JP5320899B2 - Alloyed hot-dip galvanized steel sheet with excellent plating adhesion - Google Patents
Alloyed hot-dip galvanized steel sheet with excellent plating adhesion Download PDFInfo
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本発明は、自動車の車体用途に適する、めっき密着性に優れた合金化溶融亜鉛めっき鋼板に関する。 The present invention relates to an alloyed hot-dip galvanized steel sheet having excellent plating adhesion suitable for use in automobile bodies.
合金化溶融亜鉛めっきは、鋼板の防食を目的として施され、広範囲に使用されている。その製造方法は、連続式溶融亜鉛めっきライン（以下、ＣＧＬと称する）において、脱脂洗浄後、Ｈ2及びＮ2を含む還元雰囲気にて、ラジアントチューブによる間接加熱により焼鈍し、めっき浴温度近傍まで冷却した後に、溶融亜鉛めっき浴に浸漬し、めっき浴を出た後に再加熱して合金化すると言う全還元炉方式が一般的である。 Alloying hot dip galvanizing is applied for the purpose of corrosion protection of steel sheets, and is widely used. The manufacturing method is as follows. In a continuous hot dip galvanizing line (hereinafter referred to as CGL), after degreasing and cleaning, annealing is performed by indirect heating with a radiant tube in a reducing atmosphere containing H 2 and N 2 until the temperature of the plating bath reaches An all-reduction furnace method is generally used in which the alloy is immersed in a hot dip galvanizing bath after cooling and then reheated after leaving the plating bath to form an alloy.
合金化溶融亜鉛めっき鋼板の使用用途は、自動車の外板や構造部材等、自動車用鋼板としての用途が多いが、自動車用鋼板においては、複雑化している自動車のボディ形状に対応するため、複雑な形状にプレス成形しても、めっき密着性を確保することができることが求められている。 The alloyed hot-dip galvanized steel sheet has many uses as automotive steel sheets, such as automotive outer panels and structural members. However, automotive steel sheets are complex because they correspond to the complex body shape of automobiles. Even if it is press-molded into a simple shape, it is required that plating adhesion can be ensured.
合金化溶融亜鉛めっき鋼板のめっき層の構造は、図１に示すように、めっき層と鋼板母材５の界面からΓ相（Ｚｎ10Ｆｅ3）４、Γ1相（Ｚｎ21Ｆｅ5）３、δ1相（Ｚｎ7Ｆｅ）２、ζ相（Ｚｎ13Ｆｅ）１という、ＦｅとＺｎの金属間化合物の積層構造になっている。このうち、界面に存在するΓ相は、非常に硬くて脆く、加工時に容易に破壊されるので、複雑な形状にプレス加工した後、界面のΓ相を起点としてめっき層が剥離する、所謂、パウダリングが起こることがある。 As shown in FIG. 1, the structure of the plated layer of the alloyed hot-dip galvanized steel sheet is as follows: Γ phase (Zn 10 Fe 3 ) 4, Γ 1 phase (Zn 21 Fe 5 ) 3 , Δ 1 phase (Zn 7 Fe) 2, and ζ phase (Zn 13 Fe) 1, and a laminated structure of an intermetallic compound of Fe and Zn. Of these, the Γ phase present at the interface is very hard and brittle, and is easily broken during processing, so after pressing into a complicated shape, the plating layer peels off from the Γ phase at the interface, so-called, Powdering may occur.
パウダリングが起こり難くするためには、Γ相の厚さを薄くすることが有効である。Γ相の厚さを薄くするには、加熱合金化過程において、合金化度を弱める、即ち、合金化時間を短くするか、低温で合金化すればよい。 In order to make powdering difficult to occur, it is effective to reduce the thickness of the Γ phase. In order to reduce the thickness of the Γ phase, the degree of alloying may be reduced in the heating alloying process, that is, the alloying time may be shortened or alloyed at a low temperature.
一方、Γ相を薄くするために合金化度を低くすると、めっき層表面に、ζ相が多く残存する。ζ相は、軟質であるために、めっき層表面にζ相が多いと、プレス加工時に、金型がめっき層に食い込み、鱗片状にめっき層が剥離する、所謂、フレーキングが起こる。 On the other hand, when the degree of alloying is lowered in order to make the Γ phase thinner, a lot of ζ phase remains on the surface of the plating layer. Since the ζ phase is soft, if there is a lot of ζ phase on the surface of the plating layer, so-called flaking occurs in which the mold bites into the plating layer and the plating layer peels off in a scaly manner during press working.
耐パウダリング性及び耐フレーキング性を両立させるには、めっき層中のΓ相、ζ相の両方を、できる限り少なくして、δ1相を多くすることが有効である。しかし、両者を適正範囲に制御するのは容易ではなく、これまで様々な方法が取られてきた。 In order to achieve both powdering resistance and anti-flaking resistance, it is effective to increase both the δ 1 phase by reducing both the Γ phase and the ζ phase in the plating layer as much as possible. However, it is not easy to control both to an appropriate range, and various methods have been taken so far.
例えば、特許文献１には、合金化時に、急速加熱と急速冷却を組み合わせることによりΓ相の成長を抑制して、パウダリング性を改善する技術が開示されている。 For example, Patent Document 1 discloses a technique for improving powdering properties by suppressing Γ phase growth by combining rapid heating and rapid cooling during alloying.
また、特許文献２には、ＩＦ（Interstitial Free）鋼を原板として、鋼中に、Ｓｉ、Ｐを微量添加することにより、母材結晶粒界へのＺｎの拡散を促進させ、めっき密着性を向上させた鋼板が開示されている。
しかし、特許文献１に開示の技術では、Γ相を薄くすれば、パウダリング性は向上するものの、Γ相の本質は変わっていないため、さらに強加工した場合には、めっき密着性を確保できない恐れがある。特許文献２に開示の技術は、ＩＦ鋼を原板とした場合に限られる技術であり、最初から、ＳｉやＰを多量に含有している高強度鋼板には適用することができない。
However, in the technique disclosed in Patent Document 1, if the Γ phase is thinned, the powdering property is improved, but the essence of the Γ phase is not changed. There is a fear. The technique disclosed in
本発明は、前述のような従来技術の問題点を解決し、めっき密着性に優れた合金化溶融亜鉛めっき鋼板を提供することを目的とする。 An object of the present invention is to solve the problems of the prior art as described above and to provide an alloyed hot-dip galvanized steel sheet having excellent plating adhesion.
上記問題を解決するため、本発明者らは、鋭意検討を重ねた結果、合金化溶融亜鉛めっき鋼板の鋼板母材の表層に、Ｓｎ、又はＳｎとＣｕを含有させることにより、めっき密着性、特に、耐パウダリング性が向上し、Γ相の厚さを特に制御しなくても、強加工時にも、パウダリングが起こり難くなり、これまでよりも、めっき密着性を確保することができることを見出した。
In order to solve the above problems, the present inventors have made extensive studies, and as a result, Sn or Sn and Cu are contained in the surface layer of the steel base material of the alloyed hot-dip galvanized steel sheet. In particular, the powdering resistance is improved, and even if the thickness of the Γ phase is not particularly controlled, it is difficult for powdering to occur even during strong processing, and it is possible to ensure better plating adhesion than before. I found it.
さらに、鋼板母材の表層に加えて、めっき層にも、Ｓｎ、又はＳｎとＣｕを含有させることで、めっき密着性が向上する、特に、耐フレーキング性がより高まることを見出した。
Furthermore, it has been found that, by adding Sn or Sn and Cu to the plating layer in addition to the surface layer of the steel plate base material, the plating adhesion is improved, and in particular, the flaking resistance is further improved.
上記の耐パウダリング性の向上効果と相俟って、めっき層中のＦｅ濃度、Γ相、ζ相の厚さや量を、従来のように厳しく制御することなく、強加工時にも、めっき密着性を確保することが可能であることを見出した。 Combined with the above-mentioned effect of improving the powdering resistance, it is possible to adhere to the plating even in strong processing without strictly controlling the Fe concentration, Γ phase and ζ phase thickness and amount in the plating layer as in the past. It was found that it is possible to ensure the sex.
鋼板母材の表層、及び、めっき層中に、Ｃｕ、及び、Ｓｎ、又はＳｎとＣｕを含有させることによって、めっき密着性が向上する理由の詳細については不明であるが、鋼板母材及びめっき層を、上記の構造とすることで、強加工時においても、めっき密着性を確保することができることを見出したのである。
The reason why the plating adhesion is improved by including Cu and Sn, or Sn and Cu in the surface layer and plating layer of the steel plate base material is unknown, but the steel plate base material and plating It has been found that by making the layer have the above structure, it is possible to ensure plating adhesion even during strong processing.
本発明は、上記知見に基づいて完成されたもので、その要旨とするところは、以下の通りである。 The present invention has been completed based on the above findings, and the gist thereof is as follows.
（１）質量％で、
Ｃ：０．００１〜０．３％、
Ｓｉ：０．００１〜３．０％、
Ｍｎ：０．１〜３．０％、
Ａｌ：０．００１〜２．０％、
Ｐ：０．０００１〜０．３％、
Ｓ：０．０００１〜０．１％、
Ｎ：０．０００１〜０．００７％
を含有し、残部がＦｅ及び不可避的不純物からなる鋼板母材の表面に、質量％で、
Ｆｅ：５．０〜２０．０％、
Ａｌ：０．０１〜０．５％
残部がＺｎ及び不可避的不純物からなる亜鉛めっき層を有する合金化溶融亜鉛めっき鋼板であって、鋼板母材の表層１０μｍ以内の領域に、質量％で、
Ｓｎ：０．０１〜１．０％、又は、
Ｓｎ：０．０１〜１．０％と、Ｃｕ：０．０１〜１．０％を含有する
ことを特徴とするめっき密着性に優れた合金化溶融亜鉛めっき鋼板。
(1) In mass%,
C: 0.001 to 0.3%,
Si: 0.001 to 3.0%,
Mn: 0.1 to 3.0%
Al: 0.001 to 2.0%,
P: 0.0001 to 0.3%,
S: 0.0001 to 0.1%,
N: 0.0001 to 0.007%
On the surface of the steel plate base material, the balance being Fe and inevitable impurities, in mass%,
Fe: 5.0 to 20.0%,
Al: 0.01 to 0.5%
The balance is an alloyed hot-dip galvanized steel sheet having a galvanized layer composed of Zn and inevitable impurities, and in a region within 10 μm of the surface layer of the steel sheet base material, in mass%,
Sn: 0.01 to 1.0%, or
An alloyed hot-dip galvanized steel sheet excellent in plating adhesion, characterized by containing Sn: 0.01 to 1.0% and Cu: 0.01 to 1.0% .
（２）前記鋼板母材のＳｎ、又はＳｎとＣｕを含有する領域の深さが、鋼板母材の表層１μｍ以内であることを特徴とする上記（１）に記載のめっき密着性に優れた合金化溶融亜鉛めっき鋼板。
(2) The depth of the region containing Sn or Sn and Cu of the steel plate base material is within 1 μm of the surface layer of the steel plate base material, and has excellent plating adhesion as described in (1) above Alloyed hot-dip galvanized steel sheet.
（３）前記鋼板母材の表層が含有するＣｕ、及び、Ｓｎの含有量が、質量％で、それぞれＣｕ：０．０１〜０．２％、及び、Ｓｎ：０．０１〜０．２％であることを特徴とする上記（１）又は（２）に記載のめっき密着性に優れた合金化溶融亜鉛めっき鋼板。 (3) The contents of Cu and Sn contained in the surface layer of the steel plate base material are mass%, and Cu: 0.01 to 0.2% and Sn: 0.01 to 0.2%, respectively. The alloyed hot-dip galvanized steel sheet having excellent plating adhesion as described in (1) or (2) above.
（４） 前記亜鉛めっき層中に、質量％で、Ｓｎ：０．０１〜１．０％、又はＳｎ：０．０１〜１．０％と、Ｃｕ：０．０１〜１．０％を含有することを特徴とする（１）〜（３）のいずれかに記載のめっき密着性に優れた合金化溶融亜鉛めっき鋼板。
(4) The galvanized layer contains Sn: 0.01 to 1.0%, or Sn: 0.01 to 1.0%, and Cu: 0.01 to 1.0% by mass. An alloyed hot-dip galvanized steel sheet excellent in plating adhesion according to any one of (1) to (3).
（５）前記亜鉛めっき層中のＣｕ、及び、Ｓｎの含有量が、質量％で、それぞれ、Ｃｕ：０．０１〜０．２％、及び、Ｓｎ：０．０１〜０．２％であることを特徴とする上記（４）に記載のめっき密着性に優れた合金化溶融亜鉛めっき鋼板。 (5) The contents of Cu and Sn in the galvanized layer are mass%, and are Cu: 0.01 to 0.2% and Sn: 0.01 to 0.2%, respectively. The alloyed hot-dip galvanized steel sheet having excellent plating adhesion as described in (4) above.
本発明の合金化溶融亜鉛めっき鋼板は、鋼板母材の表層近傍、及び、めっき層中に、Ｓｎ、又はＳｎとＣｕを含有することにより、強加工時にも、めっき密着性を確保することが可能なものであり、自動車の外板や構造部材等の用途に、極めて有効なものである。
The alloyed hot-dip galvanized steel sheet according to the present invention can ensure plating adhesion even during strong processing by containing Sn or Sn and Cu in the vicinity of the surface layer of the steel sheet base metal and in the plating layer. It is possible and is extremely effective for applications such as automobile outer plates and structural members.
以下、本発明を詳細に説明する。 Hereinafter, the present invention will be described in detail.
まず、上記（１）において、鋼中成分を限定している理由を説明する。 First, the reason for limiting the components in steel in (1) above will be described.
鋼板母材中のＣ含有量を０．００１〜０．３質量％の範囲に規定しているのは、０．００１質量％未満とすることは、経済的に不利となる恐れがあり、一方、溶接性を保持することが可能な上限として、０．３質量％が好ましいからである。 The C content in the steel plate base material is regulated in the range of 0.001 to 0.3% by mass, and if it is less than 0.001% by mass, it may be economically disadvantageous, This is because 0.3% by mass is preferable as the upper limit capable of maintaining weldability.
鋼板母材中のＳｉ含有量を０．００１〜３．０質量％の範囲に限定しているのは、０．００１質量％未満とすることは、経済的に不利となる恐れがあり、一方、溶接性を保持することが可能な上限として、３．０質量％が好ましいからである。 The Si content in the steel plate base material is limited to the range of 0.001 to 3.0% by mass, and if it is less than 0.001% by mass, it may be economically disadvantageous, This is because 3.0% by mass is preferable as the upper limit capable of maintaining weldability.
鋼板母材中のＭｎ含有量を０．１〜３．０質量％の範囲に限定しているのは、０．１質量％未満とすることは、経済的に不利となる恐れがあり、一方、上限を３．０質量％としたのは、これを上回る添加は、鋼板の延性に悪影響を及ぼす恐れがあるためである。 The reason why the Mn content in the steel plate base material is limited to the range of 0.1 to 3.0% by mass is to be less than 0.1% by mass, which may be economically disadvantageous. The reason why the upper limit is set to 3.0% by mass is that addition exceeding the upper limit may adversely affect the ductility of the steel sheet.
鋼板母材中のＡｌ含有量を０．００１〜２．０質量％の範囲に限定しているのは、０．００１質量％未満とすることは、経済的に不利となる恐れがあり、一方、２．０質量％を超えると、溶接性を悪化させる恐れがあるためである。 The reason for limiting the Al content in the steel sheet base metal to the range of 0.001 to 2.0 mass% is that it may be economically disadvantageous to be less than 0.001 mass%. If the content exceeds 2.0 mass%, the weldability may be deteriorated.
鋼板母材中のＰ含有量を０．０００１〜０．３質量％の範囲に限定しているのは、０．０００１質量％未満とするのは、コスト的に不利となる恐れがあり、一方、０．３質量％を超えると、溶接性を悪化させる恐れがあるためである。 The P content in the steel plate base metal is limited to the range of 0.0001 to 0.3% by mass, and if it is less than 0.0001% by mass, there is a risk that it may be disadvantageous in terms of cost. If it exceeds 0.3 mass%, the weldability may be deteriorated.
鋼板母材中のＳ含有量を０．０００１〜０．１質量％の範囲に限定しているのは、０．０００１質量％未満とするのは、コスト的に不利となる恐れがあり、一方、０．１質量％を超えると、溶接性を悪化させる恐れがあるためである。 The S content in the steel plate base material is limited to the range of 0.0001 to 0.1% by mass, and if it is less than 0.0001% by mass, there is a risk that it may be disadvantageous in cost. If it exceeds 0.1 mass%, the weldability may be deteriorated.
鋼板母在中のＮ含有量を０．０００１〜０．００７質量％の範囲に限定しているのは、０．０００１質量％未満とするのは、コスト的に不利となる恐れがあり、一方、０．００７質量％を超えると、加工性が低下する恐れがあるからである。 The N content in the base of the steel plate is limited to the range of 0.0001 to 0.007% by mass, and if it is less than 0.0001% by mass, there is a risk that it may be disadvantageous in cost. If it exceeds 0.007 mass%, the workability may be lowered.
上記（１）において、亜鉛めっき層中のＦｅ含有量を５．０〜２０．０質量％の範囲に限定しているのは、５．０質量％未満では、スポット溶接性が劣るからであり、一方、２０．０質量％を超えると、Γ相の厚さが厚くなりすぎて、本発明で規定しているような鋼板母材及びめっき層の構造としても、めっき密着性の確保が困難となるからである。 In the above (1), the reason why the Fe content in the galvanized layer is limited to the range of 5.0 to 20.0% by mass is that spot weldability is inferior at less than 5.0% by mass. On the other hand, if it exceeds 20.0% by mass, the thickness of the Γ phase becomes too thick, and it is difficult to ensure the plating adhesion even in the structure of the steel plate base material and the plating layer as defined in the present invention. Because it becomes.
めっき層中のＡｌ含有量を０．０１〜０．５質量％の範囲に限定しているのは、めっき層中にＡｌを０．０１質量％以上含有させることにより、過剰なζ相とΓ相の生成を抑制することができるからである。一方、０．５質量％を超えてＡｌを添加すると、Ａｌがめっき層表面に濃化して、スポット溶接性を悪化させる。そのため、上限を０．５質量％とした。 The reason why the Al content in the plating layer is limited to the range of 0.01 to 0.5% by mass is that by containing 0.01% by mass or more of Al in the plating layer, excess ζ phase and Γ This is because the generation of phases can be suppressed. On the other hand, when Al is added exceeding 0.5% by mass, Al is concentrated on the surface of the plating layer to deteriorate spot weldability. Therefore, the upper limit is set to 0.5% by mass.
めっき層中のＦｅ及びＡｌの濃度を測定するには、めっき層を酸で溶解し、溶解液を化学分析する方法を用いればよい。例えば、３０ｍｍ×４０ｍｍに切断した合金化溶融亜鉛めっき鋼板について、インヒビタを添加した５％ＨＣｌ水溶液で、鋼板母材の溶出を抑制しながら、めっき層のみを溶解し、溶解液をＩＣＰ発光して得られた信号強度と、濃度既知溶液から作成した検量線から、Ｆｅ及びＡｌの含有量を定量する方法を用いればよい。 In order to measure the concentration of Fe and Al in the plating layer, a method of dissolving the plating layer with an acid and chemically analyzing the solution may be used. For example, an alloyed hot-dip galvanized steel sheet cut to 30 mm × 40 mm is dissolved with a 5% HCl aqueous solution to which an inhibitor is added while only the plating layer is dissolved while suppressing dissolution of the steel sheet base material, and the solution is subjected to ICP light emission. A method of quantifying the content of Fe and Al from the obtained signal intensity and a calibration curve created from a solution having a known concentration may be used.
めっき付着量については、特に制約はないが、耐食性の観点から、片面付着量で、５ｇ／ｍ2以上が望ましい。また、めっき密着性を確保するとの観点からは、片面付着量で、１００ｇ／ｍ2を超えないことが望ましい。 Although there is no restriction | limiting in particular about the plating adhesion amount, From a corrosion-resistant viewpoint, 5 g / m < 2 > or more is desirable by the single-sided adhesion amount. Further, from the viewpoint of securing plating adhesion, it is desirable that the amount of adhesion on one side does not exceed 100 g / m 2 .
本発明の溶融亜鉛めっき鋼板上に、塗装性や、溶接性を改善する目的で、上層めっきを施すことや、各種の処理、例えば、クロメート処理、非クロメート処理、りん酸塩処理、潤滑性向上処理、溶接性向上処理等を施すことは、本発明を逸脱するものではない。 On the hot dip galvanized steel sheet of the present invention, for the purpose of improving paintability and weldability, it is possible to perform upper layer plating, various treatments such as chromate treatment, non-chromate treatment, phosphate treatment, lubricity improvement. It is not deviated from the present invention to perform processing, weldability improvement processing, and the like.
本発明の合金化溶融亜鉛めっき鋼板は、鋼板母材の表層に、Ｓｎ、又はＳｎとＣｕを含有させることにより、めっき密着性を向上させている。本発明の合金化溶融亜鉛めっき鋼板の断面構造の一例を、模式的に、図２に示す。
The alloyed hot-dip galvanized steel sheet of the present invention is improved in plating adhesion by containing Sn or Sn and Cu in the surface layer of the steel sheet base material. An example of the cross-sectional structure of the galvannealed steel sheet of the present invention is schematically shown in FIG.
鋼板母材の表層に、Ｓｎ、又はＳｎとＣｕを含有させることにより、めっき密着性が向上するのは、ＣｕやＳｎが、鋼板母材の粒界に偏析し、加工時に、鋼板母材表層の粒界が脆化して割れることにより、Γ相内に集中した応力を緩和して、Γ相を起点とする割れが生じ難くなるからであると考えられる。
By including Sn or Sn and Cu in the surface layer of the steel plate base material, the plating adhesion is improved because Cu and Sn segregate at the grain boundaries of the steel plate base material, and during processing, the steel plate base material surface layer This is considered to be because the grain boundaries of the steel become brittle and cracked, so that stress concentrated in the Γ phase is relaxed and cracks starting from the Γ phase are less likely to occur.
即ち、鋼板母材の表層に、Ｓｎ、又はＳｎとＣｕを含有させることにより、特に、耐パウダリング性を向上させることができる。
That is, the powdering resistance can be particularly improved by adding Sn or Sn and Cu to the surface layer of the steel plate base material.
鋼板母材表層のＳｎ、又はＳｎとＣｕの含有量を、質量％で、それぞれ、Ｃｕ：０．０１〜１．０％、及び、Ｓｎ：０．０１〜１．０％としたのは、Ｃｕ及び／又はＳｎを０．０１％以上含有させることにより、めっき密着性を向上させる効果が現れるからであり、一方、１．０％を超えて含有させると、逆に、鋼板母材表層の粒界同士の密着力が弱くなり、加工時に、母材ごと、めっき層が剥離する恐れがあるからである。また、鋼板母材の割れの程度がひどくなり、プレス割れ等の恐れがあるからである。
The content of Sn or Sn and Cu in the surface layer of the steel plate base material was, in mass%, Cu: 0.01 to 1.0% and Sn: 0.01 to 1.0%, This is because the effect of improving the plating adhesion appears by containing 0.01% or more of Cu and / or Sn. On the other hand, if the content exceeds 1.0%, conversely, This is because the adhesion between the grain boundaries is weakened, and the plating layer may be peeled off together with the base material during processing. In addition, the degree of cracking of the steel plate base metal becomes so severe that there is a risk of press cracking or the like.
鋼板母材の表層がＳｎ、又はＳｎとＣｕを含有している領域を、１０μｍ以内と規定したのは、１０μｍ超の領域にＳｎ、又はＳｎとＣｕを含んでいても、めっき密着性を向上させる効果が飽和するばかりか、鋼板母材の材質、特に、延性に悪影響を及ぼすからである。延性の低下が著しい場合には、プレス割れを起こすこともある。
A region where the surface layer of the steel sheet base material contains a Sn, or Sn and Cu, were defined within a 10μm also include a 10μm greater area Sn, or Sn and Cu, improve coating adhesion This is because not only the effect of saturating is saturated, but also the material of the steel plate base metal, particularly the ductility, is adversely affected. If the ductility is significantly reduced, press cracks may occur.
本発明の合金化溶融亜鉛めっき鋼板の鋼板母材は、表層以外は、Ｃｕ及びＳｎを、意図的には含有させていない。しかし、スクラップ等から不可避的に混入するトランプエレメントとしてのＣｕ及び／又はＳｎは、鋼板母材の材質に悪影響を及ぼさない程度、即ち、Ｃｕ：０．０１質量％未満、Ｓｎ：０．０１質量％未満であれば、含有していても構わない。 The steel plate base material of the galvannealed steel plate of the present invention does not intentionally contain Cu and Sn except for the surface layer. However, Cu and / or Sn as a trump element inevitably mixed from scrap or the like does not adversely affect the material of the steel plate base material, that is, Cu: less than 0.01 mass%, Sn: 0.01 mass If it is less than%, it may be contained.
鋼板母材の表層の、Ｓｎ、又はＳｎとＣｕの含有量、及び、含有している領域を確認するには、めっき鋼板の断面から組織観察を行い、鋼板母材の表層を断面から組成分析すればよい。
In order to confirm the Sn or Sn and Cu contents and the contained region of the surface layer of the steel plate base material, the structure is observed from the cross section of the plated steel plate, and the composition analysis of the surface layer of the steel plate base material is performed from the cross section. do it.
例えば、めっき鋼板を樹脂に埋め込んで、断面を鏡面研磨した後、電解放出型走査型電子顕微鏡（ＦＥ−ＳＥＭ）により観察する方法と、エネルギー分散型Ｘ線検出器（ＥＤＸ）により組成分析を行う方法が挙げられる。 For example, after embedding a plated steel plate in resin and mirror-polishing the cross section, the composition is analyzed by a method using an electron emission scanning electron microscope (FE-SEM) and an energy dispersive X-ray detector (EDX). A method is mentioned.
ＥＤＸで分析すれば、鋼板母材の表層におけるＣｕ及びＳｎの濃度、また、その存在している深さを確認することができる。 If it analyzes by EDX, the density | concentration of Cu and Sn in the surface layer of a steel plate base material, and the depth which exists can be confirmed.
ＣｕやＳｎを鋼板母材の表層に含有させるには、ＣｕやＳｎを、鋼板母材以外から供給する必要がある。 In order to contain Cu or Sn in the surface layer of the steel plate base material, it is necessary to supply Cu or Sn from other than the steel plate base material.
冷間圧延後の鋼板を、連続焼鈍ライン（ＣＡＰＬ）にて７００〜９００℃で焼鈍した後、酸洗した後に、鋼板表面に、Ｓｎ、又はＳｎとＣｕを付着させ、その後、ＣＧＬに通板して、焼鈍炉で６００〜７００℃で焼鈍して、Ｓｎ、又はＳｎとＣｕを、鋼板母材表層に加熱拡散させ、その後、通常のめっき、合金化処理を行うことにより、鋼板母材の表層に、Ｓｎ、又はＳｎとＣｕを含有させた合金化溶融亜鉛めっき鋼板を製造することができる。
The steel sheet after cold rolling is annealed at 700 to 900 ° C. in a continuous annealing line (CAPL), pickled, and then Sn or Sn and Cu are attached to the steel sheet surface, and then passed through CGL. Then, annealing is performed at 600 to 700 ° C. in an annealing furnace, Sn or Sn and Cu are heated and diffused in the surface layer of the steel plate base material, and thereafter, normal plating and alloying treatment are performed, so that the steel plate base material An alloyed hot-dip galvanized steel sheet containing Sn or Sn and Cu in the surface layer can be produced.
ＣＧＬ通板前に、鋼板表面にＳｎ、又はＳｎとＣｕを付着させる方法としては、電気めっき、無電解めっき、気相めっき、などが考えられるが、その方法は、特に限定されるものではない。
As a method for adhering Sn or Sn and Cu to the steel plate surface before passing the CGL, electroplating, electroless plating, vapor phase plating, and the like can be considered, but the method is not particularly limited.
鋼板母材の表層にＳｎ、又はＳｎとＣｕを含有している領域を、１０μｍ以内に制御するには、鋼板表面にＳｎ、又はＳｎとＣｕを付着させた後、ＣＧＬで、６００〜７００℃で焼鈍する際の焼鈍時間を、１２０秒以内とすればよい。
In order to control the region containing Sn or Sn and Cu on the surface layer of the steel plate base material within 10 μm, Sn or Sn and Cu are attached to the steel plate surface, and then CGL is used at 600 to 700 ° C. The annealing time when annealing is performed within 120 seconds.
鋼板母材の表層のＣｕ、及び、Ｓｎの含有量を、質量％で、それぞれ、Ｃｕ：０．０１〜１．０％、及び、Ｓｎ：０．０１〜１．０％とするには、ＣＧＬ通板前に、鋼板表面に付着させるＣｕ、及び、Ｓｎの付着量を、それぞれ、Ｃｕ：０．０１〜１．０ｇ／ｍ2、及び、Ｓｎ：０．０１〜１．０ｇ／ｍ2とすればよい。 To make the Cu and Sn contents of the surface layer of the steel plate base material in mass%, Cu: 0.01 to 1.0% and Sn: 0.01 to 1.0%, Prior to CGL passing, the amount of Cu and Sn deposited on the steel plate surface was Cu: 0.01 to 1.0 g / m 2 and Sn: 0.01 to 1.0 g / m 2 , respectively. do it.
上記（２）において、鋼板母材がＳｎ、又はＳｎとＣｕを含有している領域が、鋼板母材表面から１μｍ以内であると限定したのは、１μｍ以内とすることで、めっき密着性の向上効果が、特に高まるからである。
In the above (2), the region where the steel plate base material contains Sn or Sn and Cu is limited to within 1 μm from the surface of the steel plate base material. This is because the improvement effect is particularly enhanced.
上記（３）において、鋼板母材が表層近傍に含有しているＣｕ、及び、Ｓｎの含有量を、質量％で、それぞれ、Ｃｕ：０．０１〜０．２％、及び、Ｓｎ：０．０１〜０．２％に限定したのは、Ｃｕ及びＳｎの含有量を、０．０１〜０．２％の範囲とすることで、めっき密着性を向上させる効果が、特に高くなるからである。 In the above (3), the contents of Cu and Sn contained in the vicinity of the surface layer of the steel plate base material are expressed in terms of mass%, Cu: 0.01 to 0.2%, and Sn: 0.00. The reason for limiting the content to 01 to 0.2% is that the effect of improving the plating adhesion is particularly enhanced by setting the content of Cu and Sn in the range of 0.01 to 0.2%. .
上記（４）において、亜鉛めっき層中に、Ｓｎ、又はＳｎとＣｕを含有するとしたのは、鋼板母材に加え、亜鉛めっき層中にも、Ｓｎ、又はＳｎとＣｕを含有させることにより、めっき密着性の向上効果、特に、耐フレーキング性がさらに高まるからである。
In the above (4), it is assumed that Sn or Sn and Cu are contained in the galvanized layer. In addition to the steel plate base material, Sn or Sn and Cu are contained in the galvanized layer. This is because the effect of improving the plating adhesion, particularly the flaking resistance, is further enhanced.
その理由としては、めっき層の表層に存在しているζ相に、ＣｕやＳｎが固溶することにより、ζ相の硬度が上昇し、プレス成形時に、金型との滑り性がよくなるからであると考えられる。 The reason is that the hardness of the ζ phase increases due to the solid solution of Cu and Sn in the ζ phase existing in the surface layer of the plating layer, and the slipperiness with the mold is improved during press molding. It is believed that there is.
Ｓｎ、又はＳｎとＣｕは、ζ相のみに濃化しているのではなく、δ相、Γ1相、及び／又は、Γ相中にも固溶し、めっき層全体に均一に分布しているものと考えられる。
Sn, or Sn and Cu , is not concentrated only in the ζ phase, but also dissolves in the δ phase, Γ 1 phase, and / or Γ phase, and is uniformly distributed throughout the plating layer. It is considered a thing.
亜鉛めっき層中のＣｕ、及び、Ｓｎの含有量を、質量％で、それぞれ、Ｃｕ：０．０１〜１．０％、及び、Ｓｎ：０．０１〜１．０％と規定したのは、Ｃｕ及び／又はＳｎを０．０１％以上含有させることにより、めっき密着性を向上させる効果が現れるからであり、一方、１．０％超含有させても、その効果が飽和するばかりか、めっき層の硬度が上昇しすぎて、密着性が低下する恐れがあるからである。 The contents of Cu and Sn in the galvanized layer were specified in terms of mass% as Cu: 0.01 to 1.0% and Sn: 0.01 to 1.0%, respectively. This is because by containing 0.01% or more of Cu and / or Sn, the effect of improving the plating adhesion appears. On the other hand, the inclusion of more than 1.0% not only saturates the effect, but also plating. This is because the hardness of the layer is excessively increased and the adhesion may be decreased.
めっき層中のＣｕ及びＳｎの含有量を確認するには、前述した、めっき層中のＦｅ及びＡｌの濃度を測定する方法と同様の方法、即ち、めっき層を酸で溶解し、溶解液を化学分析する方法を用いればよい。 In order to confirm the contents of Cu and Sn in the plating layer, the same method as the method for measuring the concentration of Fe and Al in the plating layer described above, ie, dissolving the plating layer with an acid, A chemical analysis method may be used.
鋼板母材に加えて、めっき層中にもＳｎ、又はＳｎとＣｕを含有させるには、鋼板母材の表層近傍にＳｎ、又はＳｎとＣｕを含有させるのと同様に、ＣＡＰＬで焼鈍後、ＣＧＬの通板前に、Ｓｎ、又はＳｎとＣｕを鋼板母材表面に付着させればよいが、ＣＧＬでの焼鈍温度を低くする必要がある。即ち、焼鈍温度が高いと、Ｓｎ、又はＳｎとＣｕが、全て、鋼板母材中に拡散しまうからである。
In addition to the plate matrix, the well is contained Sn, or Sn and Cu in the plating layer, similar to the inclusion of the vicinity of the surface layer to the Sn, or Sn and Cu of the plate matrix, after annealing in CAPL, Before passing CGL, Sn or Sn and Cu may be attached to the surface of the steel plate base material, but it is necessary to lower the annealing temperature in CGL. That is, when the annealing temperature is high, Sn or Sn and Cu are all diffused into the steel plate base material.
ＣＧＬにおいて、４００〜５００℃にて１２０秒以内で焼鈍することによって、鋼板表面に、未拡散のＳｎ、又はＳｎとＣｕを残存させ、その状態で、めっき、合金化を行うことにより、鋼板母材に加えて、めっき層中にも、Ｓｎ、又はＳｎとＣｕを含有させた合金化溶融亜鉛めっき鋼板を製造することができる。
In CGL, annealing is performed at 400 to 500 ° C. within 120 seconds to leave undiffused Sn or Sn and Cu on the surface of the steel sheet, and in this state, plating and alloying are performed. In addition to the material, an alloyed hot-dip galvanized steel sheet containing Sn or Sn and Cu can also be produced in the plating layer.
上記（５）において、亜鉛めっき層が含有しているＳｎ、又はＳｎとＣｕの含有量を、質量％で、それぞれ、Ｃｕ：０．０１〜０．２％、及び、Ｓｎ：０．０１〜０．２％に限定したのは、Ｃｕ及びＳｎの含有量を、０．０１〜０．２質量％の範囲とすることで、めっき密着性を向上させる効果が、特に高くなるからである。
In the above (5), the contents of Sn or Sn and Cu contained in the galvanized layer are in mass%, Cu: 0.01 to 0.2%, and Sn: 0.01 to The reason for limiting to 0.2% is that the effect of improving the plating adhesion is particularly enhanced by setting the contents of Cu and Sn in the range of 0.01 to 0.2% by mass.
以下、実施例により本発明を具体的に説明するが、本発明は本実施例に限定されるものではない。 EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited to the examples.
表１に示す組成からなるスラブを１１５０〜１２００℃に加熱し、仕上げ温度９００〜９３０℃で熱間圧延をして、厚さ４ｍｍの熱間圧延鋼帯とし、５８０〜６８０℃で巻き取った。酸洗後、冷間圧延を施して、厚さ１．０ｍｍの冷間圧延鋼帯とした後、ＣＡＰＬに通板して７００〜９００℃で焼鈍した。 A slab having the composition shown in Table 1 was heated to 1150 to 1200 ° C. and hot-rolled at a finishing temperature of 900 to 930 ° C. to form a hot-rolled steel strip having a thickness of 4 mm and wound at 580 to 680 ° C. . After pickling, cold rolling was performed to obtain a cold-rolled steel strip having a thickness of 1.0 mm, followed by passing through CAPL and annealing at 700 to 900 ° C.
その後、酸洗を施し、表２及び表３に示す付着量で、Ｃｕ、Ｓｎを電気めっきによって付着させ、ＣＧＬの焼鈍工程において、Ｎ2―５vol％Ｈ2の雰囲気中で、表２及び表３に示すような条件で、焼鈍後、浴中Ａｌ濃度０．１〜０．２質量％、浴温４５０〜４６５℃のめっき浴に３〜１０秒浸漬し、その後、４６０〜５８０℃で１０〜２００秒間、合金化した。 Thereafter, pickling is performed, and Cu and Sn are attached by electroplating in the amounts shown in Tables 2 and 3, and in the annealing process of CGL, in an atmosphere of N 2 -5 vol% H 2 , Tables 2 and 3 is immersed in a plating bath having an Al concentration of 0.1 to 0.2% by mass in the bath and a bath temperature of 450 to 465 ° C. for 3 to 10 seconds after annealing, and then 10 to 460 to 580 ° C. Alloyed for ~ 200 seconds.
めっき層中のＦｅ濃度、Ａｌ濃度、Ｃｕ濃度、及び、Ｓｎ濃度は、前述のように、インヒビタを添加した５％ＨＣｌ水溶液でめっき層のみを溶解し、溶解液をＩＣＰ発光分析することにより測定した。 As described above, the Fe concentration, Al concentration, Cu concentration, and Sn concentration in the plating layer are measured by dissolving only the plating layer with a 5% HCl aqueous solution to which an inhibitor is added and analyzing the solution by ICP emission spectrometry. did.
鋼板母材表層のＣｕ濃度、Ｓｎ濃度、及び、存在深さは、前述のように、めっき鋼板を樹脂に埋め込んで、断面を鏡面研磨した後、ＦＥ−ＳＥＭによる観察と、ＥＤＸによる組成分析により、測定した。 As described above, the Cu concentration, the Sn concentration, and the existence depth of the surface layer of the steel plate are embedded by embedding the plated steel plate in the resin, and the cross section is mirror-polished, then observed by FE-SEM and composition analysis by EDX. ,It was measured.
耐パウダリング性の評価は、４５°Ｖ曲げ試験により、行った。評価面が、曲げの内側に来るように、先端の曲率半径が１ｍｍである金型を用いて、６０°に曲げ加工し、曲げ部内側にテープを貼り、テープを引き剥がした。テープと共に剥離しためっき層の剥離状況から、５点満点で耐パウダリング性を評価した。 The powdering resistance was evaluated by a 45 ° V bending test. Using a mold having a curvature radius of 1 mm at the tip so that the evaluation surface comes to the inside of the bend, bending was performed at 60 °, a tape was applied to the inside of the bent portion, and the tape was peeled off. From the peeling state of the plating layer peeled off with the tape, the powdering resistance was evaluated from 5 points.
評点付けは、５点：剥離幅２ｍｍ未満、４点：剥離幅２ｍｍ以上３ｍｍ未満、３点：剥離幅３ｍｍ以上５ｍｍ未満、２点：剥離幅５ｍｍ以上７ｍｍ未満、１点：剥離幅７ｍｍ以上とし、２点以上を合格とした。 Rating: 5 points: peeling width less than 2 mm, 4 points: peeling width of 2 mm or more and less than 3 mm, 3 points: peeling width of 3 mm or more and less than 5 mm, 2 points: peeling width of 5 mm or more and less than 7 mm, 1 point: peeling width of 7 mm or more Two or more points were accepted.
耐フレーキング性の評価は、ドロービード試験により、行った。ドロービード試験には、凸部先端の曲率半径が１ｍｍの凸金型と、凹部肩の曲率半径が１ｍｍ、凹部深さが３ｍｍである凹金型を組み合わせて用い、サンプルサイズ３０×３００ｍｍの鋼板に対して、押し付け加重５００ｋｇｆ、引き抜き速度２００ｍｍ／ｍｉｎ、引き抜き距離５０ｍｍでドロービード試験した。その後、ビード通過面にテープを張り、テープを引き剥がした。 The evaluation of anti-flaking property was performed by a draw bead test. In the draw bead test, a convex mold having a curvature radius of 1 mm at the tip of the convex part and a concave mold having a curvature radius of the shoulder of the concave part of 1 mm and a concave part depth of 3 mm were used in combination on a steel plate having a sample size of 30 × 300 mm. On the other hand, a draw bead test was performed at a pressing load of 500 kgf, a drawing speed of 200 mm / min, and a drawing distance of 50 mm. Thereafter, a tape was applied to the bead passage surface, and the tape was peeled off.
剥離前後の重量差から、テープと共に剥離しためっき層の重量を求め、その剥離量によって、５点満点で耐フレーキング性を評価した。 From the weight difference before and after peeling, the weight of the plating layer peeled together with the tape was determined, and the flaking resistance was evaluated based on the amount of peeling, with a maximum of 5 points.
評点付けは、５点：剥離量２ｇ／ｍ2未満、４点：２以上４未満、３点：４以上８未満、２点：８以上１２未満、１点：剥離量１２ｇ／ｍ2以上とし、２点以上を合格とした。 Rating: 5 points: peel amount less than 2 g / m 2 , 4 points: 2 to less than 4, 3 points: 4 to less than 8, 2 points: 8 to less than 12, 1 point: peel amount of 12 g / m 2 or more Two or more points were accepted.
鋼板母材の加工後の割れの有無は、４５°Ｖ曲げ試験後、及び、ドロービード試験後のサンプルを目視で確認することにより行った。鋼板母材が破断したもの、又は、目視で確認できるほど割れが生じたものを×、目視では鋼板割れが確認できなかったものを○とし、○を合格とした。 The presence or absence of cracks after the processing of the steel plate base material was performed by visually confirming samples after the 45 ° V bending test and after the draw bead test. The case where the steel plate base material was broken or the case where cracks were generated to the extent that it could be visually confirmed was evaluated as x.
評価結果を、表４及び表５に示す。表４及び表５より、本発明例は、全て、めっき密着性の評価が合格レベルを満たしている。本発明の範囲を満たさない比較例は、いずれも、めっき密着性の評価が低い。 The evaluation results are shown in Tables 4 and 5. From Tables 4 and 5, in all of the examples of the present invention, the evaluation of plating adhesion satisfies the pass level. All of the comparative examples not satisfying the scope of the present invention have a low evaluation of plating adhesion.
１ ζ相（Ｚｎ13Ｆｅ）
２ δ1相（Ｚｎ7Ｆｅ）
３ Γ1相（Ｚｎ21Ｆｅ5）
４ Γ相（Ｚｎ10Ｆｅ3）
５ 鋼板母材
６ 合金化溶融亜鉛めっき層
７ 鋼板母材の表層に、Ｃｕ、Ｓｎの１種又は２種を含有している領域
８ 鋼板母材
1 ζ phase (Zn 13 Fe)
2 δ 1 phase (Zn 7 Fe)
3 Γ 1 phase (Zn 21 Fe 5 )
4 Γ phase (Zn 10 Fe 3 )
5 Steel
Claims (5)
Ｃ：０．００１〜０．３％、
Ｓｉ：０．００１〜３．０％、
Ｍｎ：０．１〜３．０％、
Ａｌ：０．００１〜２．０％、
Ｐ：０．０００１〜０．３％、
Ｓ：０．０００１〜０．１％、
Ｎ：０．０００１〜０．００７％
を含有し、残部がＦｅ及び不可避的不純物からなる鋼板母材の表面に、質量％で、
Ｆｅ：５．０〜２０．０％、
Ａｌ：０．０１〜０．５％
残部がＺｎ及び不可避的不純物からなる亜鉛めっき層を有する合金化溶融亜鉛めっき鋼板であって、鋼板母材の表層１０μｍ以内の領域に、質量％で、
Ｓｎ：０．０１〜１．０％、又は、
Ｓｎ：０．０１〜１．０％と、Ｃｕ：０．０１〜１．０％を含有する
ことを特徴とするめっき密着性に優れた合金化溶融亜鉛めっき鋼板。 % By mass
C: 0.001 to 0.3%,
Si: 0.001 to 3.0%,
Mn: 0.1 to 3.0%
Al: 0.001 to 2.0%,
P: 0.0001 to 0.3%,
S: 0.0001 to 0.1%,
N: 0.0001 to 0.007%
On the surface of the steel plate base material, the balance being Fe and inevitable impurities, in mass%,
Fe: 5.0 to 20.0%,
Al: 0.01 to 0.5%
The balance is an alloyed hot-dip galvanized steel sheet having a galvanized layer composed of Zn and inevitable impurities, and in a region within 10 μm of the surface layer of the steel sheet base material, in mass%,
Sn: 0.01 to 1.0%, or
An alloyed hot-dip galvanized steel sheet excellent in plating adhesion, characterized by containing Sn: 0.01 to 1.0% and Cu: 0.01 to 1.0% .
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