodeposition coating was used, but after mixing, stirring was performed for one week.
Electrodeposition was performed by instantaneously applying an electrodeposition voltage of 300 V at a distance between the electrodes of 4 cm.

これらの例の各々の処理条件と調査結果を実施例につ
いて第2表、また比較例、従来例について第3表に示
す。
The processing conditions and investigation results of each of these examples are shown in Table 2 for Examples and Table 3 for Comparative Examples and Conventional Examples.

実施例では、素材Bでも耐パウダリング性に劣るもの
はなく、上限付着量である実施例No.6及び限界加熱時間
に近い実施例No.17とで、極く僅かにパウダリングが認
められたが、実用上は問題がない。耐クレータリング性
では、上層の付着量が下限である実施例No.13で1個内
至2個の小さなクレータが発見されたが、これも実用上
は問題ない。このように、実施例では全ての合金化溶融
亜鉛めっき鋼板が耐パウダリング性と耐クレータリング
性とを兼ね備えている。又、内層の鉄含有率も7wt%か
ら16wt%の範囲内にあり、塗装後耐食性を十分に確保す
るものである。
In the examples, even in the case of the material B, there was no inferior powdering resistance. In the example No. 6 and the example No. 17 near the limit heating time, the powdering was very slightly observed. However, there is no problem in practical use. Regarding the cratering resistance, in Example No. 13 in which the amount of the upper layer attached was the lower limit, one to two small craters were found, but this also has no practical problem. Thus, in the examples, all the alloyed hot-dip galvanized steel sheets have both powdering resistance and cratering resistance. In addition, the iron content of the inner layer is in the range of 7 wt% to 16 wt%, which ensures sufficient corrosion resistance after painting.

一方、発明の範囲から外れた条件で処理された比較例
では、亜鉛めっき浴中にAlを含まない比較例No.1、加熱
時間過剰の比較例No.2、浴中Pbの多い比較例No.3、付着
量の多すぎる比較例No.4、上層めっきを施さない比較例
No.5、加熱温度の高過ぎる比較例No.6等でNo.5は耐クレ
ータリング性に、他は耐パウダリング性か耐クレータリ
ング性の何れかに問題がある。
On the other hand, in Comparative Examples treated under conditions outside the scope of the invention, Comparative Example No. 1 containing no Al in the zinc plating bath, Comparative Example No. 2 with excessive heating time, and Comparative Example No. .3, Comparative Example No. 4 with too much adhesion, Comparative Example without upper layer plating
No. 5, Comparative Example No. 6 where the heating temperature is too high, etc. No. 5 has a problem with cratering resistance, and others have problems with either powdering resistance or cratering resistance.

従来例では、従来例No.1は急速昇温高温加熱のみによ
り合金化したもので両特性に問題があり、従来例No.2は
急速昇温高温加熱の後低温で合金化調整したもので耐ク
レータリングが劣り、従来例No.3は急速昇温高温加熱に
よって合金化しその上に鉄含有率の高いめっき層を付し
たもので、耐パウダリング性に劣る。このように、両特
性が同時には満足されていない。
In the conventional example, the conventional example No. 1 was alloyed only by rapid heating and high temperature heating, and there were problems in both characteristics.The conventional example No. 2 was alloyed and adjusted at low temperature after rapid heating and high temperature heating. Cratering resistance is inferior. Conventional example No. 3 is alloyed by rapid temperature rise and high temperature heating, and is further provided with a plating layer having a high iron content, which is inferior in powdering resistance. Thus, both characteristics are not satisfied at the same time.

次に本発明によるめっき皮膜の内層部の鉄含有率分布
を調べた。
Next, the distribution of iron content in the inner layer portion of the plating film according to the present invention was examined.

ここでは実施例No.14の合金化溶融亜鉛めっきコイル
(幅1800mm)の幅方向について、200mm間隔でめっき内
層部の鉄含有率を調べた。この場合従来例No.2と比較し
た。この結果を第2図に示す。図において横軸はコイル
左端からの距離、縦軸は鉄含有率であり、○印は実施例
No.14をプロットしたものであり、●印は従来例No.2を
プロットしたものであ。図から明らかなように実施例N
o.14の鉄含有率は平均9.7wt%であり、全ての測定点が
9.4wt%から9.8wt%の間に分布していた。これに対して
従来例No.2の鉄含有率は平均8.3wt%であり、全ての測
定点が7.8wt%から8.8wt%の間に分布しバラツキが大き
かった。
Here, in the width direction of the alloyed hot-dip galvanized coil of Example No. 14 (width 1800 mm), the iron content of the inner layer of the plating was examined at intervals of 200 mm. In this case, comparison was made with Conventional Example No. 2. The result is shown in FIG. In the figure, the horizontal axis is the distance from the left end of the coil, the vertical axis is the iron content,
No. 14 is plotted, and ● marks are plots of No. 2 of the conventional example. As is clear from the figure, Example N
The iron content of o.14 is 9.7 wt% on average, and all measurement points
It was distributed between 9.4 wt% and 9.8 wt%. On the other hand, the iron content of Conventional Example No. 2 was 8.3% by weight on average, and all the measurement points were distributed between 7.8% by weight and 8.8% by weight.

更にめっき皮膜の底部にΓ相が存在しているか否かに
ついて、実施例No.1からNo.25迄の合金化溶融亜鉛めっ
き処理を施した試料について、めっき皮膜の上層約三分
の二を取り除きX線回折を行った結果、何れの試料につ
いてもΓ相は検出されなかった。
Further, regarding whether or not a Γ phase is present at the bottom of the plating film, about two thirds of the upper layer of the plating film was subjected to the alloyed hot-dip galvanizing treatment of Examples No. 1 to No. 25. As a result of X-ray diffraction after removal, no Γ phase was detected in any of the samples.

[発明の効果] 本発明のめっき鋼板は、めっき皮膜中にΓ相が実質的
に存在せず、表層は鉄含有率が高く、合金化処理時に第
二層添加元素の作用もあって内層の合金化も適切に行な
われ、表層と内層とが一体構造になっており、しかも合
金成分の分布が面方向に均一な皮膜を持っているので、
十分な耐食性に加えて優れた耐パウダリング性と耐クレ
ータリング性とを共に有しており、また本発明の方法は
このように優れためっき鋼板を簡単な工程で容易に製造
出来るので産業上効果の大きい発明である。
[Effect of the Invention] The plated steel sheet of the present invention has substantially no Γ phase in the plating film, has a high iron content in the surface layer, and has an effect of the second layer additive element during the alloying treatment, so that the inner layer has Alloying is also performed properly, the surface layer and the inner layer have an integral structure, and the distribution of alloy components has a uniform film in the plane direction,
In addition to having sufficient corrosion resistance, it has both excellent powdering resistance and cratering resistance, and the method of the present invention can easily produce such excellent plated steel sheets in a simple process, so that it is industrially useful. This is a highly effective invention.

【図面の簡単な説明】[Brief description of the drawings]

第1図はこの発明の主要部を説明するための熱処理条件
と特性適正との関係を示す図、第2図は本発明の一実施
例の鉄含有率の分布を示す図である。
FIG. 1 is a diagram showing the relationship between heat treatment conditions and proper properties for explaining the main part of the present invention, and FIG. 2 is a diagram showing the distribution of iron content in one embodiment of the present invention.

フロントページの続き (56)参考文献 特開 平2−88752(JP,A) 特開 平2−73953(JP,A) 特開 昭61−253397(JP,A) 特開 昭60−67690(JP,A) 特開 昭57−79160(JP,A) 特開 昭57−114692(JP,A) 特開 昭58−39792(JP,A) 特開 昭61−119663(JP,A) 特開 昭58−34169(JP,A) 特開 昭56−158864(JP,A) 特公 昭58−15554(JP,B2) 特公 昭59−14541(JP,B2) 鉄と鋼、72[13](1986),(昭61− 9−9),p.S1331Continuation of the front page (56) References JP-A-2-88752 (JP, A) JP-A-2-73953 (JP, A) JP-A-61-253397 (JP, A) JP-A-60-67690 (JP) JP-A-57-79160 (JP, A) JP-A-57-114692 (JP, A) JP-A-58-39792 (JP, A) JP-A-61-119663 (JP, A) 58-34169 (JP, A) JP-A-56-158864 (JP, A) JP-B-58-15554 (JP, B2) JP-B-59-14541 (JP, B2) Iron and steel, 72 [13] ( 1986), (1986-9-9), p. S1331

Claims (3)

(57)【特許請求の範囲】(57) [Claims] 【請求項1】鋼板の少なくとも片面に、溶融亜鉛めっき
による第一層とその上のFe95.0wt%以上100wt%未満で
残りがCu,Co,Mo,Ni,Sn,V,Wから選ばれた一種または二種
以上を合計0.001wt%以上5wt%以下含有するFe基合金め
っきによる第二層とを熱処理して形成しためっき皮膜を
有し、該めっき皮膜は、表層が前記第二層のFe含有率で
あるFe基合金めっきで内層が厚さ0.5μmの鋼素地との
境界層を除いてδ相とζ相からなる合金化亜鉛めっき
であって、面方向に鉄含有率が均一に分布していること
を特徴とする加工性、塗装性に優れた合金化溶融亜鉛め
っき鋼板。
At least one side of a steel sheet has a first layer formed by hot-dip galvanizing, and Fe95.0% by weight or more and less than 100% by weight and the remainder selected from Cu, Co, Mo, Ni, Sn, V and W. A plating layer formed by heat-treating a second layer formed by plating an Fe-based alloy containing one or more kinds in total of 0.001 wt% or more and 5 wt% or less, and the plating film has a surface layer of Fe of the second layer. Alloyed zinc plating consisting of δ 1 phase and ζ phase except for the boundary layer between the inner layer and the 0.5 μm thick steel substrate in the Fe-based alloy plating, which has a uniform iron content in the plane direction. Alloyed hot-dip galvanized steel sheet with excellent workability and paintability characterized by being distributed.
【請求項2】以下の工程を含むことを特徴とする加工
性、塗装性に優れた合金化溶融亜鉛めっき鋼板の製造方
法。 (イ)通常の前処理を施した鋼板をAl0.05wt%以上0.3w
t%以下且つPb0.2wt%以下を含有する溶融亜鉛めっき浴
に浸漬して30g/m2以上90g/m2以下の第一層のめっきを施
す工程、 (ロ)めっき皮膜が溶融状態であるうちにスパングルの
微細化処理を施す工程、 (ハ)めっき皮膜が固化した後スキンパス処理を行い、
溶融亜鉛めっき皮膜の表面を平滑化する工程、 (ニ)この溶融亜鉛めっき鋼板の片面又は両面に0.5g/m
2以上10g/m2以下のFe95.0wt%以上100wt%未満で残りが
Cu,Co,Mo,Ni,Sn,V,Wから選ばれた一種または二種以上を
合計0.001wt%以上5wt%以下含有する第二層のFe基合金
めっきを施す工程、 (ホ)前記工程でめっきを施した鋼板を非酸化性又は還
元性雰囲気に維持したバッチ式焼鈍炉内でオープンコイ
ルの状態で320℃以上亜鉛の融点以下の温度範囲で10分
から50時間加熱する工程。
2. A method for producing an alloyed hot-dip galvanized steel sheet having excellent workability and paintability, comprising the following steps. (B) A steel sheet that has been subjected to normal pretreatment is treated with Al
a step of immersing in a hot-dip galvanizing bath containing t% or less and Pb 0.2 wt% or less to apply a first layer of 30 g / m 2 or more and 90 g / m 2 or less, (b) the plating film is in a molten state (C) performing a skin pass treatment after the plating film is solidified,
Step of smoothing the surface of the hot-dip galvanized film, (d) 0.5 g / m on one or both sides of this hot-dip galvanized steel sheet
2 to 10 g / m 2 Fe95.0 wt% to less than 100 wt%
Applying a second layer Fe-based alloy plating containing a total of 0.001 wt% or more and 5 wt% or less of one or more selected from Cu, Co, Mo, Ni, Sn, V and W; Heating the steel sheet plated in step 2 in a batch type annealing furnace maintained in a non-oxidizing or reducing atmosphere in an open coil state at a temperature in the range of 320 ° C. or more and the melting point of zinc for 10 minutes to 50 hours.
【請求項3】以下の工程を含むことを特徴とする加工
性、塗装性に優れた合金化溶融亜鉛めっき鋼板の製造方
法。 (イ)通常の前処理を施した鋼板をAl0.05wt%以上0.3w
t%以下且つPb0.2wt%以下を含有する溶融亜鉛めっき浴
に浸漬して30g/m2以上90g/m2以下の第一層のめっきを施
す工程、 (ロ)めっき皮膜が溶融状態であるうちに鋼板の片面又
は両面にFe95.0wt%以上100wt%未満で残りがCu,Co,Mo,
Ni,Sn,V,Wから選ばれた一種または二種以上を合計0.001
wt%以上5wt%以下含有するFe基合金パウダーを吹き付
けて0.5g/m2以上10g/m2以下の第二層のめっきを施す工
程、 (ハ)めっき皮膜が固化した後スキンパス処理を行い溶
融亜鉛めっき皮膜の表面を平滑化する工程、 (ニ)前記工程で平滑化しためっき皮膜を有する鋼板を
非酸化性又は還元性雰囲気に維持したバッチ式焼鈍炉内
でオープンコイルの状態で320℃以上亜鉛の融点以下の
温度範囲で10分から50時間加熱する工程。
3. A method for producing an alloyed hot-dip galvanized steel sheet having excellent workability and coatability, comprising the following steps. (B) A steel sheet that has been subjected to normal pretreatment is treated with Al
a step of immersing in a hot-dip galvanizing bath containing t% or less and Pb 0.2 wt% or less to apply a first layer of 30 g / m 2 or more and 90 g / m 2 or less, (b) the plating film is in a molten state One or both sides of the steel sheet, Fe95.0wt% or more and less than 100wt%, the remainder is Cu, Co, Mo,
One, two or more selected from Ni, Sn, V, W total 0.001
step of blowing Fe-based alloy powder plating of 0.5 g / m 2 or more 10 g / m 2 or less of the second layer containing less wt% or more 5 wt%, melting performs skin pass process after solidification is (iii) plating film (D) a step of flattening the surface of the galvanized film, (d) 320 ° C. or higher in an open coil state in a batch annealing furnace in which the steel sheet having the plated film smoothed in the above step is maintained in a non-oxidizing or reducing atmosphere. Heating in a temperature range below the melting point of zinc for 10 minutes to 50 hours.
JP27043688A 1988-10-26 1988-10-26 Alloyed hot-dip galvanized steel sheet excellent in workability and paintability and method for producing the same Expired - Lifetime JP2727598B2 (en)

Priority Applications (1)

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Publication Number Publication Date
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JP2727598B2 true JP2727598B2 (en) 1998-03-11

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Country Link
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4884606B2 (en) * 2001-07-11 2012-02-29 新日本製鐵株式会社 Heating method of steel sheet for thermoforming
KR102359203B1 (en) * 2018-12-19 2022-02-08 주식회사 포스코 Zinc alloy coated steel having excellent corrosion resistance and surface property, method for manufacturing the same
JPWO2020222305A1 (en) * 2019-04-27 2020-11-05

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
鉄と鋼、72[13](1986),(昭61−9−9),p.S1331

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