JP3735339B2 - Method for producing alloyed hot-dip galvanized steel sheet with excellent workability - Google Patents
Method for producing alloyed hot-dip galvanized steel sheet with excellent workability Download PDFInfo
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Description
【０００１】
【発明の属する技術分野】
本発明は、高Ｓｉ系鋼板または高Ｐ系鋼板を基材とする外観およびめっき密着性と加工性に優れた合金化溶融亜鉛めっき鋼板の製造方法に関するものである。
【０００２】
【従来の技術】
近年、自動車の軽量化対策と腐食防止を目的として自動車の外板または内板用に高強度鋼板を下地とする合金化溶融亜鉛めっき鋼板を使用する需要が増大してきている。この高強度鋼板には、Ｓｉを０．２〜２．０％含有するか、または、Ｐが０．０３〜０．２％で含有されているため、被めっき鋼板表面に不均一な酸化膜や鋼中成分の不均一な濃化を有しやすく、従来の溶融亜鉛めっき法においては不めっきを生じたり、また、界面のバリア層が強化され合金化が十分進行しなかったり、めっき層中の合金層が局部的に異常発生するなどの問題があった。
【０００３】
上述したような問題を解消するために、例えば特開平４−３４６６４４号公報（特許文献１）で提案しているように、高張力鋼板の表面をサンドペーパーや研磨、ブラシ研磨、ショットブラスト、電解研磨などで表面層を除去した後、プレＮｉめっきをして溶融亜鉛の不めっきをなくし、めっき密着性をよくする方法や特開平４−３０４３４６号公報（特許文献２）で提案しているように、被めっき鋼板の表面を０．１〜５μｍ研削し、該鋼板を、Ｓｉ：０．００１〜０．２重量％、Ａｌ：０．０５〜０．２０質量％、残部Ｚｎおよび不可避的不純物からなる溶融亜鉛めっき浴を用いためっきを行ない、その後加熱合金化処理を行う方法、または、特開平１０−８１９４８号公報で提案しているように、被めっき鋼板の表面を１〜８ｇ／ｍ2 研削除去した鋼板への合金化溶融亜鉛めっき鋼板の製造方法が開示されている。
【０００４】
【引用文献】
（１）特許文献１（特開平４−３４６６４４号公報）
（２）特許文献２（特開平４−３０４３４６号公報）
（３）特許文献３（特開平１０−８１９４８号公報）
【０００５】
【発明が解決しようとする課題】
上述した特許文献１はプレＮｉめっきを条件としている。また、特許文献２はめっき浴組成にＳｉ濃度の限定を加え、ＳｉとＡｌの役割としてＦｅ−Ｚｎ合金相の成長過程でＳｉ，Ａｌは少なくとも地鉄界面、δ1 相およびその表面に濃化偏析し、このＳｉ，Ａｌ偏析帯がバリアーとなって合金相の生成形態の加工応力を分散させやすい入り乱れた構造とするため、合金化溶融亜鉛めっき鋼板の加工性が向上するというものである。さらに、特開平１０−８１９４８号公報（特許文献３）はＰを含む極低炭素鋼にＳｉを含有させ、かつめっき前に行う還元加熱後の冷却条件とめっき後の合金化処理条件とを管理することにより耐パウダリング性および耐チッピング性の向上を図るものである。しかし、これらはいずれも鋼板表面のＲａ値との関係から解明したものではない。
【０００６】
（１）鋼中Ｓｉ濃度０．２〜２．０％の合金化溶融亜鉛めっき鋼板の製造方法において、被めっき鋼板の表面を研削してＲａ：０．３〜０．６とし、この鋼板を研削したままの状態で加熱焼鈍し、Ａｌ：０．０５〜０．２０質量％、残部Ｚｎおよび不可避的不純物からなる溶融亜鉛めっき浴に浸漬した後、加熱合金化処理を行なうことを特徴とする加工性の優れた合金化溶融亜鉛めっき鋼板の製造方法。
【０００７】
（２）鋼中Ｐ濃度０．０３％以上の合金化溶融亜鉛めっき鋼板の製造方法において、被めっき鋼板の表面を研削してＲａ：０．３〜０．６とし、この鋼板を研削したままの状態で加熱焼鈍し、Ａｌ：０．０５〜０．２０質量％、残部Ｚｎおよび不可避的不純物からなる溶融亜鉛めっき浴に浸漬した後、加熱合金化処理を行なうことを特徴とする加工性の優れた合金化溶融亜鉛めっき鋼板の製造方法である。
【０００８】
【発明の実施の形態】
以下、本発明について詳細に説明する。
本発明において、鋼中Ｓｉ濃度０．２〜２．０％の鋼板の表面を研削してＲａ：０．３〜０．６とするのは、鋼中Ｓｉによる地鉄表面へのＳｉの拡散による濃縮および鋼板表面の酸化による鋼板表面のＳｉＯ2 を含む酸化被膜を除去することにより溶融亜鉛めっき時の濡れ性および合金化反応を改善することは勿論のこと合金化溶融亜鉛めっき鋼板の表面上に縦縞模様を生じて外観性を阻害するのを防止するためである。鋼中Ｓｉ濃度が０．２％未満では外観不良の問題は生じず、また、２．０％を超えると本発明法を適用しても十分な効果が得られない。従って、その範囲を０．２〜２．０％とした。
【０００９】
また、鋼板の表面をＲａ：０．３〜０．６としたのは、上記した溶融亜鉛めっき時の濡れ性および合金化反応を改善することは勿論のこと、特に合金化溶融亜鉛めっき鋼板の表面に縦縞模様を生じて外観性を阻害するのを防止するためで、０．３未満ではＲａ：０．３μｍと比較してそれ以上外観改善効果が得られずプロセスロールとのスリップ発生の問題があり、また、０．６を超えると合金化溶融亜鉛めっき鋼板の表面上に縦縞模様を生じて外観性を阻害することから、その範囲を０．３〜０．６とした。
【００１０】
また、鋼板の表面をＲａ：０．３〜０．６にするためには、鋼板の表面をサンドペーパー研磨、ブラシ研磨、ショットブラストなどの種々の方法で除去する。特にブラシ研磨を用いる場合は、例えばブラシ糸径：０．８〜１．６ｍｍ、ブラシ糸材質：ナイロン、金属等、ブラシ砥粒の番手：２４０番、１００番、８０番等を選択し、ブラシ回転数を６００〜１２００ｒｐｍの範囲で制御することにより行う。
【００１１】
さらに、鋼中Ｐについても、Ｓｉと同様に鋼板表面へのＰの拡散による濃縮および鋼板表面の酸化膜が発生しやすく、溶融亜鉛めっき性が悪くて合金化の進行が妨げられる。そのために、特に鋼中Ｐ濃度が０．０３％以上の高Ｐ含有鋼板についても、その表面を研磨し、所定のＲａ値にすることにより、溶融亜鉛めっき後、合金化処理後のめっき層の均一性および加工部の密着性の向上を図るものである。しかし、鋼中Ｐ濃度が０．０３％未満では外観不良の問題は生じないことから、その下限を０．０３％とした。
【００１２】
Ａｌ：０．０５〜０．２０質量％とした理由は、Ａｌが０．０５％未満であると、めっき界面に脆いＦｅ−Ｚｎ層が生成し、めっき密着性を損なう。また、０．２０％を超えるとＡｌによるＦｅ拡散抑制効果が強く、めっき層の合金化処理を完成するのに長時間を要するとともに外観が損なわれることから、その上限を０．２０％とした。このような溶融亜鉛めっき浴に浸漬した後、加熱合金化処理を行う。合金化処理時の加熱温度は、４４０〜６００℃の範囲で行う。４４０℃に満たない温度域の場合には合金化が不十分になり、また、６００℃を超える温度域では合金化が進みすぎ、Γ相が発生しやすくなり、めっき密着性が劣化する。また、合金化時間については、合金化温度とのバランスで決まるが、１０〜４０秒の範囲が最適である。１０秒未満では合金化が進みにくく、４０秒を超えると合金化が進みすぎ、Γ相が発生しやすくなり、めっき密着性が劣化する。
【００１３】
【実施例】
（実施例１）
以下、本発明について実施例によって具体的に説明する。
ゼンジマー式溶融亜鉛めっきラインにて、板厚１．２ｍｍで板幅９００ｍｍの鋼中Ｓｉ濃度０．４〜１．５％の鋼板をブラシ研磨にて鋼板表面を研磨し続いて加熱焼鈍した後、溶融亜鉛めっき浴に浸漬しガスワイピング方式にて所定の付着量にめっきし、直ちに加熱処理炉内に導き板温度４８０〜５５０℃、保持時間１５〜３０秒間の条件にて合金化溶融めっき鋼板を製造した。その際、前処理条件としての鋼板のＲａ値、用いた溶融亜鉛めっき浴の組成、および得られた合金化溶融めっき鋼板の外観および加工性評価結果を表１に示す。
【００１４】
（実施例２）
実施例１と同様の条件で、ゼンジマー式溶融亜鉛めっきラインにて、板厚１．２ｍｍで板幅９００ｍｍの鋼中Ｐ濃度０．０３５〜０．０９％の鋼板をブラシ研磨にて鋼板表面を研磨し続いて加熱焼鈍した後、溶融亜鉛めっき浴に浸漬しガスワイピング方式にて所定の付着量にめっきし、直ちに加熱処理炉内に導き板温度４８０〜５５０℃、保持時間１５〜２０秒間の条件にて合金化溶融めっき鋼板を製造した。その際、前処理条件としての鋼板のＲａ値、用いた溶融亜鉛めっき浴の組成、および得られた合金化溶融めっき鋼板の外観および加工性評価結果を表１に示す。
【００１５】
表面外観性（視覚による合金化溶融亜鉛めっき鋼板の表面外観）
○：縦縞模様な認められない
△：縦縞模様が少し認められる
×：縦縞模様が認めらる
加工性（６０度Ｖ曲げ、曲げ戻しテープ剥離テスト）
○：片側剥離幅５ｍｍ未満
△：片側剥離幅５ｍｍ以上８ｍｍ未満
×：片側剥離幅８ｍｍ以上
【００１６】
【表１】
表１に示すように、Ｎｏ．１〜１０は本発明例であり、Ｎｏ．１１〜１８は比較例である。Ｎｏ．１１〜１２は前処理条件としての鋼板への研磨によるＲａ値が０．７と高い（研削が十分でない）場合であり、縦縞模様が発生し外観性が悪い。同じく、Ｎｏ．１３は研磨するもＲａ値が０．７と高く、縦縞模様が少し認められ外観性に劣る。Ｎｏ．１４はＲａ値が１．０と高く、この場合は不めっきが生じた。Ｎｏ．１５は研磨するもＲａ値が０．８と高く、この場合は縦縞模様が少し認められ外観性に劣り、しかも加工性が悪い。同様に、Ｎｏ．１６は研磨するもＲａ値が０．８と高く、縦縞模様が認められ外観性が悪い。さらに、Ｎｏ．１７〜１８はＲａ値が１．０と高く、この場合は縦縞模様が発生し外観性が悪く、特にＮｏ．１７の場合は加工性が劣ることが判る。これに対し、本発明例であるＮｏ．１〜１０のいずれも縦縞模様のない外観性の優れた合金化溶融亜鉛めっき鋼板が得られ、かつめっき密着性のよい加工性に優れた合金化溶融亜鉛めっき鋼板が得られることが判る。
【００１８】
【発明の効果】
以上述べたように、本発明を用いることにより加工部のめっき密着性が従来になく優れ、かつ縦縞模様のない外観性の優れた合金化溶融亜鉛めっき鋼板が得られることから、その工業的意義は極めて大きいものである。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a method for producing an alloyed hot-dip galvanized steel sheet excellent in appearance, plating adhesion and workability using a high Si steel plate or a high P steel plate as a base material.
[0002]
[Prior art]
In recent years, there has been an increasing demand for using alloyed hot-dip galvanized steel sheets based on high-strength steel sheets for automobile outer or inner plates for the purpose of reducing the weight of automobiles and preventing corrosion. This high-strength steel sheet contains Si in an amount of 0.2 to 2.0% or P in an amount of 0.03 to 0.2%. In the conventional hot dip galvanizing method, non-plating occurs, and the barrier layer at the interface is strengthened and alloying does not proceed sufficiently. There was a problem that the alloy layer of this was locally abnormal.
[0003]
In order to solve the above problems, for example, as proposed in JP-A-4-346644 (Patent Document 1), the surface of a high-tensile steel plate is sandpaper, polished, brushed, shot blasted, electrolyzed. After removing the surface layer by polishing or the like, a method for improving the plating adhesion by pre-Ni plating to eliminate the unplating of molten zinc, or as proposed in Japanese Patent Laid-Open No. 4-304346 (Patent Document 2) Then, the surface of the steel plate to be plated is ground by 0.1 to 5 μm, and the steel plate is Si: 0.001 to 0.2% by weight, Al: 0.05 to 0.20% by mass, the balance Zn and unavoidable impurities. Or a method of performing a heat alloying treatment thereafter, or as proposed in Japanese Patent Laid-Open No. 10-81948, the surface of the steel sheet to be plated is 1 to 8 g / m. 2 laboratories A method for producing a galvannealed steel sheet on a removed steel sheet is disclosed.
[0004]
[Cited document]
(1) Patent Document 1 (Japanese Patent Laid-Open No. 4-346644)
(2) Patent Document 2 (Japanese Patent Laid-Open No. 4-304346)
(3) Patent Document 3 (Japanese Patent Laid-Open No. 10-81948)
[0005]
[Problems to be solved by the invention]
Patent Document 1 described above is based on pre-Ni plating. Further, Patent Document 2 limits the Si concentration to the plating bath composition, and Si and Al are concentrated at least in the iron-iron interface, δ 1 phase and its surface in the growth process of the Fe—Zn alloy phase as a role of Si and Al. Segregation occurs, and the Si and Al segregation bands serve as a barrier to form a disordered structure that easily disperses the processing stress in the form of the alloy phase, so that the workability of the galvannealed steel sheet is improved. Furthermore, Japanese Patent Laid-Open No. 10-81948 (Patent Document 3) contains Si in an ultra-low carbon steel containing P, and manages cooling conditions after reduction heating performed before plating and alloying conditions after plating. By doing so, the powdering resistance and chipping resistance are improved. However, none of these have been elucidated from the relationship with the Ra value of the steel sheet surface.
[0006]
(1) In the production method of Si concentration from 0.2 to 2.0% of the galvannealed steel sheet in the steel, by grinding the surface of the plated steel sheet Ra: is 0.3 to 0.6, the steel plate It is characterized by performing heat alloying after being immersed in a hot dip galvanizing bath composed of Al: 0.05-0.20% by mass, the balance Zn and inevitable impurities, after being heat-annealed in a ground state. A method for producing an alloyed hot-dip galvanized steel sheet with excellent workability.
[0007]
(2) In the method for producing an alloyed hot-dip galvanized steel sheet having a P concentration of 0.03% or more in steel, the surface of the steel sheet to be plated is ground to Ra: 0.3 to 0.6, and this steel sheet is still ground Heat-annealed in the state of Al, and after being immersed in a hot dip galvanizing bath comprising Al: 0.05-0.20 mass%, the balance Zn and inevitable impurities, a heat alloying treatment is performed. This is a method for producing an excellent galvannealed steel sheet.
[0008]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, the present invention will be described in detail.
In the present invention, the surface of a steel sheet having a Si concentration in the steel of 0.2 to 2.0% is ground to Ra: 0.3 to 0.6. On the surface of alloyed hot-dip galvanized steel sheet, as well as improving wettability and alloying reaction during hot-dip galvanizing by removing the oxide film containing SiO 2 on the steel sheet surface due to concentration by oxidation and oxidation of the steel sheet surface This is to prevent vertical stripes from being formed and hindering the appearance. If the Si concentration in the steel is less than 0.2%, the problem of poor appearance does not occur, and if it exceeds 2.0%, a sufficient effect cannot be obtained even if the method of the present invention is applied. Therefore, the range was made 0.2 to 2.0%.
[0009]
In addition, the surface of the steel sheet is set to Ra: 0.3 to 0.6, in addition to improving the wettability and alloying reaction at the time of hot dip galvanizing as described above, particularly of the galvannealed steel sheet. This is to prevent vertical stripes on the surface and hinder the appearance, and if it is less than 0.3, the effect of improving the appearance is not obtained any more than Ra: 0.3 μm, and the problem of slippage with the process roll occurs. If the ratio exceeds 0.6, vertical stripes are formed on the surface of the galvannealed steel sheet to hinder the appearance, so the range was set to 0.3 to 0.6.
[0010]
Moreover, in order to make Ra: 0.3-0.6 the surface of a steel plate, the surface of a steel plate is removed by various methods, such as sandpaper grinding | polishing, brush grinding | polishing, and shot blasting. In particular, when brush polishing is used, for example, brush thread diameter: 0.8 to 1.6 mm, brush thread material: nylon, metal, etc., brush abrasive count: 240, 100, 80, etc. are selected and brush This is done by controlling the number of revolutions in the range of 600 to 1200 rpm.
[0011]
Further, P in steel is also likely to be concentrated by diffusion of P to the steel sheet surface and an oxide film on the steel sheet surface as in the case of Si, and the hot dip galvanizing property is poor, preventing the progress of alloying. Therefore, especially for high P-containing steel sheets having a P concentration of 0.03% or more in steel, the surface of the steel layer is polished to a predetermined Ra value, so that the plated layer after the alloying treatment after hot dip galvanization It is intended to improve uniformity and adhesion of the processed part. However, if the P concentration in the steel is less than 0.03%, the problem of poor appearance does not occur, so the lower limit was made 0.03%.
[0012]
The reason for Al: 0.05 to 0.20 mass% is that when Al is less than 0.05%, a brittle Fe—Zn layer is formed at the plating interface, and the plating adhesion is impaired. Further, if it exceeds 0.20%, the effect of suppressing Fe diffusion by Al is strong, and it takes a long time to complete the alloying treatment of the plating layer and the appearance is impaired, so the upper limit was made 0.20% . After dipping in such a hot dip galvanizing bath, a heat alloying treatment is performed. The heating temperature during the alloying treatment is in the range of 440 to 600 ° C. In the case of a temperature range below 440 ° C., alloying becomes insufficient, and in a temperature range exceeding 600 ° C., alloying proceeds excessively, and a Γ phase is likely to be generated, resulting in deterioration of plating adhesion. The alloying time is determined by the balance with the alloying temperature, but the range of 10 to 40 seconds is optimal. If it is less than 10 seconds, alloying is difficult to proceed, and if it exceeds 40 seconds, alloying proceeds too much, the Γ phase is easily generated, and the plating adhesion deteriorates.
[0013]
【Example】
Example 1
Hereinafter, the present invention will be specifically described with reference to examples.
In a Sendzimer type hot dip galvanizing line, a steel plate having a plate thickness of 1.2 mm and a plate width of 900 mm having a Si concentration of 0.4 to 1.5% was polished by brush polishing and subsequently heat-annealed. Immersed in a hot dip galvanizing bath and plated to a predetermined amount by gas wiping method, immediately led into the heat treatment furnace, plated alloyed hot dip plated steel plate under conditions of plate temperature 480-550 ° C and holding time 15-30 seconds Manufactured. Table 1 shows the Ra value of the steel sheet as pretreatment conditions, the composition of the hot dip galvanizing bath used, and the appearance and workability evaluation results of the obtained galvannealed steel sheet.
[0014]
(Example 2)
Under the same conditions as in Example 1, the surface of the steel plate was brush-polished on a Zenzimer hot-dip galvanizing line with a steel plate having a plate thickness of 1.2 mm and a plate width of 900 mm having a P concentration of 0.035 to 0.09%. After polishing and subsequently heat-annealed, it is immersed in a hot dip galvanizing bath and plated to a predetermined adhesion amount by a gas wiping method, immediately led into a heat treatment furnace, and a plate temperature of 480 to 550 ° C. and a holding time of 15 to 20 seconds. An alloyed hot-dip galvanized steel sheet was produced under the conditions. Table 1 shows the Ra value of the steel sheet as pretreatment conditions, the composition of the hot dip galvanizing bath used, and the appearance and workability evaluation results of the obtained galvannealed steel sheet.
[0015]
Surface appearance (visual appearance of alloyed hot-dip galvanized steel sheet)
○: Vertical stripe pattern is not recognized Δ: Vertical stripe pattern is slightly recognized ×: Workability where vertical stripe pattern is recognized (60 degree V-bend, bent back tape peeling test)
○: One side peel width less than 5 mm Δ: One side peel width 5 mm or more and less than 8 mm ×: One side peel width 8 mm or more
[Table 1]
As shown in Table 1, no. 1 to 10 are examples of the present invention. 11 to 18 are comparative examples. No. Nos. 11 to 12 are cases where the Ra value by polishing on a steel plate as a pretreatment condition is as high as 0.7 (grinding is not sufficient), and vertical stripes are generated and the appearance is poor. Similarly, no. Although No. 13 is polished, the Ra value is as high as 0.7, and a vertical stripe pattern is slightly recognized, resulting in poor appearance. No. No. 14 had a high Ra value of 1.0, and in this case, non-plating occurred. No. Although 15 is polished, the Ra value is as high as 0.8. In this case, a slight vertical stripe pattern is observed, the appearance is inferior, and the workability is poor. Similarly, no. No. 16 is polished but has a high Ra value of 0.8, and a vertical stripe pattern is recognized and the appearance is poor. Furthermore, no. Nos. 17 to 18 have a high Ra value of 1.0. In this case, vertical stripes appear and the appearance is poor. In the case of 17, it turns out that workability is inferior. On the other hand, No. which is an example of the present invention. It can be seen that an alloyed hot-dip galvanized steel sheet excellent in appearance without vertical stripes is obtained in any of 1 to 10, and an alloyed hot-dip galvanized steel sheet excellent in workability with good plating adhesion is obtained.
[0018]
【The invention's effect】
As described above, by using the present invention, an alloyed hot-dip galvanized steel sheet having an excellent appearance and no vertical stripe pattern, which is superior in plating adhesion of the processed part, can be obtained. Is extremely large.
Claims (2)
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| JP5098190B2 (en) * | 2006-03-08 | 2012-12-12 | Ｊｆｅスチール株式会社 | Manufacturing method of high strength hot dip galvanized steel sheet |
| TWI396772B (en) | 2009-02-03 | 2013-05-21 | Nippon Steel & Sumitomo Metal Corp | Alloyed hot dip galvanized steel sheet and producing method therefor |
| MX2015004208A (en) | 2012-10-03 | 2015-06-10 | Nippon Steel & Sumitomo Metal Corp | Alloyed hot-dip zinc-coated steel sheet and method for producing same. |
| KR102468036B1 (en) | 2020-11-12 | 2022-11-17 | 주식회사 포스코 | High-strength hot-dip galvanized steel sheet with excellent formability and process for producing same |
| KR102484992B1 (en) | 2020-11-18 | 2023-01-05 | 주식회사 포스코 | Plated steel sheet having excellent strength, formability and surface property and method for manufacturing the same |
| KR102485003B1 (en) | 2020-12-11 | 2023-01-05 | 주식회사 포스코 | High strength plated steel sheet having excellent formability and surface property, and manufacturing method for the same |
| KR20220168836A (en) | 2021-06-17 | 2022-12-26 | 주식회사 포스코 | Bake hardening hot-dip galvannealed steel sheet having excellent coated surface quality and method for manufacturing the same |
| KR20230072728A (en) | 2021-11-18 | 2023-05-25 | 주식회사 포스코 | Bake hardening cold rolled steel sheet, hot dip galvannealed steel sheet having less anisotropy and excellent coated surface quality and method for manufacturing thereof |
| CN115613030A (en) * | 2022-05-05 | 2023-01-17 | 首钢集团有限公司 | Production method of phosphorus-containing galvanized steel with excellent surface quality for automobiles |
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