JPH0770723A - Production of galvanized steel sheet and galvannealed steel sheet - Google Patents
Production of galvanized steel sheet and galvannealed steel sheetInfo
- Publication number
- JPH0770723A JPH0770723A JP2977594A JP2977594A JPH0770723A JP H0770723 A JPH0770723 A JP H0770723A JP 2977594 A JP2977594 A JP 2977594A JP 2977594 A JP2977594 A JP 2977594A JP H0770723 A JPH0770723 A JP H0770723A
- Authority
- JP
- Japan
- Prior art keywords
- steel sheet
- hot
- annealing
- galvanized steel
- plating
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Links
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- Coating With Molten Metal (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、自動車車体用などに用
いられる高強度鋼板を素材とした溶融亜鉛めっき鋼板お
よび合金化溶融亜鉛めっき鋼板の製造方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a hot-dip galvanized steel sheet and a method for producing an alloyed hot-dip galvanized steel sheet using a high-strength steel sheet used for automobile bodies and the like.
【０００２】[0002]
【従来の技術】従来より自動車用鋼板として耐食性の優
れた種々の表面処理鋼板が用いられている。その中で
も、再結晶焼鈍およびめっきを同一ラインで行う連続式
溶融亜鉛めっき設備において製造されている溶融亜鉛め
っき鋼板は高度な耐食性と安価な製造が可能であり、ま
た、溶融亜鉛めっきに加熱処理を施した合金化溶融亜鉛
めっき鋼板は耐食性に加え、溶接性やプレス加工性に優
れていることから多く用いられている。2. Description of the Related Art Conventionally, various surface-treated steel sheets having excellent corrosion resistance have been used as steel sheets for automobiles. Among them, hot-dip galvanized steel sheets manufactured in continuous hot-dip galvanizing equipment that performs recrystallization annealing and plating in the same line are highly corrosion resistant and can be manufactured inexpensively. The alloyed hot-dip galvanized steel sheet that has been applied is often used because it has excellent weldability and press workability in addition to corrosion resistance.
【０００３】一方近年、地球環境問題がクローズアップ
され、自動車の燃費向上のため軽量化が迫られている。
そのため、鋼板の強度を高めた高強度鋼板が開発され、
現在では耐食性のため溶融亜鉛めっき化および合金化溶
融亜鉛めっき化が必要となってきている。高強度鋼板は
一般にＰやＳｉ、Ｍｎ、Ｃｒなどの元素を添加すること
により得られる。On the other hand, in recent years, the problem of global environment has been highlighted, and the weight reduction has been urged to improve the fuel efficiency of automobiles.
Therefore, a high-strength steel plate with higher strength was developed,
At present, hot dip galvanizing and alloying hot dip galvanizing are required for corrosion resistance. High strength steel sheets are generally obtained by adding elements such as P, Si, Mn and Cr.
【０００４】Ｐを含む鋼板において溶融亜鉛めっき装置
（以下、ＣＧＬと称す）での再結晶焼鈍により表面結晶
粒界にＰの析出が生じ合金化が遅くなることが知られて
いる。これは、合金化時の鉄の亜鉛めっき中への溶出が
主に粒界において起こっているが、Ｐを含む鋼板では粒
界Ｐが鉄の溶出経路を塞いでいるためと考えられてい
る。It is known that in a steel sheet containing P, recrystallization annealing in a hot dip galvanizing apparatus (hereinafter referred to as CGL) causes precipitation of P at surface crystal grain boundaries and slows alloying. It is considered that this is because the elution of iron into zinc plating during alloying mainly occurs at the grain boundaries, but the grain boundary P blocks the elution route of iron in the steel sheet containing P.
【０００５】また、Ｓｉ、Ｍｎ、Ｃｒなどを含む鋼板で
はこれらの元素が再結晶焼鈍時に表面濃化しめっき濡れ
性を阻害することが知られている。これは、再結晶焼鈍
雰囲気はＦｅについては還元性であるため鉄酸化物の生
成はみられないが、ＳｉやＭｎ、Ｃｒについては酸化性
雰囲気となるためこれらの元素が鋼板表面に酸化物とし
て濃化し酸化膜を形成し、溶融亜鉛と鋼板の接触面積を
低下させているためである。It is known that, in a steel sheet containing Si, Mn, Cr, etc., these elements concentrate on the surface during recrystallization annealing and hinder the plating wettability. This is because in the recrystallization annealing atmosphere, since Fe is reducing, iron oxide is not generated, but Si, Mn, and Cr are in an oxidizing atmosphere, and thus these elements become oxides on the surface of the steel sheet. This is because the oxide film is thickened and the contact area between the molten zinc and the steel sheet is reduced.
【０００６】めっき濡れ性を改善する従来方法として
は、ＣＧＬに鋼板を導入する前に電気めっきを行う方法
（特開平２−１９４１５６号公報）あるいはクラッド法
によりＳｉ、Ｍｎ等の含有量の少ない鋼を表層にしてめ
っき濡れ性を改善する方法（特開平３−１９９３６３号
公報）が考案されている。一方、鋼中にさらにＴｉを添
加して、溶融亜鉛との濡れ性を改善する方法（特開平４
−１４８０７３号公報）も考案されている。As a conventional method for improving the plating wettability, a method of electroplating before introducing a steel plate into CGL (Japanese Patent Laid-Open No. 2-194156) or a steel containing a small amount of Si, Mn, etc. by a clad method is used. Has been devised (JP-A-3-199363) to improve the wettability of the plating. On the other hand, a method of further adding Ti to the steel to improve the wettability with molten zinc (Japanese Patent Laid-Open No. Hei 4)
No. 148073) has also been devised.
【０００７】一方、合金化の著しい遅滞により、めっき
層を十分に合金化するためには、合金化温度を上げるま
たはラインスピードを低下し合金化時間を長くするなど
の方法をとる必要がある。しかし、合金化温度を上げる
ことによっては、めっき層中鉄含有率の制御が困難とな
り、必要以上に高くなりやすい、まためっき密着性が劣
化するなどの問題が生じるとともに、製造コストの上昇
にもつながる。また、ラインスピードを低下させ長時間
合金化を行う場合、生産性が悪くなりまた、製造コスト
上昇の原因となる。On the other hand, due to a marked delay in alloying, it is necessary to take a method such as increasing the alloying temperature or decreasing the line speed to prolong the alloying time in order to sufficiently alloy the plating layer. However, increasing the alloying temperature makes it difficult to control the iron content in the plating layer, tends to increase it more than necessary, and causes problems such as deterioration of plating adhesion and also increases manufacturing costs. Connect Further, when the line speed is reduced and alloying is performed for a long time, the productivity is deteriorated and the manufacturing cost is increased.
【０００８】合金化を促進する従来方法は、特開昭５８
−１２０７７１号公報において開示されているように、
還元焼鈍前にＮｉまたはＣｕめっきを行うことにより、
Ｆｅ−Ｚｎの合金化促進を図るものである。しかし、こ
の方法では、ＮｉまたはＣｕめっきする設備を還元焼鈍
前に設置する必要がある。A conventional method for promoting alloying is disclosed in Japanese Patent Laid-Open No. 58-58.
As disclosed in Japanese Patent Publication No. 120771
By performing Ni or Cu plating before reduction annealing,
This is for promoting the alloying of Fe-Zn. However, in this method, it is necessary to install equipment for Ni or Cu plating before reduction annealing.
【０００９】特公昭６４−１１１１１号公報にはＺｎ浴
中Ａｌ濃度および浴温を変更して合金化条件を一定化さ
せる方法が開示されているが、この方法ではＺｎ浴条件
を変化させるには時間がかかりラインを停止する必要が
あるため、生産性を悪化させる。また、同公報に開示の
実施例では鋼中Ｓｉ量０．２％以下、Ｐ量０．１％以下
の鋼板に適応可能であることが開示されている。しか
し、本発明の対象とするＳｉ：２．０％まで、Ｐ：０．
２％までと多量に添加された鋼板に適用できない。Japanese Patent Publication No. 64-11111 discloses a method of keeping the alloying conditions constant by changing the Al concentration and the bath temperature in the Zn bath. It takes time and the line has to be stopped, which reduces productivity. Further, in the examples disclosed in the publication, it is disclosed that the steel can be applied to steel sheets having a Si content in steel of 0.2% or less and a P content of 0.1% or less. However, in the present invention, Si: up to 2.0%, P: 0.
It cannot be applied to steel sheets added in large amounts up to 2%.
【００１０】特開平３−２４３７５１号公報にはＰ添加
鋼において焼鈍後酸洗してＰ濃化層を除去し合金化を促
進する方法が開示されている。この公報に開示されてい
る技術は、一般に引張強度が３５kgf/mm2 クラスといわ
れるＰ添加鋼の合金化の促進を目的としており、本発明
の対象とする、さらに強度を増すためにＰ以外にＳｉや
Ｍｎ、Ｃｒを複合添加した鋼板、いわゆる引張強度が４
５kgf/mm2 以上の鋼板の不めっき欠陥の改善の技術では
ない。Japanese Unexamined Patent Publication (Kokai) No. 3-243751 discloses a method of accelerating alloying by removing the P-enriched layer by pickling after annealing in P-added steel. The technology disclosed in this publication is aimed at promoting alloying of P-added steel, which is generally said to have a tensile strength of 35 kgf / mm 2 class, and other than P in order to increase the strength, which is the object of the present invention. Steel sheet with composite addition of Si, Mn, and Cr, so-called tensile strength is 4
It is not a technique for improving non-plating defects in steel sheets of 5 kgf / mm 2 or more.
【００１１】[0011]
【発明が解決しようとする課題】本発明は、上記従来技
術の問題点を解決すべくなされたもので、ＰおよびＳ
ｉ、Ｍｎ、Ｃｒを含有する高強度鋼板を素地鋼板に用い
て溶融亜鉛めっき鋼板または合金化溶融亜鉛めっき鋼板
を製造するにあたり、できるだけ工程の煩雑化や生産性
低下を最低限にとどめ、品質がよく安価に製造すること
のできる溶融亜鉛めっき鋼板および合金化溶融亜鉛めっ
き鋼板の製造方法を提供することを目的とする。SUMMARY OF THE INVENTION The present invention has been made to solve the above-mentioned problems of the prior art. P and S
In producing a hot-dip galvanized steel sheet or an alloyed hot-dip galvanized steel sheet using a high-strength steel sheet containing i, Mn, and Cr as a base steel sheet, the complexity of the process and the reduction in productivity are minimized as much as possible. An object of the present invention is to provide a hot-dip galvanized steel sheet and a method for manufacturing an alloyed hot-dip galvanized steel sheet that can be manufactured at low cost.
【００１２】[0012]
【課題を解決するための手段】本発明において上記問題
点を解決する手段は以下の通りである。本発明者らは、
本発明が目的とするＰとＳｉ、Ｍｎ、Ｃｒが複合添加さ
れている鋼板における再結晶焼鈍後の鋼板表面濃化状態
を、結晶粒界のＰ濃度については脆性破断により結晶粒
界を露出させオージェ分析法（ＡＥＳ）により行い、鋼
板表面のＳｉ、Ｍｎ、Ｃｒ濃度についてはグロー放電分
光分析法（ＧＤＳ）により行った。図１ａ）に再結晶焼
鈍後の表層結晶粒界のＡＥＳスペクトルを、図１ｂ）に
鋼板内部の結晶粒界のＡＥＳスペクトルを示す。また、
図２ａ）に再結晶焼鈍後の鋼板表面のＧＤＳスペクトル
を示す。これらの結果により、ＰおよびＳｉ、Ｍｎ、Ｃ
ｒの複合添加鋼板において、これらのすべての元素が表
面に濃化していることがわかった。Means for solving the above problems in the present invention are as follows. We have
The steel sheet surface enrichment state after recrystallization annealing in the steel sheet to which P, Si, Mn, and Cr are added in combination, which is the object of the present invention, is defined as the P concentration of the grain boundaries by exposing the grain boundaries by brittle fracture. Auger analysis (AES) was performed, and Si, Mn, and Cr concentrations on the surface of the steel sheet were measured by glow discharge spectroscopy (GDS). FIG. 1 a) shows the AES spectrum of the surface grain boundaries after recrystallization annealing, and FIG. 1 b) shows the AES spectrum of the grain boundaries inside the steel sheet. Also,
Figure 2a) shows the GDS spectrum of the steel sheet surface after recrystallization annealing. These results show that P and Si, Mn, C
It was found that all of these elements were concentrated on the surface of the r-added steel sheet.
【００１３】よって、めっき濡れ性の改善や合金化速度
の促進のためには、溶融亜鉛めっき浴に鋼板が導かれる
時点において、これらの元素の表面濃化層量を少なくす
ればよいと考えられる。Therefore, in order to improve the coating wettability and accelerate the alloying rate, it is considered that the amount of the surface concentrated layer of these elements should be reduced at the time when the steel sheet is introduced into the hot dip galvanizing bath. .
【００１４】そこで本発明者らは、還元焼鈍条件、表面
濃化層量とめっき濡れ性や合金化速度を詳細に検討した
結果、高強度鋼板の冷延板を再結晶温度で焼鈍した後に
酸洗により表面濃化層を除去した場合、溶融亜鉛めっき
前の再還元焼鈍において再度のＰ、Ｓｉ、Ｍｎ、Ｃｒの
表面濃化が起こり難く、めっき濡れ性の改善や合金化速
度の促進効果がみられることを知見した。Therefore, as a result of a detailed study of the reduction annealing conditions, the amount of surface concentrated layer, the plating wettability and the alloying rate, the present inventors have found that the cold rolled sheet of high strength steel sheet is annealed at the recrystallization temperature and then acidified. When the surface concentrated layer is removed by washing, the surface concentration of P, Si, Mn, and Cr is unlikely to occur again in the re-reduction annealing before hot dip galvanizing, and the effect of improving the plating wettability and promoting the alloying rate is obtained. I found that you can see it.
【００１５】図１ｃ）に焼鈍後酸洗した後、再度還元焼
鈍した鋼板の表面結晶粒界のＡＥＳスペクトルの結果を
示す。図１ａ）に比べ、酸洗後の焼鈍により粒界Ｐ量が
減少していることがわかる。また、図２ｂ）にはＧＤＳ
により求めた焼鈍酸洗後さらに再還元した高強度鋼板の
表面濃化の様子を示す。また、図３にはＭｎを例に取っ
て焼鈍温度あるいは焼鈍酸洗後の再還元温度の表面濃化
におよぼす影響を示す。これらの結果より焼鈍後酸洗に
より表面濃化層を除去し再焼鈍することにより表面濃化
層量の少ない状態で溶融亜鉛めっき浴に浸漬できること
がわかった。FIG. 1c) shows the results of the AES spectrum of the surface grain boundaries of the steel sheet which was annealed and then pickled and then reduction annealed again. It can be seen that the amount of grain boundary P is decreased by annealing after pickling as compared with FIG. 1a). Also, in FIG.
The state of surface thickening of the high-strength steel sheet obtained by annealing after pickling and further re-reduced is shown. Further, FIG. 3 shows the effect of annealing temperature or re-reduction temperature after annealing pickling on the surface concentration by taking Mn as an example. From these results, it was found that the surface concentrated layer can be immersed in the hot dip galvanizing bath with a small amount of the surface concentrated layer by removing the surface concentrated layer by pickling after annealing and re-annealing.
【００１６】従って、本発明者らは、冷延、焼鈍鋼板を
高生産性で生産できる連続焼鈍設備（以下、ＣＡＬと称
す）を用いて焼鈍処理を行った後に、表面のＰ、Ｓｉ、
Ｍｎ、Ｃｒ等の濃化層を酸洗により除去後、ＣＧＬで容
易に不めっき欠陥のないめっきが可能でありさらに迅速
な合金化ができることを見いだした。すなわち、本発明
は、上記知見によってはじめてなされたもので、重量％
でＰ：０．０３％以上０．２％以下を含み、さらにＳ
ｉ：０．１％以上２．０％以下、Ｍｎ：０．５％以上
２．０％以下、およびＣｒ：０．１％以上２．０％以下
のうち少なくとも一種以上を含有する鋼板を連続焼鈍設
備で再結晶焼鈍し、冷却後に鋼板表面の鋼中成分の濃化
層を酸洗により除去し、連続溶融亜鉛めっき設備にて再
度前記鋼板を６５０℃以上、かつ連続焼鈍設備での再結
晶焼鈍温度以下で加熱して溶融亜鉛めっきを行うことを
特徴とする溶融亜鉛めっき鋼板の製造方法を提供するも
のである。Therefore, the inventors of the present invention carried out annealing treatment using a continuous annealing facility (hereinafter referred to as CAL) capable of producing cold-rolled and annealed steel sheets with high productivity, and then P, Si,
After removing the concentrated layers of Mn, Cr, etc. by pickling, it was found that plating with CGL can be easily performed without non-plating defects and more rapid alloying can be performed. That is, the present invention has been made for the first time based on the above findings, and is
And P: 0.03% to 0.2% inclusive, and S
i: 0.1% or more and 2.0% or less, Mn: 0.5% or more and 2.0% or less, and Cr: 0.1% or more and 2.0% or less. After recrystallization annealing in an annealing equipment, after cooling, the concentrated layer of steel components on the surface of the steel sheet is removed by pickling, and the steel sheet is recrystallized in a continuous hot dip galvanizing equipment at 650 ° C or higher and in a continuous annealing equipment. The present invention provides a method for producing a hot-dip galvanized steel sheet, which comprises heating at an annealing temperature or lower to carry out hot-dip galvanizing.
【００１７】また、本発明は、上記製造方法によって得
られた溶融亜鉛めっき鋼板に、さらに合金化を行うこと
を特徴とする合金化溶融亜鉛めっき鋼板の製造方法を提
供するものである。The present invention also provides a method for producing an alloyed hot-dip galvanized steel sheet, characterized by further alloying the hot-dip galvanized steel sheet obtained by the above-mentioned production method.
【００１８】ここで、上記各製造方法によって得られた
溶融亜鉛めっき鋼板および合金化溶融亜鉛めっき鋼板に
上層めっきを行うのが好ましい。Here, it is preferable to perform the upper layer plating on the hot-dip galvanized steel sheet and the alloyed hot-dip galvanized steel sheet obtained by the above manufacturing methods.
【００１９】[0019]
【作用】本発明は、それぞれ、重量％でＰ：０．０３％
以上０．２％以下を含み、さらにＳｉ：０．１％以上
２．０％以下、Ｍｎ：０．５％以上２．０％以下、およ
びＣｒ：０．１％以上２．０％以下のうち少なくとも一
種以上を含有する鋼板を素地鋼板として用いる場合に、
連続焼鈍設備にて再結晶焼鈍温度で焼鈍し、冷却後に鋼
板表面の鋼中成分の濃化層を酸洗により除去し、連続溶
融亜鉛めっき設備にて再度前記鋼板をＣＧＬでの鋼板の
加熱温度が６５０℃以上、ＣＡＬでの焼鈍温度以下で加
熱（還元）して溶融亜鉛めっきを行う方法および以上の
ように製造された溶融亜鉛めっき鋼板に、さらに合金化
処理を行う方法である。また、合金化に際しての加熱処
理は、４６０℃より低温の場合長時間の加熱が必要であ
り生産性が低下するため４６０℃以上、プレス成形時の
密着性より５６０℃以下がよい。以上のようにして得ら
れた溶融亜鉛めっき鋼板および合金化溶融亜鉛めっき鋼
板は必要に応じて上層にさらにめっきを施してもよい。In the present invention, P: 0.03% by weight, respectively
Or more and 0.2% or less, Si: 0.1% or more and 2.0% or less, Mn: 0.5% or more and 2.0% or less, and Cr: 0.1% or more and 2.0% or less. When using a steel sheet containing at least one of them as a base steel sheet,
It is annealed at a recrystallization annealing temperature in a continuous annealing facility, and after cooling, the concentrated layer of the steel components on the surface of the steel sheet is removed by pickling, and in the continuous hot dip galvanizing facility, the steel sheet is heated again at the CGL heating temperature. Is a method of performing hot dip galvanizing by heating (reducing) at 650 ° C. or higher and an annealing temperature of CAL or lower, and a method of further alloying the hot dip galvanized steel sheet produced as described above. Further, the heat treatment for alloying requires heating for a long time when the temperature is lower than 460 ° C., which lowers the productivity, so that it is preferably 460 ° C. or higher, and 560 ° C. or lower in view of adhesion at the time of press molding. The hot dip galvanized steel sheet and the alloyed hot dip galvanized steel sheet obtained as described above may be further plated on the upper layer, if necessary.
【００２０】以下に本発明をさらに詳細に説明する。ま
ず、本発明に用いられるＰ添加高強度鋼板にＣＡＬおよ
びＣＧＬにて溶融亜鉛めっきおよびその後の合金化を行
う方法について述べる。めっき素材となる鋼板は熱延お
よび冷延によって板厚を調整された後、ＣＡＬにより再
結晶温度で焼鈍される。ＣＡＬの雰囲気はスケールの発
生を防止するため、鋼板に対し還元性が必要であり、一
般的に数％Ｈ2 を含有するＮ2 ガスを用いればよい。Ｃ
ＡＬでの鋼板到達温度は鋼中成分および目標材質により
異なるが７５０℃から９５０℃の範囲が一般的である。The present invention will be described in more detail below. First, a method of hot dip galvanizing and subsequently alloying the P-added high-strength steel sheet used in the present invention with CAL and CGL will be described. A steel sheet as a plating material has its thickness adjusted by hot rolling and cold rolling, and then annealed at a recrystallization temperature by CAL. The atmosphere of CAL needs to be reducible with respect to the steel sheet in order to prevent the generation of scale, and in general, N 2 gas containing several% H 2 may be used. C
The temperature reached by the steel plate at AL varies depending on the steel composition and target material, but is generally in the range of 750 ° C to 950 ° C.
【００２１】ＣＡＬにて再結晶温度で焼鈍された鋼板は
表面に鋼中成分によりＰが鋼板表面結晶粒界に析出し、
Ｓｉ、Ｍｎ、Ｃｒなどが酸化物として濃化する。この表
面濃化層を酸洗により除去後、ＣＧＬへ鋼板を導入す
る。ＣＧＬでの還元焼鈍はＳｉ、Ｍｎ、Ｃｒの添加の少
ない（熱延仕上げ）鋼板では６００℃程度で十分で、め
っき可能であるが、Ｓｉ、Ｍｎ、Ｃｒを添加した冷延後
再結晶焼鈍した鋼板では、めっき濡れ性および合金化速
度の観点から、再焼鈍還元温度が６５０℃以上で改善効
果が現れ、７００℃以上で好適範囲にはいる。しかし、
再表面濃化防止のためおよび鋼板材質上、ＣＡＬでの再
結晶焼鈍温度以下、さらには（ＣＡＬでの再結晶焼鈍温
度−３０）℃以下が再焼鈍還元温度として好ましい（図
４および図５参照）。ＣＧＬでの再還元焼鈍雰囲気は、
ＣＡＬと同様に数％Ｈ2 を含有するＮ2 を用いればよ
い。On the surface of the steel sheet annealed at the recrystallization temperature by CAL, P precipitates on the surface grain boundary of the steel sheet due to the components in the steel,
Si, Mn, Cr, etc. are concentrated as oxides. After removing this surface concentrated layer by pickling, a steel plate is introduced into CGL. About 600 ° C. is sufficient for reduction annealing with CGL for a steel sheet with little addition of Si, Mn, and Cr (hot rolled finish), and plating is possible, but recrystallization annealing after cold rolling with addition of Si, Mn, and Cr was performed. In terms of plating wettability and alloying rate, the steel sheet shows an improving effect at a reannealing reduction temperature of 650 ° C or higher, and falls within a suitable range at 700 ° C or higher. But,
In order to prevent re-surface enrichment and in view of steel sheet material, a recrystallization annealing temperature of CAL or lower, and a recrystallization annealing temperature of -30 (° C) or lower is preferable as the reannealing reduction temperature (see FIGS. 4 and 5). ). The re-reduction annealing atmosphere in CGL is
As with CAL, N 2 containing several% H 2 may be used.
【００２２】上記温度で再還元焼鈍された鋼板は、通常
の溶融亜鉛めっきと同様に５００℃前後に降温後、４６
０〜５００℃程度、溶解Ａｌ濃度０．１３〜０．１４ｗ
ｔ％程度の溶融亜鉛めっき浴に導入され亜鉛めっきさ
れ、浴からの立ち上がり時にガスワイピングにより目付
量が調整される。こうして、溶融亜鉛めっき鋼板が製造
される。必要に応じてその後直ちに加熱合金化処理さ
れ、合金化溶融亜鉛めっき鋼板が製造される。合金化温
度は生産性より４６０℃以上、また、プレス成形時のめ
っき密着性より５６０℃以下とする。溶融亜鉛めっき後
あるいは合金化溶融亜鉛めっき後、必要に応じて上層め
っきを行い、めっき特性の改善をはかることも可能であ
る。例えば、上層めっきとして、プレス時の慴動性改善
のために行われるＦｅ−ＺｎやＦｅ−Ｐめっきなどを施
してもよい。この上層めっきは用途に応じて如何なるめ
っきでもよい。The steel sheet re-reduced and annealed at the above temperature is cooled to around 500 ° C. as in the case of normal hot dip galvanizing and then cooled to 46 ° C.
0-500 ° C, dissolved Al concentration 0.13-0.14w
It is introduced into a hot-dip galvanizing bath of about t% for galvanizing, and the basis weight is adjusted by gas wiping when rising from the bath. Thus, the galvanized steel sheet is manufactured. Immediately thereafter, if necessary, a heat-alloying treatment is performed to produce a galvannealed steel sheet. The alloying temperature is 460 ° C. or higher for productivity, and 560 ° C. or lower for plating adhesion during press molding. After hot dip galvanizing or alloying hot dip galvanizing, an upper layer plating may be performed as necessary to improve the plating characteristics. For example, as the upper layer plating, Fe-Zn or Fe-P plating, which is performed to improve slidability during pressing, may be applied. This upper layer plating may be any plating depending on the application.
【００２３】本発明に用いられる素地鋼板の鋼中成分に
ついて以下に説明する。Ｐ、Ｓｉ、Ｍｎ、Ｃｒは鋼に強
度を持たせるために添加している。Ｐは少量の添加で強
度を持たせることが可能であり、比較的安価であるが、
２次加工脆性を起こし易く、また深絞り性にも悪影響で
あるため、０．０３％以上０．２％以下とする。The steel components of the base steel sheet used in the present invention will be described below. P, Si, Mn, and Cr are added to give strength to the steel. P can be given strength by adding a small amount and is relatively inexpensive,
Secondary workability is liable to occur, and deep drawability is also adversely affected, so the content is made 0.03% or more and 0.2% or less.
【００２４】Ｓｉは鋼の強度を高める効果の現れる０．
１％以上とし、表面に酸化膜を形成しめっき浴との密着
性を低下させるため２．０％以下とする。Ｍｎは鋼の強
度を高める効果の現れる０．５％以上とし、また、深絞
り性に悪影響を及ぼすため２．０％以下とする。Ｃｒは
鋼の強度を高める効果の現れる０．１％以上とし、強度
向上効果の飽和と経済性より０．１％以上２．０％以下
とする。Si has an effect of increasing the strength of steel.
It is 1% or more and is 2.0% or less in order to form an oxide film on the surface and reduce the adhesion with the plating bath. Mn is 0.5% or more, which has an effect of increasing the strength of steel, and 2.0% or less because it adversely affects deep drawability. Cr is set to 0.1% or more where the effect of increasing the strength of steel appears, and 0.1% or more and 2.0% or less from the viewpoint of saturation of the effect of improving strength and economy.
【００２５】本発明は、Ｐに加えてＳｉ、Ｍｎ、Ｃｒを
添加した鋼板において効果がみられるが、これらの鋼板
に成形性改善のために添加される炭窒化物形成元素であ
るＴｉやＮｂを添加した鋼板においても、本発明は有効
である。また、Ｐ、Ｓｉ、Ｍｎ、Ｃｒ、Ｔｉ、Ｎｂを添
加した鋼板に２次加工脆性改善および溶接性のためＢを
添加した鋼板を用いてもよい。The present invention is effective in the steel sheets to which Si, Mn, and Cr are added in addition to P, but Ti and Nb which are carbonitride forming elements added to these steel sheets for improving formability. The present invention is also effective for a steel sheet to which is added. Moreover, you may use the steel plate which added B to the steel plate which added P, Si, Mn, Cr, Ti, and Nb for secondary work embrittlement improvement and weldability.
【００２６】[0026]
【実施例】以下に本発明を実施例に基づいて具体的に説
明する。表１に供試鋼板の組成を示す。予め清浄化処理
をした鋼板に、従来方法である焼鈍のみの処理、あるい
は本発明方法である焼鈍−濃化層除去（塩酸酸洗）−再
還元焼鈍の処理を施した後、溶融亜鉛めっきを行い、溶
融亜鉛めっき鋼板を得た。この後、この溶融亜鉛めっき
鋼板を合金化処理して合金化亜鉛めっき鋼板を得た。得
られた鋼板のめっき外観評価、めっき層中の鉄含有率お
よび耐パウダリング性を評価した。EXAMPLES The present invention will be specifically described below based on examples. Table 1 shows the composition of the test steel sheet. The steel sheet that has been subjected to a cleaning treatment in advance is subjected to a conventional method of only annealing, or an inventive method of annealing-concentrated layer removal (hydrochloric acid pickling) -reduction annealing, and then hot-dip galvanizing. Then, a galvanized steel sheet was obtained. Then, this hot dip galvanized steel sheet was alloyed to obtain an alloyed galvanized steel sheet. The obtained steel sheet was evaluated for plating appearance, iron content in the plating layer, and powdering resistance.
【００２７】ここで、１回目焼鈍後濃化層を除去するこ
となく溶融亜鉛めっきした例（従来方法）、および１回
目焼鈍後濃化層を除去した後２回目の焼鈍を行った例
（本発明方法）を表２示す。焼鈍条件、濃化層除去処理
条件、亜鉛めっき条件および合金化処理条件ならびに得
られた鋼板の評価方法を以下に示す。Here, an example of hot-dip galvanizing without removing the concentrated layer after the first annealing (conventional method), and an example of performing the second annealing after removing the concentrated layer after the first annealing (this) Inventive method) is shown in Table 2. The annealing conditions, concentrated layer removal treatment conditions, zinc plating conditions, alloying treatment conditions and the evaluation method of the obtained steel sheet are shown below.
【００２８】・焼鈍条件（１回、２回目とも含む） 雰囲気 ５％Ｈ2 −Ｎ2 ガス（露点−２０℃） 温 度 表２ 時 間 ２０秒 １回焼鈍法は、焼鈍後鋼板が所定温度になった時点でめ
っき浴に投入する。２回焼鈍法は、焼鈍後一旦室温まで
冷却し、濃化層を除去した後、再度焼鈍し 、鋼板が所
定温度まで降温した時点でめっき浴に投入する。Annealing conditions (including both the first and second times) Atmosphere 5% H 2 -N 2 gas (dew point -20 ° C) Temperature Table 2 time 20 seconds 1 time annealing method, after annealing When it becomes, add it to the plating bath. In the two-time annealing method, after annealing, the temperature is once cooled to room temperature, the concentrated layer is removed, and then annealing is performed again, and when the steel sheet is cooled to a predetermined temperature, it is put into a plating bath.
【００２９】・濃化層除去処理条件 塩酸酸洗 濃度 ５％ＨＣｌ水溶液 温度 ６０℃ 浸漬時間 ６秒Condensed layer removal treatment conditions Hydrochloric acid pickling Concentration 5% HCl aqueous solution Temperature 60 ° C Immersion time 6 seconds
【００３０】・めっき条件 めっき浴 Ａｌ濃度 ０．１３ｗｔ％ 浴温 ４７５℃ 板温 ４７５℃ 浸漬時間 ３秒 目付量 ４５ｇ／ｍ2 ・合金化条件 温度 表２ 時間 表２Plating conditions Plating bath Al concentration 0.13 wt% Bath temperature 475 ° C Plate temperature 475 ° C Immersion time 3 seconds Basis weight 45 g / m 2 Alloying conditions Temperature Table 2 hours Table 2
【００３１】・評価方法 不めっき欠陥の判定は目視により行い、不めっき欠陥が
全くないものを「１」、最も不めっきの多いものを
「５」とした。めっき層中鉄含有率は硫酸にてめっき層
を溶解し、原子吸光にて測定した。耐パウダリング性は
９０℃曲げ戻し試験の後、セロテープに付着した亜鉛粉
を蛍光Ｘ線にて測定した。その結果を表２に示す。Evaluation Method The determination of non-plating defects was made by visual inspection. The one with no non-plating defects was "1", and the one with the most non-plating defects was "5". The iron content in the plating layer was determined by dissolving the plating layer with sulfuric acid and measuring by atomic absorption. The powdering resistance was measured by a fluorescent X-ray of the zinc powder attached to the cellophane tape after the 90 ° C. bending back test. The results are shown in Table 2.
【００３２】 [0032]
【００３３】[0033]
【表１】 [Table 1]
【００３４】[0034]
【表２】 [Table 2]
【００３５】[0035]
【表３】 [Table 3]
【００３６】[0036]
【表４】 [Table 4]
【００３７】[0037]
【表５】 [Table 5]
【００３８】[0038]
【表６】 [Table 6]
【００３９】[0039]
【表７】 [Table 7]
【００４０】[0040]
【表８】 [Table 8]
【００４１】[0041]
【発明の効果】以下、詳述したように、本発明によれ
ば、溶融亜鉛めっきにおいて難めっき性を示し、合金化
が著しく遅いＰおよびＳｉ、Ｍｎ、Ｃｒを複合添加され
た高強度鋼板であっても、不めっき欠陥がない鋼板を得
ることができ、さらに低温合金化が可能であり合金化の
制御がしやすい。また、ラインの煩雑化や生産性の低下
を招くことはない。また、本発明によれば、上記効果を
得るのに、従来の設備を使用することができるので、設
備投資が不要であるという効果もある。As described in detail below, according to the present invention, a high-strength steel sheet which exhibits difficulty in galvanizing and has a significantly slow alloying and which contains P and Si, Mn, and Cr in combination is added. Even if it exists, it is possible to obtain a steel sheet having no non-plating defect, and it is possible to alloy at a low temperature and control the alloying easily. In addition, the line is not complicated and the productivity is not reduced. Further, according to the present invention, since the conventional equipment can be used to obtain the above effect, there is also an effect that equipment investment is unnecessary.
【図１】 鋼板表面の結晶粒界のＰ量をＡＥＳによって
測定した図であり、（ａ）は、焼鈍後の表層結晶粒界、
（ｂ）は、焼鈍後の内部結晶粒界、（ｃ）は焼鈍−塩酸
酸洗−再還元焼鈍後の表層結晶粒界のスペクトルであ
る。FIG. 1 is a diagram in which the amount of P at a crystal grain boundary on the surface of a steel sheet is measured by AES, and (a) is a surface layer grain boundary after annealing,
(B) is a spectrum of internal crystal grain boundaries after annealing, and (c) is a spectrum of surface layer grain boundaries after annealing-hydrochloric acid pickling-reduction annealing.
【図２】 高強度鋼板の表面濃化の状態を示すグロー放
電分光分析法により求めた図であり、（ａ）は焼鈍後、
（ｂ）は焼鈍−塩酸酸洗−再還元焼鈍後の図である。FIG. 2 is a diagram showing the state of surface concentration of a high-strength steel sheet obtained by glow discharge spectroscopy, where (a) shows the result after annealing.
(B) is a figure after annealing-hydrochloric acid pickling-re-reduction annealing.
【図３】 Ｍｎについての表面濃化に及ぼす焼鈍、再還
元焼鈍温度の影響を示す図である。FIG. 3 is a diagram showing the effects of annealing and re-reduction annealing temperatures on the surface concentration of Mn.
【図４】 不めっき欠陥に及ぼす還元焼鈍温度の影響を
示す図である。FIG. 4 is a diagram showing the effect of reduction annealing temperature on non-plating defects.
【図５】 合金化速度に及ぼす還元焼鈍温度の影響を示
す図である。FIG. 5 is a diagram showing the effect of reduction annealing temperature on the alloying rate.
─────────────────────────────────────────────────────
─────────────────────────────────────────────────── ───
【手続補正書】[Procedure amendment]
【提出日】平成６年６月２７日[Submission date] June 27, 1994
【手続補正１】[Procedure Amendment 1]
【補正対象書類名】図面[Document name to be corrected] Drawing
【補正対象項目名】図３[Name of item to be corrected] Figure 3
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【図３】 [Figure 3]
───────────────────────────────────────────────────── フロントページの続き (72)発明者 磯 部 誠 千葉県千葉市中央区川崎町１番地 川崎製 鉄株式会社技術研究本部内 (72)発明者 戸 塚 信 夫 千葉県千葉市中央区川崎町１番地 川崎製 鉄株式会社技術研究本部内 (72)発明者 森 戸 延 行 千葉県千葉市中央区川崎町１番地 川崎製 鉄株式会社技術研究本部内 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Makoto Isobe 1 Kawasaki-cho, Chuo-ku, Chiba-shi, Chiba Kawasaki Steel Corporation Technical Research Headquarters (72) Inventor Nobuo Totsuka Kawasaki, Chuo-ku, Chiba-shi, Chiba Town No. 1 Kawasaki Steel Co., Ltd. Technical Research Headquarters (72) Inventor Nobu Morito No. 1 Kawasaki-cho, Chuo-ku, Chiba City Chiba Prefecture Kawasaki Steel Co., Ltd. Technical Research Headquarters
Claims (4)
を含み、さらにＳｉ：０．１％以上２．０％以下、Ｍ
ｎ：０．５％以上２．０％以下、およびＣｒ：０．１％
以上２．０％以下のうち少なくとも一種以上を含有する
鋼板を連続焼鈍設備で再結晶焼鈍し、冷却後に鋼板表面
の鋼中成分の濃化層を酸洗により除去し、連続溶融亜鉛
めっき設備にて再度前記鋼板を６５０℃以上、かつ連続
焼鈍設備での再結晶焼鈍温度以下で加熱して溶融亜鉛め
っきを行うことを特徴とする溶融亜鉛めっき鋼板の製造
方法。1. By weight%, P: 0.03% or more and 0.2% or less is included, Si: 0.1% or more and 2.0% or less, M
n: 0.5% or more and 2.0% or less, and Cr: 0.1%
A steel sheet containing at least one of 2.0% or more is recrystallized by a continuous annealing equipment, and after cooling, the concentrated layer of the steel components on the surface of the steel sheet is removed by pickling to obtain a continuous hot dip galvanizing equipment. A method for producing a hot-dip galvanized steel sheet, wherein the hot-dip galvanized steel sheet is heated by heating the steel sheet again at 650 ° C. or higher and at a temperature lower than the recrystallization annealing temperature in a continuous annealing facility.
造方法であって、溶融亜鉛めっき後、上層めっきを行う
ことを特徴とする溶融亜鉛めっき鋼板の製造方法。2. The method for producing a hot-dip galvanized steel sheet according to claim 1, wherein the hot-dip galvanized steel sheet is subjected to upper layer plating after hot-dip galvanizing.
て製造された溶融亜鉛めっき鋼板に、さらに合金化を行
うことを特徴とする合金化溶融亜鉛めっき鋼板の製造方
法。3. A method for producing an alloyed hot-dip galvanized steel sheet, which further comprises alloying the hot-dip galvanized steel sheet produced by the production method according to claim 1.
板の製造方法であって、合金化後、さらに上層めっきを
行うことを特徴とする合金化溶融亜鉛めっき鋼板の製造
方法。4. The method for producing an alloyed hot-dip galvanized steel sheet according to claim 3, wherein the alloyed hot-dip galvanized steel sheet is further subjected to upper layer plating after alloying.
Priority Applications (8)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP06029775A JP3110238B2 (en) | 1993-06-25 | 1994-02-28 | Method for producing hot-dip galvanized steel sheet and alloyed hot-dip galvanized steel sheet |
| CA002142096A CA2142096C (en) | 1993-06-25 | 1994-06-24 | Method of hot-dip-zinc-plating high-tension steel plate reduced in unplated portions |
| EP94918566A EP0657560B1 (en) | 1993-06-25 | 1994-06-24 | Method of hot-dip-zinc-plating high-tension steel plate reduced in unplated portions |
| US08/381,971 US5677005A (en) | 1993-06-25 | 1994-06-24 | Method for hot dip galvanizing high tensile steel strip with minimal bare spots |
| CN94190540A CN1055510C (en) | 1993-06-25 | 1994-06-24 | Method of hot-dip-zinc-plating high-tension steel plate reduced in unplated portions |
| PCT/JP1994/001017 WO1995000675A1 (en) | 1993-06-25 | 1994-06-24 | Method of hot-dip-zinc-plating high-tension steel plate reduced in unplated portions |
| KR1019950700679A KR100260225B1 (en) | 1993-06-25 | 1994-06-24 | The method of hot high tension zinc plating with reduced unplated portions |
| DE69407937T DE69407937T2 (en) | 1993-06-25 | 1994-06-24 | METHOD FOR HOT-GALNIFYING HIGH-STRENGTH STEEL SHEET WITH LESS UNCOATED AREAS |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15511093 | 1993-06-25 | ||
| JP5-155110 | 1993-06-25 | ||
| JP06029775A JP3110238B2 (en) | 1993-06-25 | 1994-02-28 | Method for producing hot-dip galvanized steel sheet and alloyed hot-dip galvanized steel sheet |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0770723A true JPH0770723A (en) | 1995-03-14 |
| JP3110238B2 JP3110238B2 (en) | 2000-11-20 |
Family
ID=26368007
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP06029775A Expired - Fee Related JP3110238B2 (en) | 1993-06-25 | 1994-02-28 | Method for producing hot-dip galvanized steel sheet and alloyed hot-dip galvanized steel sheet |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3110238B2 (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6797410B2 (en) | 2000-09-11 | 2004-09-28 | Jfe Steel Corporation | High tensile strength hot dip plated steel and method for production thereof |
| JP2006097094A (en) * | 2004-09-29 | 2006-04-13 | Jfe Steel Kk | Hot-dip galvanized steel plate, and its manufacturing method |
| JP2007169696A (en) * | 2005-12-20 | 2007-07-05 | Nippon Steel Corp | Galvannealed steel superior in appearance quality, and manufacturing method therefor |
| JP2007321169A (en) * | 2006-05-30 | 2007-12-13 | Jfe Steel Kk | Method for producing high-strength hot-dip galvanized steel sheet having excellent formability |
| JP2011514436A (en) * | 2008-01-22 | 2011-05-06 | ティッセンクルップ スチール ヨーロッパ アクチェンゲゼルシャフト | Method of coating a metal protective layer on a hot rolled flat steel material or a cold rolled flat steel material containing 6 to 30% by weight of Mn |
| KR20180072809A (en) | 2015-11-26 | 2018-06-29 | 제이에프이 스틸 가부시키가이샤 | A method for producing a high-strength hot-dip galvanized steel sheet, a method for producing a hot-rolled steel sheet for a high-strength hot-dip galvanized steel sheet, a method for producing a cold- |
-
1994
- 1994-02-28 JP JP06029775A patent/JP3110238B2/en not_active Expired - Fee Related
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6797410B2 (en) | 2000-09-11 | 2004-09-28 | Jfe Steel Corporation | High tensile strength hot dip plated steel and method for production thereof |
| JP2006097094A (en) * | 2004-09-29 | 2006-04-13 | Jfe Steel Kk | Hot-dip galvanized steel plate, and its manufacturing method |
| JP4631379B2 (en) * | 2004-09-29 | 2011-02-16 | Ｊｆｅスチール株式会社 | Hot-dip galvanized steel sheet and manufacturing method thereof |
| JP2007169696A (en) * | 2005-12-20 | 2007-07-05 | Nippon Steel Corp | Galvannealed steel superior in appearance quality, and manufacturing method therefor |
| JP4757622B2 (en) * | 2005-12-20 | 2011-08-24 | 新日本製鐵株式会社 | Method for producing alloyed hot-dip galvanized steel with excellent appearance quality |
| JP2007321169A (en) * | 2006-05-30 | 2007-12-13 | Jfe Steel Kk | Method for producing high-strength hot-dip galvanized steel sheet having excellent formability |
| JP4715637B2 (en) * | 2006-05-30 | 2011-07-06 | Ｊｆｅスチール株式会社 | Method for producing high-strength hot-dip galvanized steel sheet with excellent formability |
| JP2011514436A (en) * | 2008-01-22 | 2011-05-06 | ティッセンクルップ スチール ヨーロッパ アクチェンゲゼルシャフト | Method of coating a metal protective layer on a hot rolled flat steel material or a cold rolled flat steel material containing 6 to 30% by weight of Mn |
| KR20180072809A (en) | 2015-11-26 | 2018-06-29 | 제이에프이 스틸 가부시키가이샤 | A method for producing a high-strength hot-dip galvanized steel sheet, a method for producing a hot-rolled steel sheet for a high-strength hot-dip galvanized steel sheet, a method for producing a cold- |
| US11814695B2 (en) | 2015-11-26 | 2023-11-14 | Jfe Steel Corporation | Method for manufacturing high-strength galvanized steel sheet and high-strength galvanized steel sheet |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3110238B2 (en) | 2000-11-20 |
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