JPH07331403A - Production of high strength galvannealed steel sheet - Google Patents
Production of high strength galvannealed steel sheetInfo
- Publication number
- JPH07331403A JPH07331403A JP12551694A JP12551694A JPH07331403A JP H07331403 A JPH07331403 A JP H07331403A JP 12551694 A JP12551694 A JP 12551694A JP 12551694 A JP12551694 A JP 12551694A JP H07331403 A JPH07331403 A JP H07331403A
- Authority
- JP
- Japan
- Prior art keywords
- steel sheet
- zinc
- annealing
- aqueous solution
- coated
- 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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- Chemically Coating (AREA)
- Coating With Molten Metal (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は高強度合金化溶融亜鉛メ
ッキ鋼板の製造方法に係り、さらに詳しくは、例えば自
動車用鋼板として使用される高強度鋼板、特にＰおよび
／またはＳｉを含有する高強度鋼板、において、迅速か
つ低コストで合金化溶融亜鉛メッキを施す方法に関す
る。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a high-strength hot-dip galvanized steel sheet, more specifically, a high-strength steel sheet used as a steel sheet for automobiles, especially a high-strength steel sheet containing P and / or Si. TECHNICAL FIELD The present invention relates to a method for performing galvannealing of a high-strength steel plate rapidly and at low cost.
【０００２】[0002]
【従来の技術】近年、自動車の腐食防止と軽量化という
２つの課題を同時に満足させるものとして、高強度合金
化溶融亜鉛メッキ鋼板の使用が増加している。かかる鋼
板は、その素地鋼板として、ＳｉやＰを含有させた高強
度鋼板を使用しているが、亜鉛の合金化速度が遅いとい
う難点があった。このため、操業面からの対策として、
製造時のライン速度を低下させる方法が取られている
が、これは生産性を低下させ、製造コストを増大させる
ため好ましくない。従って、生産性を低下させないで高
強度合金化溶融亜鉛メッキ鋼板を製造できる方法が強く
望まれている。2. Description of the Related Art In recent years, the use of high-strength hot-dip galvanized steel sheets has been increasing in order to simultaneously satisfy the two problems of corrosion prevention and weight reduction of automobiles. This steel sheet uses a high-strength steel sheet containing Si or P as its base steel sheet, but has a drawback that the alloying rate of zinc is slow. Therefore, as a measure from the operational aspect,
Although a method of reducing the line speed during manufacturing has been adopted, this is not preferable because it lowers the productivity and increases the manufacturing cost. Therefore, there is a strong demand for a method capable of producing a high-strength hot-dip galvanized steel sheet without lowering productivity.
【０００３】合金化反応を促進する方法として、特開昭
６０−１１０８５９号公報において、溶融亜鉛メッキ前
の鋼板表面に、ＮｉあるいはＮｉ合金をプレめっきする
方法が提案されている。しかし、この方法ではプレめっ
き設備が必要であり、設備設置スペースや生産コスト上
昇の点から、実用化には難点がある。As a method for accelerating the alloying reaction, JP-A-60-110859 proposes a method of pre-plating Ni or Ni alloy on the surface of a steel sheet before hot dip galvanizing. However, this method requires pre-plating equipment, and there is a difficulty in putting it to practical use in terms of equipment installation space and production cost increase.
【０００４】また、Ｐを含有する高強度合金化溶融亜鉛
メッキ鋼板の製造方法としては、特開平５−１４８６０
３号公報において、溶融亜鉛メッキ前の鋼板表面に、濃
度０．１％以上の硫黄化合物水溶液を塗布した後、非酸
化性雰囲気で焼鈍する方法が提案されている。この方法
はＰのみを添加して高強度化した鋼板には有効である
が、他の合金元素、例えばＳｉなど、が多量に含まれて
いる場合には、必ずしもその効果が充分ではなく、ま
た、硫黄化合物水溶液を塗布しただけであるために、効
果が不安定であるという難点を有している。Further, as a method for producing a high-strength galvannealed steel sheet containing P, there is disclosed in Japanese Patent Laid-Open No. 5-14860.
In Japanese Patent Laid-Open No. 3 (1993), a method of applying a sulfur compound aqueous solution having a concentration of 0.1% or more to the surface of a steel sheet before hot dip galvanizing and then annealing in a non-oxidizing atmosphere is proposed. This method is effective for a steel plate that has been strengthened by adding only P, but when other alloy elements such as Si are contained in a large amount, the effect is not always sufficient, and However, the effect is unstable because the sulfur compound aqueous solution is simply applied.
【０００５】Ｓｉを含有する鋼板を母材として、溶融亜
鉛メッキを施す方法としては、特開平５−２４７６１４
号公報において、該鋼板表面に予め硫黄単体および／ま
たは硫黄化合物を、Ｓの量に換算して０．０１ｍｇ／ｍ
2 以上含有する皮膜を形成させた後、非酸化性雰囲気で
加熱し、続いて溶融亜鉛メッキを行なう方法が提案され
ている。この方法は、焼鈍炉内で硫黄化合物が炉材と反
応しやすく、炉材コストを上昇させるとともに、環境対
策のために製造コストが増加するという欠点がある。A method of performing hot dip galvanizing using a steel sheet containing Si as a base material is disclosed in Japanese Patent Laid-Open No. 5-247614.
In Japanese Patent Laid-Open Publication No. 2003-242242, simple substance of sulfur and / or sulfur compound is converted into the amount of S in advance and 0.01 mg / m 2
A method has been proposed in which after forming a film containing two or more, heating is performed in a non-oxidizing atmosphere, and then hot dip galvanizing is performed. This method has the drawbacks that the sulfur compound easily reacts with the furnace material in the annealing furnace, increasing the furnace material cost and increasing the manufacturing cost due to environmental measures.
【０００６】[0006]
【発明が解決しようとする課題】本発明は、上記の現状
に鑑みて、高強度鋼板に、迅速かつ低コストで合金化溶
融亜鉛メッキを施す方法を提供することを目的としてい
る。SUMMARY OF THE INVENTION In view of the above situation, it is an object of the present invention to provide a method for galvannealing a high-strength steel sheet quickly and at low cost.
【０００７】[0007]
【課題を解決するための手段】本発明者らは、上記の課
題を解決するために詳細に検討した結果、Ｐおよび／あ
るいはＳｉが焼鈍時に鋼板表面に濃化して、亜鉛の合金
化速度を著しく低下させていることを見出した。そし
て、この問題を解決する手段を種々検討した結果、つい
に、溶融亜鉛メッキ前の焼鈍の前あるいは焼鈍中に、鋼
板表面に無機亜鉛化合物の被膜を形成させ、その後に還
元性あるいは非酸化性の雰囲気で焼鈍し、さらに溶融亜
鉛メッキして加熱合金化すれば、Ｐおよび／またはＳｉ
を含有する高強度鋼板であっても、亜鉛の合金化速度が
大きく増加し、高強度合金化溶融亜鉛メッキ鋼板を工業
的かつ低コストで製造可能にできることを見出した。Means for Solving the Problems The inventors of the present invention have studied in detail in order to solve the above-mentioned problems, and as a result, P and / or Si are concentrated on the surface of the steel sheet during annealing, and the alloying rate of zinc is increased. It was found that it was significantly reduced. Then, as a result of various investigations on means for solving this problem, finally, before or during annealing before hot dip galvanizing, a film of an inorganic zinc compound is formed on the surface of the steel sheet, and then a reducing or non-oxidizing agent is formed. P and / or Si can be obtained by annealing in an atmosphere and then hot dip galvanizing to form a heat alloy.
It has been found that even for a high-strength steel sheet containing the alloy, the alloying rate of zinc is greatly increased, and a high-strength hot-dip galvanized steel sheet can be manufactured industrially and at low cost.
【０００８】本発明はこれらの知見に基づいてなされた
もので、本発明の第１発明が要旨とするところは、鋼板
表面を清浄化した後、該鋼板表面に無機亜鉛化合物をＺ
ｎの量に換算して０．０５ｇ／ｍ2 以上５００ｇ／ｍ2
以下の厚さで被覆し、還元性あるいは非酸化性の雰囲気
で焼鈍した後、該鋼板を大気に接触させること無く溶融
亜鉛中に通板せしめ、さらに加熱合金化処理することを
特徴とする高強度合金化溶融亜鉛メッキ鋼板の製造方
法、にある。The present invention has been made on the basis of these findings. The gist of the first invention of the present invention is that the surface of a steel sheet is cleaned and then an inorganic zinc compound is added to the surface of the steel sheet.
in terms of the amount of n 0.05 g / m 2 or more 500 g / m 2
After being coated in the following thickness and annealed in a reducing or non-oxidizing atmosphere, the steel sheet is passed through molten zinc without contact with the atmosphere, and further heat alloying treatment is performed. A method of manufacturing a strength alloyed hot-dip galvanized steel sheet.
【０００９】また、本発明の第２発明が要旨とするとこ
ろは、第１発明において、無機亜鉛化合物が、水酸化亜
鉛、酸化亜鉛、硫化亜鉛、硝酸亜鉛、硫酸亜鉛のいずれ
か、あるいはこれらの混合物である方法、にある。The gist of the second invention of the present invention is that, in the first invention, the inorganic zinc compound is any one of zinc hydroxide, zinc oxide, zinc sulfide, zinc nitrate and zinc sulfate, or a combination thereof. The method is a mixture.
【００１０】さらに、本発明の第３発明が要旨とすると
ころは、第１発明において、無機亜鉛化合物として、水
酸化亜鉛、硝酸亜鉛のいずれか、あるいは両者の混合物
を被覆し、焼鈍前あるいは焼鈍の加熱によって、該水酸
化亜鉛あるいは硝酸亜鉛を酸化亜鉛に変化せしめ、その
後還元性あるいは非酸化性の雰囲気で焼鈍した後、溶融
亜鉛メッキし、その後に加熱合金化処理する方法、にあ
る。Further, the gist of the third invention of the present invention is that, in the first invention, either zinc hydroxide or zinc nitrate, or a mixture of both is coated as the inorganic zinc compound, before or after annealing. Heating the zinc hydroxide or zinc nitrate to zinc oxide, followed by annealing in a reducing or non-oxidizing atmosphere, hot dip galvanizing, and then heat alloying treatment.
【００１１】次に、本発明の第４発明が要旨とするとこ
ろは、鋼板表面を清浄化した後、該鋼板表面に亜鉛イオ
ンを含有する酸性溶液を付着後、該鋼板表面をアルカリ
性水溶液と接触せしめて、鋼板表面に水酸化亜鉛の被膜
を生成せしめ、さらに還元性あるいは非酸化性の雰囲気
で焼鈍した後、該鋼板を大気に接触させること無く溶融
亜鉛中に通板せしめ、さらに加熱合金化処理する高強度
合金化溶融亜鉛メッキ鋼板の製造方法、にあり、本発明
の第５発明が要旨とするところは、鋼板表面を清浄化し
た後、該鋼板表面に亜鉛イオンを含有する酸性溶液の被
膜を付着後、該鋼板表面を硫化物イオンを含有するアル
カリ性水溶液と接触せしめて、鋼板表面に硫化亜鉛の被
膜を生成せしめ、還元性あるいは非酸化性の雰囲気で焼
鈍した後、該鋼板を大気に接触させること無く溶融亜鉛
中に通板せしめ、さらに加熱合金化処理ことを特徴とす
る高強度合金化溶融亜鉛メッキ鋼板の製造方法、にあ
る。Next, the gist of the fourth invention of the present invention is that after cleaning the surface of a steel sheet, after attaching an acidic solution containing zinc ions to the surface of the steel sheet, the surface of the steel sheet is contacted with an alkaline aqueous solution. At the very least, a zinc hydroxide film is formed on the surface of the steel sheet, and after annealing in a reducing or non-oxidizing atmosphere, the steel sheet is passed through molten zinc without contact with the atmosphere, and then heat alloying is performed. The method for producing a high-strength galvannealed steel sheet to be treated, which is the subject matter of the fifth invention of the present invention, is that after the steel sheet surface is cleaned, the steel sheet surface is treated with an acidic solution containing zinc ions. After the coating is applied, the steel sheet surface is contacted with an alkaline aqueous solution containing sulfide ions to form a zinc sulfide coating on the steel sheet surface, and the steel sheet is annealed in a reducing or non-oxidizing atmosphere. It allowed passing plate during no molten zinc contacting the atmosphere, a method of manufacturing a high-strength alloyed hot-dip galvanized steel sheet, wherein a further heat alloying treatment, in.
【００１２】[0012]
【作用】以下に本発明を詳細に説明する。The present invention will be described in detail below.
【００１３】まず、本発明においては、鋼板表面を清浄
化した後に、鋼板表面に無機亜鉛化合物を被覆するもの
であるが、無機亜鉛化合物がＺｎ量に換算して０．０５
ｇ／ｍ2 未満では、鋼板表面を均一かつ有効に被覆でき
ないために、鋼板表面の一部が露出した状態となり、亜
鉛の合金化を促進する効果が発揮されない。合金化をよ
り確実かつ迅速になすためには、無機亜鉛化合物の被覆
は０．５ｇ／ｍ2 以上とするとさらに好ましい。一方、
亜鉛の合金化を促進する目的からは、無機亜鉛化合物被
覆の厚さに上限はないが、あまりに厚い被覆を施すには
長時間を要して、かえって生産性が低下するので、上限
は５００ｇ／ｍ2 とし、さらに高速で処理するために
は、１００ｇ／ｍ2 以下とすることがより好ましい。な
お、鋼板表面の清浄化は、従来から通常適用されている
方法を使用することができ、例えば、アルカリ脱脂、電
解脱脂、酸洗のいずれか、あるいはこれらの組み合わせ
を適用することができる。First, in the present invention, after the surface of the steel sheet is cleaned, the surface of the steel sheet is coated with an inorganic zinc compound.
If it is less than g / m 2 , the steel sheet surface cannot be uniformly and effectively covered, so that a part of the steel sheet surface is exposed and the effect of promoting alloying of zinc is not exhibited. In order to make the alloying more reliable and rapid, the coating of the inorganic zinc compound is more preferably 0.5 g / m 2 or more. on the other hand,
For the purpose of promoting alloying of zinc, there is no upper limit to the thickness of the inorganic zinc compound coating, but it takes a long time to apply an excessively thick coating, and the productivity is rather lowered. Therefore, the upper limit is 500 g / In order to obtain m 2 and to process at a higher speed, it is more preferable to set it to 100 g / m 2 or less. For cleaning the surface of the steel sheet, a method that has been conventionally applied can be used. For example, any one of alkali degreasing, electrolytic degreasing, pickling, or a combination thereof can be applied.
【００１４】無機亜鉛化合物は、溶融亜鉛中で鋼板表面
に亜鉛がめっきされるのを、阻害しない物質であること
が必要である。かかる物質であれば特に限定されるもの
ではないが、水酸化亜鉛、酸化亜鉛、硫化亜鉛、硝酸亜
鉛、硫酸亜鉛が、特にこの目的に適している。またこれ
らは単独で適用しても良く、２種以上の混合物としても
良い。これらが単独で存在する場合、あるいは混合して
いる場合のいずれにおいても、Ｚｎ量に換算した無機亜
鉛化合物の量は、前述の値であることが必要であるのは
言うまでもない。また、前述の物質が混合物である場合
には、２種以上の物質が板厚方向に積層されていてもよ
く、あるいは２種以上の物質が例えば粒状、あるいは微
粒子で相互に混ざりあっている状態でも、いずれでも良
い。重要なことは、Ｚｎ量に換算した無機亜鉛化合物の
総量が、前述の範囲を満足することである。The inorganic zinc compound must be a substance that does not inhibit the plating of zinc on the surface of the steel sheet in molten zinc. The substance is not particularly limited as long as it is such a substance, but zinc hydroxide, zinc oxide, zinc sulfide, zinc nitrate, and zinc sulfate are particularly suitable for this purpose. These may be applied alone or as a mixture of two or more kinds. It is needless to say that the amount of the inorganic zinc compound converted to the amount of Zn needs to be the above-mentioned value regardless of whether these are present alone or when they are mixed. When the above substances are a mixture, two or more types of substances may be laminated in the plate thickness direction, or a state in which two or more types of substances are mixed with each other, for example, in the form of particles or fine particles. But either is fine. What is important is that the total amount of the inorganic zinc compounds converted into the Zn amount satisfies the above range.
【００１５】鋼板表面を無機亜鉛化合物で被覆した後
に、鋼板の材質を所望のものとするために、鋼板を焼鈍
する。このとき、無機亜鉛化合物被覆の効果を阻害しな
いため、および後続の溶融亜鉛メッキを効果的に行なう
ためには、少なくとも最終段階を還元性あるいは非酸化
性の雰囲気で焼鈍することが必要である。これ以外は、
従来から通常適用されている方法に準じて行なえば良
い。例えば、鋼板を還元性雰囲気で予熱した後、水素を
３〜２５％含有する窒素あるいはアルゴンガス中で、６
００〜８５０℃に加熱して焼鈍することができる。ある
いは、鋼板を酸素を微量含有する弱酸化性の雰囲気で予
熱した後、水素を３〜２５％含有する窒素あるいはアル
ゴンガス中で、６００〜８５０℃に加熱して焼鈍するこ
ともできる。いずれにしても最終の焼鈍雰囲気が還元性
あるいは非酸化性であれば良い。最終段階の焼鈍の雰囲
気の露点は低いほど良く、−２０℃以下が好ましく、−
３０℃以下とするとさらに良好な結果が得られる。After coating the surface of the steel sheet with the inorganic zinc compound, the steel sheet is annealed in order to obtain the desired material for the steel sheet. At this time, it is necessary to anneal at least the final stage in a reducing or non-oxidizing atmosphere in order not to impair the effect of the inorganic zinc compound coating and to effectively perform the subsequent hot dip galvanizing. Other than this,
It suffices to carry out according to a method that is conventionally applied. For example, after preheating a steel sheet in a reducing atmosphere, a nitrogen or argon gas containing 3 to 25% hydrogen is used to
It can be annealed by heating at 00 to 850 ° C. Alternatively, the steel sheet may be preheated in a weakly oxidizing atmosphere containing a small amount of oxygen, and then annealed by heating at 600 to 850 ° C. in nitrogen or argon gas containing 3 to 25% hydrogen. In any case, the final annealing atmosphere may be reducing or non-oxidizing. The lower the dew point of the annealing atmosphere in the final stage, the better, and it is preferably −20 ° C. or lower, −
When the temperature is 30 ° C. or lower, a better result can be obtained.
【００１６】かかる雰囲気で焼鈍した後の鋼板を大気中
に曝すと、鋼板表面が酸化あるいは汚染されて、後続の
亜鉛メッキが不良となる場合があるので、焼鈍後の鋼板
は大気に接触させないで、直接溶融亜鉛中に浸漬するこ
とが必要である。溶融亜鉛メッキは従来から通常適用さ
れている方法に準じて行なえば良い。例えば、Ａｌを
０．０１〜５重量％程度含有するメッキ浴で、浴温４５
０〜４８０℃、といった条件を用いることができる。溶
融亜鉛に浸漬した後、通常の方法で鋼板表面の溶融亜鉛
の厚さを調整した後、鋼板を加熱することによって、メ
ッキした亜鉛を鋼板と合金化させる。合金化のための加
熱は、４６０℃以上であることが好ましく、短時間で確
実に合金化させるためには４８０℃以上がさらに好まし
い。加熱方式には特に制約はなく、従来から一般的に用
いられている方法、例えば、燃焼ガス炎による直接加
熱、誘導加熱、直接通電加熱、等の任意の方式を用いる
ことができる。If the steel sheet after being annealed in such an atmosphere is exposed to the atmosphere, the surface of the steel sheet may be oxidized or contaminated, and the subsequent galvanization may become defective. Therefore, the annealed steel sheet should not be exposed to the atmosphere. It is necessary to directly immerse in molten zinc. The hot dip galvanizing may be performed according to a method that has been conventionally applied. For example, a plating bath containing about 0.01 to 5% by weight of Al and a bath temperature of 45
Conditions such as 0 to 480 ° C. can be used. After being immersed in the molten zinc, the thickness of the molten zinc on the surface of the steel sheet is adjusted by a normal method, and then the steel sheet is heated to alloy the plated zinc with the steel sheet. The heating for alloying is preferably 460 ° C. or higher, and more preferably 480 ° C. or higher for reliable alloying in a short time. The heating method is not particularly limited, and any conventionally used method such as direct heating with a combustion gas flame, induction heating, or direct current heating can be used.
【００１７】上記の無機亜鉛化合物を鋼板表面に被覆す
る工程は、オンラインで圧延工程の後処理工程としして
も良く、あるいは溶融亜鉛メッキのオンライン前処理工
程としても良い。また、本発明方法はオンラインで処理
するばかりでなく、ライン外で単独の工程として処理し
ても良い。The step of coating the surface of the steel sheet with the above-mentioned inorganic zinc compound may be an online post-treatment step of a rolling step or an online pre-treatment step of hot dip galvanizing. Further, the method of the present invention may be processed not only online but also as a single process outside the line.
【００１８】無機亜鉛化合物として、水酸化亜鉛、硝酸
亜鉛のいずれか、あるいは両者の混合物を被覆した場合
には、少なくとも最終段階が還元性あるいは非酸化性の
雰囲気中で焼鈍することによって、これらを酸化亜鉛に
変化せしめると、溶融亜鉛のメッキと合金化に特に有効
である。このとき、水酸化亜鉛、硝酸亜鉛のいずれか、
あるいは両者の混合物を酸化亜鉛に変化せしめる目的の
ためだけであれば、雰囲気は必ずしも還元性あるいは非
酸化性である必要はなく、弱酸化性あるいは酸化性で予
備加熱した後に、還元性あるいは非酸化性の雰囲気中で
焼鈍しても良い。重要なことは、少なくとも最終段階が
還元性あるいは非酸化性の雰囲気中で焼鈍することであ
り、水酸化亜鉛、硝酸亜鉛のいずれか、あるいは両者の
混合物を酸化亜鉛に変化せしめる目的の加熱の雰囲気
は、最終段階の焼鈍に支障の無いものであれば良い。水
酸化亜鉛、硝酸亜鉛のいずれか、あるいは両者の混合物
を酸化亜鉛に変化せしめるためには、予備加熱あるいは
焼鈍の温度は３００℃以上が好ましく、５００℃以上と
すると短時間で処理することが容易である。When any one of zinc hydroxide, zinc nitrate, or a mixture of both is coated as the inorganic zinc compound, at least the final stage is annealed in a reducing or non-oxidizing atmosphere, and these are annealed. When changed to zinc oxide, it is particularly effective for plating and alloying of molten zinc. At this time, either zinc hydroxide or zinc nitrate,
Alternatively, the atmosphere does not necessarily have to be reducing or non-oxidizing, as long as it is only for the purpose of changing the mixture of the two into zinc oxide. It may be annealed in a natural atmosphere. What is important is that at least the final step is annealing in a reducing or non-oxidizing atmosphere, and a heating atmosphere for the purpose of changing either zinc hydroxide, zinc nitrate, or a mixture of both to zinc oxide. May be any as long as it does not hinder the final stage annealing. In order to change either zinc hydroxide or zinc nitrate, or a mixture of both, to zinc oxide, the preheating or annealing temperature is preferably 300 ° C or higher, and when it is 500 ° C or higher, the treatment is easy in a short time. Is.
【００１９】鋼板表面に水酸化亜鉛の被膜を生成せしめ
る方法としては、鋼板表面を清浄化した後に、該鋼板表
面に、亜鉛イオンを含有する酸性水溶液の被膜を形成塗
布する。このとき、該水溶液中の亜鉛イオンの濃度は
０．０１モル／ｌ以上が好ましく、水溶液のｐＨ（水素
イオン濃度指数）は２以上５以下が好ましい。亜鉛イオ
ン濃度が０．０１モル未満では、鋼板表面に水酸化亜鉛
の被覆を充分に形成することが困難である。また、ｐＨ
が２未満では、鋼板の腐食が著しくなって鋼板の表面性
状を劣化させるし、ｐＨが６を超えると水溶液中に水酸
化亜鉛が析出してしまう恐れがある。亜鉛イオンを含有
する酸性水溶液の被膜を鋼板表面に形成するには、例え
ばロール転写法、即ちロールにまず該水溶液を塗布し、
このロールと鋼板とを回転接触せしめて、該水溶液を鋼
板表面に連続的に塗布する方法、あるいは噴霧、スプレ
ー、浸漬、といった方法を適用することができる。該水
溶液の温度は室温でも良いが、９５℃までの高温として
も良く、温度に制約はない。As a method of forming a zinc hydroxide film on the surface of a steel sheet, after cleaning the surface of the steel sheet, a film of an acidic aqueous solution containing zinc ions is formed and applied on the surface of the steel sheet. At this time, the concentration of zinc ions in the aqueous solution is preferably 0.01 mol / l or more, and the pH (hydrogen ion concentration index) of the aqueous solution is preferably 2 or more and 5 or less. If the zinc ion concentration is less than 0.01 mol, it is difficult to sufficiently form a zinc hydroxide coating on the surface of the steel sheet. Also, the pH
When the value is less than 2, corrosion of the steel sheet becomes remarkable and the surface properties of the steel sheet are deteriorated, and when the pH exceeds 6, zinc hydroxide may be precipitated in the aqueous solution. To form a film of an acidic aqueous solution containing zinc ions on the surface of a steel sheet, for example, a roll transfer method, that is, a roll is first coated with the aqueous solution,
A method in which the roll and the steel sheet are brought into rotational contact with each other to continuously apply the aqueous solution to the surface of the steel sheet, or a method such as spraying, spraying or dipping can be applied. The temperature of the aqueous solution may be room temperature, but may be a high temperature up to 95 ° C., and the temperature is not limited.
【００２０】次に、亜鉛イオンを含有する酸性溶液を塗
布した鋼板を、アルカリ性水溶液と接触せしめて、該鋼
板表面に水酸化亜鉛の被膜を生成せしめるのであるが、
アルカリ性水溶液のｐＨは８以上１２以下がより好まし
い。ｐＨが８未満あるいは１２を超えると、いずれも水
酸化亜鉛が不安定になって、鋼板表面に有効に被覆する
ことが困難になる。アルカリ性水溶液としては、例えば
水酸化ナトリウム、水酸化カリウム、などの水溶液を用
いることができる。アルカリ性水溶液の温度は室温とし
ても良く、５５℃までの高温としても良いが、６０℃以
上では水酸化亜鉛が生成し難くなるので、あまり高温に
することは好ましくない。また、亜鉛イオンを含有する
酸性水溶液の被膜を形成した鋼板をアルカリ性水溶液と
接触せしめる方法としては、例えば、冷延鋼帯などの形
状の鋼板を、連続的にアルカリ性水溶液の槽中に浸漬・
通板せしめる方法、あるいはアルカリ性水溶液を噴霧ま
たはスプレーする、といった方法、を適用することがで
きる。Next, the steel sheet coated with an acidic solution containing zinc ions is brought into contact with an alkaline aqueous solution to form a zinc hydroxide film on the surface of the steel sheet.
The pH of the alkaline aqueous solution is more preferably 8 or more and 12 or less. When the pH is less than 8 or more than 12, zinc hydroxide becomes unstable and it becomes difficult to effectively coat the surface of the steel sheet. As the alkaline aqueous solution, for example, an aqueous solution of sodium hydroxide, potassium hydroxide or the like can be used. The temperature of the alkaline aqueous solution may be room temperature or a high temperature up to 55 ° C. However, if the temperature is 60 ° C. or higher, it is difficult to form zinc hydroxide, so it is not preferable to raise the temperature too high. Further, as a method of bringing a steel sheet on which a film of an acidic aqueous solution containing zinc ions is formed into contact with an alkaline aqueous solution, for example, a steel sheet having a shape such as a cold rolled steel strip is continuously immersed in a tank of the alkaline aqueous solution.
A method of passing through a plate or a method of spraying or spraying an alkaline aqueous solution can be applied.
【００２１】鋼板表面に硫化亜鉛の被膜を生成せしめる
方法としては、鋼板表面を清浄化した後に、該鋼板表面
に亜鉛イオンを含有する酸性水溶液の被膜を、まず形成
する。このとき、該水溶液中の亜鉛イオンの濃度は０．
０１モル／ｌ以上が好ましく、水溶液のｐＨ（水素イオ
ン濃度指数）は２以上５以下が好ましい。亜鉛イオン濃
度が０．０１モル未満では、鋼板表面に硫化亜鉛の被覆
を充分に形成することが困難である。また、ｐＨが２未
満では鋼板の腐食が著しくなって、鋼板の表面性状を劣
化させるし、ｐＨが６を超えると水溶液中に水酸化亜鉛
が析出してしまう恐れがある。亜鉛イオンを含有する酸
性水溶液の被膜を鋼板表面に形成するには、例えばロー
ル転写法、即ちロールにまず該水溶液を塗布し、このロ
ールと鋼板とを回転接触せしめて、該水溶液を鋼板表面
に連続的に塗布する方法、あるいは噴霧、スプレー、浸
漬、といった方法を適用することができる。該水溶液の
温度は室温でも良いが、９５℃までの高温としても良
く、温度に制約はない。As a method of forming a zinc sulfide film on the surface of a steel sheet, after cleaning the surface of the steel sheet, a film of an acidic aqueous solution containing zinc ions is first formed on the surface of the steel sheet. At this time, the concentration of zinc ions in the aqueous solution was 0.
The amount (pH of hydrogen ion concentration) of the aqueous solution is preferably 2 or more and 5 or less. If the zinc ion concentration is less than 0.01 mol, it is difficult to sufficiently form a zinc sulfide coating on the surface of the steel sheet. On the other hand, if the pH is less than 2, corrosion of the steel sheet becomes remarkable and the surface properties of the steel sheet are deteriorated, and if the pH exceeds 6, zinc hydroxide may be precipitated in the aqueous solution. To form a coating film of an acidic aqueous solution containing zinc ions on the surface of a steel sheet, for example, a roll transfer method, that is, the aqueous solution is first applied to a roll, and the roll and the steel sheet are brought into rotational contact, so that the aqueous solution is applied to the steel sheet surface. A method of continuously applying or a method of spraying, spraying, dipping or the like can be applied. The temperature of the aqueous solution may be room temperature, but may be a high temperature up to 95 ° C., and the temperature is not limited.
【００２２】次に、亜鉛イオンを含有する酸性水溶液の
被膜を形成した鋼板を、硫化物イオンを含有するアルカ
リ性水溶液と接触せしめて、鋼板表面に硫化亜鉛の被膜
を生成せしめるのであるが、アルカリ性水溶液のｐＨは
８以上がより好ましい。ｐＨが８未満では硫化亜鉛が不
安定になって、鋼板表面に有効に被覆することが困難に
なる。硫化物イオンを含有するアルカリ性水溶液として
は、例えば硫化ナトリウム、硫化カリウム、などの水溶
液のｐＨを調整して用いることができる。ここで、硫化
物イオンの濃度は、０．００１モル／ｌ以上がより好ま
しい。アルカリ性水溶液の温度は室温としても良く、９
５℃までの高温としても良く、温度に制約はない。ま
た、亜鉛イオンを含有する酸性水溶液を塗布した鋼板
を、硫化物イオン含有アルカリ性水溶液と接触せしめる
方法としては、例えば、冷延鋼帯などの形状の鋼板を、
連続的に硫化物イオン含有アルカリ性水溶液の槽中に浸
漬・通板せしめる方法、あるいはアルカリ性水溶液を噴
霧またはスプレーする、といった方法、を適用すること
ができる。Next, the steel sheet on which a film of an acidic aqueous solution containing zinc ions is formed is brought into contact with an alkaline aqueous solution containing sulfide ions to form a film of zinc sulfide on the surface of the steel sheet. The pH of 8 is more preferably 8 or more. If the pH is less than 8, zinc sulfide becomes unstable and it becomes difficult to effectively coat the surface of the steel sheet. As the alkaline aqueous solution containing sulfide ions, for example, the pH of an aqueous solution of sodium sulfide, potassium sulfide, or the like can be adjusted and used. Here, the concentration of sulfide ions is more preferably 0.001 mol / l or more. The temperature of the alkaline aqueous solution may be room temperature.
The temperature may be as high as 5 ° C, and there is no restriction on the temperature. Further, as a method of contacting a steel sheet coated with an acidic aqueous solution containing zinc ions with a sulfide ion-containing alkaline aqueous solution, for example, a steel sheet having a shape such as a cold rolled steel strip,
It is possible to apply a method of continuously immersing and passing through a bath of an alkaline aqueous solution containing sulfide ions, or a method of spraying or spraying an alkaline aqueous solution.
【００２３】この方法によれば、亜鉛メッキ浴中に、Ａ
ｌの他に、Ｐｂ、Ｓｂ、Ｓｉ、Ｆｅ、Ｓｎ、Ｍｇ、Ｍ
ｎ、Ｎｉ、Ｃｒ、Ｃｏ、Ｃａ、Ｌｉ、Ｔｉ、希土類元素
の１種または２種以上を含有あるいは混入した浴であっ
ても、支障をきたすことはない。According to this method, in the zinc plating bath, A
l, Pb, Sb, Si, Fe, Sn, Mg, M
Even a bath containing or mixed with one or more of n, Ni, Cr, Co, Ca, Li, Ti, and rare earth elements will not cause any trouble.
【００２４】本方法が対象とする鋼板は、Ｐおよび／ま
たはＳｉを含有する鋼板が主たる対象であるが、Ｚｎよ
りも酸化物生成能力が高い元素を含有する鋼板に適用し
ても同様の効果が得られるとともに、さらに通常の鋼板
に本発明を適用しても、勿論何ら問題はない。The steel sheet targeted by the present method is mainly a steel sheet containing P and / or Si, but the same effect can be obtained by applying it to a steel sheet containing an element having a higher oxide forming ability than Zn. When the present invention is applied to an ordinary steel plate, there is of course no problem.
【００２５】当然のことながら、本発明の方法で得られ
た合金化溶融亜鉛メッキ鋼板上に、塗装性、溶接性等を
改善する目的で、各種の電気メッキを施すことも勿論可
能であり、本願発明を逸脱するものではない。また、本
発明の方法で得られた合金化溶融亜鉛メッキ鋼板上に、
各種の処理を付加して施すことも勿論可能であり、例え
ば、クロメート処理、リン酸塩処理、リン酸塩処理性を
向上させるための処理、潤滑性向上処理、溶接性向上処
理、樹脂塗布処理、等を施したとしても、本願発明の範
囲を逸脱するものではなく、付加して必要とする特性に
応じて、各種の処理を施すことができる。As a matter of course, it is of course possible to perform various electroplating on the alloyed hot-dip galvanized steel sheet obtained by the method of the present invention for the purpose of improving paintability, weldability and the like. It does not depart from the invention of the present application. Further, on the alloyed hot dip galvanized steel sheet obtained by the method of the present invention,
It is of course possible to add various kinds of treatments, for example, chromate treatment, phosphate treatment, treatment for improving phosphate treatment, lubricity improving treatment, weldability improving treatment, resin coating treatment. , Etc. do not depart from the scope of the invention of the present application, and various treatments can be carried out according to the characteristics additionally required.
【００２６】[0026]
［実施例１］第１表に成分を示す冷延鋼板を供試材とし
た。ここで板厚は０．６ｍｍとし、第２表に組成および
条件を示す無機亜鉛化合物を被覆した後、溶融亜鉛メッ
キして、合金化完了までの時間を調べた。メッキに際し
ては、焼鈍雰囲気は５％水素＋９５％窒素混合ガスと
し、焼鈍温度は８００℃、焼鈍時間は７５秒とし、溶融
亜鉛浴の組成はＡｌを０．１％含有する溶融亜鉛とし、
ガスワイパーで亜鉛の付着量を６０ｇ／ｍ2 に調整し
た。合金化は誘導加熱方式の加熱設備で行ない、加熱温
度は４９０℃とした。[Example 1] A cold rolled steel sheet having the components shown in Table 1 was used as a test material. Here, the plate thickness was set to 0.6 mm, and after coating with an inorganic zinc compound whose composition and conditions are shown in Table 2, hot dip galvanizing was performed, and the time until completion of alloying was examined. At the time of plating, the annealing atmosphere is 5% hydrogen + 95% nitrogen mixed gas, the annealing temperature is 800 ° C., the annealing time is 75 seconds, and the composition of the molten zinc bath is molten zinc containing 0.1% Al.
The amount of zinc adhered was adjusted to 60 g / m 2 with a gas wiper. The alloying was performed with induction heating type heating equipment, and the heating temperature was 490 ° C.
【００２７】第２表において、１Ａおよび２Ａにおける
水酸化亜鉛の被膜は、亜鉛イオン０．０３モル／ｌを含
有しｐＨを２．８〜３．０に調整した水溶液に連続的に
通板した後に、ｐＨを９．５〜９．８に調整したアルカ
リ性水溶液をスプレーして形成した。１Ｂおよび２Ｂに
おける硫化亜鉛の被膜は、亜鉛イオン０．５モル／ｌを
含有しｐＨを３．５〜３．８に調整した水溶液に連続的
に通板した後に、硫化物イオンを含有しｐＨを１２．３
〜１２．５に調整したアルカリ性水溶液をスプレーして
形成した。１Ｃおよび２Ｃにおける硝酸亜鉛、１Ｄおよ
び２Ｄにおける硫酸亜鉛の被膜は、それぞれ硝酸亜鉛水
溶液あるいは硫酸亜鉛水溶液を、鋼板表面にロールコー
タで塗布して形成した。１Ｅおよび２Ｅにおける水酸化
亜鉛と硝酸亜鉛の混合物は、まず鋼板表面に硝酸亜鉛水
溶液を付着させた後に、ｐＨをおよそ９に調整したアル
カリ性水溶液をスプレーして、硝酸亜鉛の一部を水酸化
亜鉛に変化せしめて形成した。In Table 2, the coatings of zinc hydroxide in 1A and 2A were continuously passed through an aqueous solution containing 0.03 mol / l of zinc ions and having a pH adjusted to 2.8 to 3.0. After that, it was formed by spraying an alkaline aqueous solution whose pH was adjusted to 9.5 to 9.8. The zinc sulfide coatings in 1B and 2B were continuously passed through an aqueous solution containing zinc ions at 0.5 mol / l and having a pH adjusted to 3.5 to 3.8, and then containing sulfide ions at pH. To 12.3
It was formed by spraying an alkaline aqueous solution adjusted to ˜12.5. The zinc nitrate coatings in 1C and 2C and the zinc sulfate coatings in 1D and 2D were formed by applying an aqueous solution of zinc nitrate or an aqueous solution of zinc sulfate, respectively, onto the surface of the steel sheet with a roll coater. The mixture of zinc hydroxide and zinc nitrate in 1E and 2E was prepared by first adhering a zinc nitrate aqueous solution to the surface of the steel sheet and then spraying an alkaline aqueous solution whose pH was adjusted to approximately 9 to part of zinc nitrate. It was formed by changing to.
【００２８】第２表に、結果をあわせて示す。第２表に
おいて、◎は合金化完了までの時間が１５秒以下であっ
たものを表わし、○は合金化完了までの時間が２５秒以
下であったものを表わし、×は合金化完了までの時間が
２５秒を超えていたことを表わす。第２表から明らかな
ように、本発明方法に従って鋼板表面に無機亜鉛化合物
を被覆したＮｏ．１Ａ〜１Ｅおよび２Ａ〜２Ｅは、容易
に合金化溶融亜鉛メッキ鋼板が得られた。また、不メッ
キの発生はなく、表面品質にも優れていた。これに対し
て、無処理のＮｏ．１Ｆ、２Ｆおよび条件が不充分であ
った１Ｇ、２Ｇでは、合金化完了までに長時間を要して
いるし、一部に不メッキがみられた。The results are also shown in Table 2. In Table 2, ⊚ represents that the time to complete alloying was 15 seconds or less, ∘ represents that the time to completion of alloying was 25 seconds or less, and × represents the time until completion of alloying. Indicates that the time has exceeded 25 seconds. As is apparent from Table 2, No. 1 in which the surface of the steel sheet was coated with the inorganic zinc compound according to the method of the present invention. For 1A to 1E and 2A to 2E, galvannealed steel sheets were easily obtained. Moreover, no plating occurred and the surface quality was excellent. On the other hand, the unprocessed No. In 1F and 2F and 1G and 2G where the conditions were insufficient, it took a long time to complete alloying, and non-plating was partially observed.
【００２９】[0029]
【表１】 [Table 1]
【００３０】[0030]
【表２】 [Table 2]
【００３１】［実施例２］第３表に成分を示す冷延鋼板
を供試材とした。ここで板厚は０．８ｍｍとし、第４表
に組成および条件を示す無機亜鉛化合物を被覆した後、
溶融亜鉛メッキして、合金化完了までの時間を調べた。
メッキに際しては、焼鈍雰囲気は７％水素＋９３％窒素
混合ガスとし、焼鈍温度は８１０℃、焼鈍時間は９０秒
とし、溶融亜鉛浴の組成はＡｌを０．１２％含有する溶
融亜鉛とし、ガスワイパーで亜鉛の付着量を６０ｇ／ｍ
2 に調整した。合金化は誘導加熱方式の加熱設備で行な
い、加熱温度は５００℃とした。酸化亜鉛の被膜は、Ｎ
ｏ．３Ａ〜３Ｂ、４Ａ〜４Ｂ、３Ｆおよび４Ｆでは、硝
酸亜鉛水溶液を鋼板表面にロールコータで塗布した後
に、第４表にあわせて示す条件で加熱して、硝酸亜鉛を
酸化亜鉛に変化せしめて形成し、Ｎｏ．３Ｃ〜３Ｄおよ
び４Ｃ〜４Ｄでは鋼板表面に水酸化亜鉛の被膜を形成さ
せた後に、第４表にあわせて示す条件で加熱して水酸化
亜鉛を酸化亜鉛に変化せしめて形成した。[Example 2] A cold rolled steel sheet having the components shown in Table 3 was used as a test material. Here, the plate thickness is 0.8 mm, and after coating with an inorganic zinc compound whose composition and conditions are shown in Table 4,
Hot-dip galvanizing was performed, and the time until the completion of alloying was examined.
At the time of plating, the annealing atmosphere was a mixed gas of 7% hydrogen and 93% nitrogen, the annealing temperature was 810 ° C., the annealing time was 90 seconds, the composition of the molten zinc bath was molten zinc containing 0.12% Al, and the gas wiper was used. The amount of zinc adhered is 60 g / m
Adjusted to 2 . The alloying was performed with induction heating type heating equipment, and the heating temperature was 500 ° C. The zinc oxide coating is N
o. In 3A to 3B, 4A to 4B, 3F, and 4F, after applying a zinc nitrate aqueous solution to the surface of the steel sheet with a roll coater, heating was performed under the conditions shown in Table 4 to transform zinc nitrate into zinc oxide. No. In 3C to 3D and 4C to 4D, after forming a film of zinc hydroxide on the surface of the steel sheet, it was heated under the conditions shown in Table 4 to change zinc hydroxide to zinc oxide.
【００３２】第４表に結果をあわせて示す。第４表にお
いて、合金化時間の評価は第２表と同じである。第４表
から明らかなように、本発明方法に従って鋼板表面に無
機亜鉛化合物を被覆したＮｏ．３Ａ〜３Ｄおよび４Ａ〜
４Ｄは、容易に合金化溶融亜鉛メッキ鋼板が得られた。
また、不メッキの発生はなく、表面品質にも優れてい
た。これに対して、無処理のＮｏ．３Ｅ、４Ｅおよび条
件が不充分であった３Ｆ、４Ｆでは合金化完了までに長
時間を要しているし、鋼板の一部に不メッキがみられ
た。The results are also shown in Table 4. In Table 4, the evaluation of alloying time is the same as in Table 2. As is clear from Table 4, No. 1 in which the surface of the steel sheet was coated with an inorganic zinc compound according to the method of the present invention. 3A to 3D and 4A to
In 4D, a galvannealed steel sheet was easily obtained.
Moreover, no plating occurred and the surface quality was excellent. On the other hand, the unprocessed No. In 3E and 4E and 3F and 4F where the conditions were insufficient, it took a long time to complete alloying, and non-plating was observed on a part of the steel sheet.
【００３３】[0033]
【表３】 [Table 3]
【００３４】[0034]
【表４】 [Table 4]
【００３５】[0035]
【発明の効果】以上に述べたように、本発明は高強度合
金化溶融亜鉛メッキ鋼板を生産性良く、低コストでの製
造することを可能としたものであって、かつ鋼板の組成
に対する制限を著しく軽減して、種々の高強度合金化溶
融亜鉛メッキ鋼板の製造を可能とし、従って産業の発展
に貢献するところは極めて大である。INDUSTRIAL APPLICABILITY As described above, the present invention makes it possible to produce a high-strength galvannealed steel sheet with high productivity and at low cost, and limits on the composition of the steel sheet. It is possible to produce various high-strength alloy hot-dip galvanized steel sheets by significantly reducing the above-mentioned problem, and therefore, it is very important to contribute to the development of the industry.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 庁内整理番号 ＦＩ 技術表示箇所 Ｃ２３Ｃ 18/12 ─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 6 Identification code Internal reference number FI technical display location C23C 18/12
Claims (5)
無機亜鉛化合物をＺｎの量に換算して０．０５ｇ／ｍ2
以上５００ｇ／ｍ2 以下の厚さで被覆し、還元性あるい
は非酸化性の雰囲気で焼鈍した後、該鋼板を大気に接触
させること無く溶融亜鉛中に通板せしめ、さらに加熱合
金化処理することを特徴とする高強度合金化溶融亜鉛メ
ッキ鋼板の製造方法。1. After cleaning the surface of a steel sheet, the inorganic zinc compound is converted into the amount of Zn on the surface of the steel sheet in an amount of 0.05 g / m 2
After coating with a thickness of not less than 500 g / m 2 and annealing in a reducing or non-oxidizing atmosphere, the steel sheet is passed through molten zinc without contact with the atmosphere, and further heat alloyed. A method for producing a high-strength galvannealed steel sheet, characterized by:
鉛、硫化亜鉛、硝酸亜鉛、硫酸亜鉛のいずれか、あるい
はこれらの混合物である請求項１に記載の高強度合金化
溶融亜鉛メッキ鋼板の製造方法。2. The high-strength galvannealed steel sheet according to claim 1, wherein the inorganic zinc compound is any one of zinc hydroxide, zinc oxide, zinc sulfide, zinc nitrate, zinc sulfate, or a mixture thereof. Production method.
酸亜鉛のいずれか、あるいは両者の混合物を被覆し、焼
鈍前あるいは焼鈍の加熱によって、該水酸化亜鉛あるい
は硝酸亜鉛を酸化亜鉛に変化せしめ、その後還元性ある
いは非酸化性の雰囲気で焼鈍した後、溶融亜鉛メッキ
し、その後に加熱合金化処理する請求項１に記載の高強
度合金化溶融亜鉛メッキ鋼板の製造方法。3. As the inorganic zinc compound, either zinc hydroxide or zinc nitrate or a mixture of both is coated, and the zinc hydroxide or zinc nitrate is converted to zinc oxide by heating before annealing or by heating during annealing, The method for producing a high-strength hot-dip galvanized steel sheet according to claim 1, further comprising annealing in a reducing or non-oxidizing atmosphere, hot dip galvanizing, and then heat alloying treatment.
亜鉛イオンを含有する酸性溶液を付着後、該鋼板表面を
アルカリ性水溶液と接触せしめて、鋼板表面に水酸化亜
鉛の被膜を生成せしめ、さらに還元性あるいは非酸化性
の雰囲気で焼鈍した後、該鋼板を大気に接触させること
無く溶融亜鉛中に通板せしめ、さらに加熱合金化処理す
ることを特徴とする高強度合金化溶融亜鉛メッキ鋼板の
製造方法。4. After cleaning the surface of a steel sheet, after adhering an acidic solution containing zinc ions to the surface of the steel sheet, the surface of the steel sheet is contacted with an alkaline aqueous solution to form a zinc hydroxide film on the surface of the steel sheet. After further annealing in a reducing or non-oxidizing atmosphere, the steel sheet is passed through hot-dip zinc without contact with the atmosphere, and further heat-alloying treatment is performed, and high-strength hot-dip galvannealing is performed. Steel plate manufacturing method.
亜鉛イオンを含有する酸性溶液を付着後、該鋼板表面を
硫化物イオンを含有するアルカリ性水溶液と接触せしめ
て、鋼板表面に硫化亜鉛の被膜を生成せしめ、還元性あ
るいは非酸化性の雰囲気で焼鈍した後、該鋼板を大気に
接触させること無く溶融亜鉛中に通板せしめ、さらに加
熱合金化処理することを特徴とする高強度合金化溶融亜
鉛メッキ鋼板の製造方法。5. After cleaning the surface of a steel sheet, after adhering an acidic solution containing zinc ions to the surface of the steel sheet, the surface of the steel sheet is contacted with an alkaline aqueous solution containing sulfide ions to form zinc sulfide on the surface of the steel sheet. A high-strength alloy characterized by producing a coating film of 1), annealing it in a reducing or non-oxidizing atmosphere, then passing the steel sheet through molten zinc without contacting it with the atmosphere, and further heat-alloying it. Method for producing hot-dip galvanized steel sheet.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12551694A JPH07331403A (en) | 1994-06-07 | 1994-06-07 | Production of high strength galvannealed steel sheet |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12551694A JPH07331403A (en) | 1994-06-07 | 1994-06-07 | Production of high strength galvannealed steel sheet |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH07331403A true JPH07331403A (en) | 1995-12-19 |
Family
ID=14912087
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP12551694A Withdrawn JPH07331403A (en) | 1994-06-07 | 1994-06-07 | Production of high strength galvannealed steel sheet |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH07331403A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002256406A (en) * | 2001-03-06 | 2002-09-11 | Nkk Corp | Galvannealed steel sheet |
| JP2009079291A (en) * | 2007-09-04 | 2009-04-16 | Jfe Steel Kk | Galvanized steel sheet |
| JP2009174047A (en) * | 2007-12-27 | 2009-08-06 | Jfe Steel Corp | Galvanized steel sheet, and method for producing the same |
| WO2010074435A3 (en) * | 2008-12-26 | 2010-09-10 | 주식회사 포스코 | Steel sheet annealing device, device for producing plated steel sheet comprising the same, and production method for plated steel sheet using the same |
| CN112030091A (en) * | 2020-09-11 | 2020-12-04 | 霸州市青朗环保科技有限公司 | Method for preparing composite coating on surface of metal product |
| WO2022085434A1 (en) * | 2020-10-23 | 2022-04-28 | 日本製鉄株式会社 | Plated steel sheet for precoated steel sheet, precoated plated steel sheet, and molded article |
-
1994
- 1994-06-07 JP JP12551694A patent/JPH07331403A/en not_active Withdrawn
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002256406A (en) * | 2001-03-06 | 2002-09-11 | Nkk Corp | Galvannealed steel sheet |
| JP4696376B2 (en) * | 2001-03-06 | 2011-06-08 | Ｊｆｅスチール株式会社 | Alloy hot-dip galvanized steel sheet |
| JP2009079291A (en) * | 2007-09-04 | 2009-04-16 | Jfe Steel Kk | Galvanized steel sheet |
| JP2009174047A (en) * | 2007-12-27 | 2009-08-06 | Jfe Steel Corp | Galvanized steel sheet, and method for producing the same |
| WO2010074435A3 (en) * | 2008-12-26 | 2010-09-10 | 주식회사 포스코 | Steel sheet annealing device, device for producing plated steel sheet comprising the same, and production method for plated steel sheet using the same |
| US10053749B2 (en) | 2008-12-26 | 2018-08-21 | Posco | Production method for plated steel sheet using a steel sheet annealing device |
| CN112030091A (en) * | 2020-09-11 | 2020-12-04 | 霸州市青朗环保科技有限公司 | Method for preparing composite coating on surface of metal product |
| WO2022085434A1 (en) * | 2020-10-23 | 2022-04-28 | 日本製鉄株式会社 | Plated steel sheet for precoated steel sheet, precoated plated steel sheet, and molded article |
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