JPH0645853B2 - Method for producing galvannealed steel sheet - Google Patents
Method for producing galvannealed steel sheetInfo
- Publication number
- JPH0645853B2 JPH0645853B2 JP63186394A JP18639488A JPH0645853B2 JP H0645853 B2 JPH0645853 B2 JP H0645853B2 JP 63186394 A JP63186394 A JP 63186394A JP 18639488 A JP18639488 A JP 18639488A JP H0645853 B2 JPH0645853 B2 JP H0645853B2
- Authority
- JP
- Japan
- Prior art keywords
- steel sheet
- hot
- dip galvanized
- producing
- galvanized steel
- 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.)
- Expired - Fee Related
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- Coating With Molten Metal (AREA)
Description
【発明の詳細な説明】 （産業上の利用分野） 本発明は、合金化溶融亜鉛めっき鋼板の製造方法に関
し、詳しくは、合金化層にミクロの凹凸模様や筋ムラが
なく表面外観が美麗で均一な合金化溶融亜鉛めっき鋼板
を製造する方法に関するものである。Description: TECHNICAL FIELD The present invention relates to a method for producing an alloyed hot-dip galvanized steel sheet, and more specifically, it has a beautiful surface appearance without micro uneven patterns or streaks in the alloyed layer. The present invention relates to a method for producing a uniform galvannealed steel sheet.
（従来の技術） 合金化溶融亜鉛めっき鋼板は、耐食性に優れるだけでな
く塗装仕上り外観、塗膜密着性も優れていることから自
動車や家電製品等の外装材に広く使用されている。かか
る合金化溶融亜鉛めっき鋼板は、通常、冷延鋼板を加熱
（焼鈍）・還元した後、溶融亜鉛めっき浴に浸漬してめ
っきし、次いで、材温 250〜750 ℃で加熱してFe−Znの
相互拡散を起こさせて合金層を形成させる、いわゆる合
金化処理を施して製造される。(Prior Art) Alloyed hot-dip galvanized steel sheets are widely used as exterior materials for automobiles, home appliances, etc. because they have not only excellent corrosion resistance, but also excellent finished appearance and coating adhesion. Such alloyed hot-dip galvanized steel sheet is usually prepared by heating (annealing) and reducing a cold-rolled steel sheet, immersing it in a hot-dip galvanizing bath for plating, and then heating at a material temperature of 250 to 750 ° C to produce Fe-Zn. It is manufactured by subjecting a so-called alloying treatment that causes mutual diffusion of to form an alloy layer.
ところで、近年、かかる溶融亜鉛めっき鋼板にも様々な
特性が要求されるようになってきた。例えば、自動車用
防錆鋼板としては、従来製品よりも一段と厳しい成形加
工が可能なもの、或いは車体の軽量化要求に伴ない、従
来の製品よりも板厚が薄くても同等以上の強さが得られ
る高強度のものが望まれている。かかる要求に応えるた
め、母材の被めっき鋼板として、極低炭素鋼にTi、Nb等
を添加したもの、さらに、Si、Mn、 Aｌ、Cr等の合金元
素を１種又は２種以上添加したもの、などが用いられる
ようになってきた。特に、高度の深絞り性の要求される
ものでは、Tiを添加して固溶Ｃを固低した鋼板（所謂sl
abilized steel）、その中でも極低炭素鋼にTiを添加し
たＩＦ鋼（Interstitial Free 鋼）が合金化溶融亜鉛め
っき鋼板の母材として注目されている。By the way, in recent years, various characteristics have come to be required for such hot-dip galvanized steel sheets. For example, as an anticorrosive steel sheet for automobiles, it is possible to perform more severe forming processing than conventional products, or with the demand for weight reduction of vehicle bodies, even if the plate thickness is thinner than conventional products, it is equivalent or stronger. A high-strength product that can be obtained is desired. In order to meet such demands, as a base steel sheet to be plated, ultra low carbon steel to which Ti, Nb, etc. are added, and one or more alloy elements such as Si, Mn, Al, Cr are added. Things have come to be used. Particularly, in the case where a high degree of deep drawability is required, a steel sheet in which Ti is added to lower the solid solution C (so-called sl
abilized steel), especially IF steel (Interstitial Free steel) obtained by adding Ti to ultra-low carbon steel, is drawing attention as a base material for galvannealed steel sheets.
しかし、上記のような Aｌ、Si、Mn、Ti等の金属を含む
鋼板は、これら元素の表面濃化、表面介在物の偏析、表
面酸化、表面結晶粒度等が局所的に不均一となったり変
動しやすい傾向にある。即ち、鋼板表面は、その界面エ
ネルギーにより製鋼、連続鋳造、熱間圧延および冷間圧
延という製造工程、さらには溶融亜鉛めっきラインでの
加熱・還元および冷却工程の中で、上記のような不均一
性が不可避的に発生するが、 Aｌ、Si、Mn、Ti等を含む
鋼板は、この不均一性が一層促進される傾向にある。However, in steel sheets containing metals such as Al, Si, Mn, and Ti as described above, surface concentration of these elements, segregation of surface inclusions, surface oxidation, surface grain size, etc. may become locally uneven. It tends to fluctuate. That is, the surface of the steel sheet is uneven due to the interfacial energy during the manufacturing steps of steelmaking, continuous casting, hot rolling and cold rolling, and the heating / reduction and cooling steps in the hot dip galvanizing line. However, the nonuniformity tends to be further promoted in the steel sheet containing Al, Si, Mn, Ti and the like.
かかる表面の局所的不均一が存在する鋼板を、溶融亜鉛
めっき後に合金化処理すれば、合金化層にミクロの凹凸
模様が生じ易いことが知られており、甚だしいものは目
視でもわかる白スジや黒スジと称する筋ムラが生じる。It is known that if a steel sheet having such a local unevenness on the surface is subjected to an alloying treatment after hot dip galvanizing, a micro uneven pattern is likely to occur in the alloyed layer, and extremely streaky white stripes and visually Streak unevenness called black stripes occurs.
合金化層に凹凸模様が生じる理由は、前記の不均一部分
では表面位置により不均一な速度でZn−Fe合金化が進行
するためである。The reason why the uneven pattern is formed on the alloyed layer is that the Zn—Fe alloying proceeds at a non-uniform speed depending on the surface position in the non-uniform portion.
一方、このような鋼板表面の不均一性からもたらされる
不均一な合金化の進行は、溶融亜鉛浴中の有効 Aｌ濃度
（すなわち、浴中の全 Aｌ濃度からFeの濃度をひいたも
の）、浴温、鋼板の浴への浸入温度、加熱・還元および
冷却等のヒートパターン等、種々のめっき操業条件の変
動に対して敏感に応答する。このために、 Aｌ、Si、M
n、Ti等の金属を含む鋼板から外観が美麗な合金化溶融
亜鉛めっき鋼板を高速で且つ安定して製造することは著
しく困難である。また、鋼板表面の不均一性は鋼種の相
違や製鋼および熱延条件等のバラッキにより異なるため
に、外観が美麗な合金化溶融亜鉛めっき鋼板の製造は極
めて不安定であって、製造能率および歩留りが著しく低
い。On the other hand, the progress of non-uniform alloying caused by such non-uniformity of the steel sheet surface is due to the effective Al concentration in the molten zinc bath (that is, the total Al concentration in the bath minus the Fe concentration), It responds sensitively to changes in various plating operating conditions such as bath temperature, infiltration temperature of steel sheet into the bath, and heat patterns such as heating / reduction and cooling. For this purpose, Al, Si, M
It is extremely difficult to manufacture a galvannealed steel sheet with a beautiful appearance from a steel sheet containing a metal such as n or Ti at high speed and stably. In addition, since the non-uniformity of the steel sheet surface varies depending on the type of steel and variations in steel making and hot rolling conditions, etc., the production of alloyed hot-dip galvanized steel sheets with a beautiful appearance is extremely unstable. Is extremely low.
さらには、合金化溶融亜鉛めっき鋼板の製造には通常の
亜鉛めっき鋼板を製造するめっき設備が兼用されてお
り、溶融亜鉛めっき浴には少量（有効 Aｌ濃度で0.05〜
0.20％濃度）の Aｌが含まれている。この浴中の Aｌ濃
度が高い程、めっき皮膜の加工性が改善されるが、 Aｌ
濃度が高いとその後の合金化処理において、表面の位置
により不均一な速度で合金化が進行し、凹凸模様が合金
化層に生じ易くなることが知られている。即ち、めっき
皮膜の加工性を高めようとすれば凹凸模様が発生しやす
くなるという問題がある。Furthermore, the galvanizing equipment for producing normal galvanized steel sheets is also used for the production of galvannealed steel sheets, and a small amount (effective Al concentration of 0.05-
0.20% concentration) Al is included. The higher the Al concentration in this bath, the better the processability of the plating film.
It is known that when the concentration is high, in the subsequent alloying treatment, alloying proceeds at a non-uniform speed depending on the position of the surface, and an uneven pattern is likely to occur in the alloyed layer. That is, if the workability of the plating film is increased, there is a problem that an uneven pattern is likely to occur.
なお、予め鋼板表面を下地被覆処理した後に溶融亜鉛め
っきを行い、次いで熱拡散合金化処理して合金化溶融亜
鉛めっき鋼板を製造する方法として、特開昭57−76176
号公報、特開昭58−120771号公報および特開昭58−1207
72号公報に開示されている方法がある。しかし、これら
の方法はめっき皮膜の密着性や耐食性の向上を意図した
もので、前記のような合金元素の濃化や偏析が生じ易い
鋼板を母材とする合金化溶融亜鉛めっき鋼板における合
金化層の凹凸模様を抑制するというものではない。As a method for producing an alloyed hot-dip galvanized steel sheet by performing hot dip galvanizing after subjecting the steel sheet surface to an undercoating treatment in advance, and then performing a thermal diffusion alloying treatment, JP-A-57-76176
JP-A-58-120771 and JP-A-58-1207
There is a method disclosed in Japanese Patent Laid-Open No. 72. However, these methods are intended to improve the adhesion and corrosion resistance of the plating film, and alloying in a hot-dip galvanized steel sheet with a steel sheet as a base material in which the concentration and segregation of alloying elements as described above easily occur It does not suppress the uneven pattern of the layer.
（発明が解決しようとする課題） 本発明の課題は、表面に、 Aｌ、Si、Mn、Ti等の成分の
濃化や介在物の偏析等の不均一性がある鋼板でも、或い
はめっき操業条件等に変動が生じても、ミクロな凹凸模
様（筋ムラ）のない合金化層を有し、表面が美麗な合金
化溶融亜鉛めっき鋼板を安定して製造する方法を提供す
ることにある。(Problems to be Solved by the Invention) An object of the present invention is to provide a steel sheet having unevenness such as concentration of components such as Al, Si, Mn, and Ti and segregation of inclusions on the surface, or plating operation conditions. It is an object of the present invention to provide a method for stably producing an alloyed hot-dip galvanized steel sheet having a beautiful surface having an alloyed layer having no micro uneven pattern (streak unevenness) even when variations occur in the above.
（課題を解決するための手段） 本発明者らは、溶融亜鉛めっきに先立ち、鋼板表面に一
定厚さのＰ、Ｂ、Ｓ等の半金属元素を含むFe系被覆を施
すことにより、鋼板表面に成分の濃化や介在物の偏析の
ような不均一であっても、或いはめっき操業条件に変動
が生じても、ミクロの凹凸模様や筋ムラのない合金化層
が得られることを種々の実験結果から見出し、本発明を
なすに至った。(Means for Solving the Problems) Prior to hot dip galvanizing, the inventors of the present invention applied a Fe-based coating containing a semi-metal element such as P, B, and S having a certain thickness to the surface of the steel sheet to obtain a steel sheet surface. Even if there is non-uniformity such as concentration of components or segregation of inclusions, or if there is a change in plating operating conditions, it is possible to obtain an alloyed layer free from micro uneven patterns and streaks. The present invention has been completed based on the findings from the experimental results.
本発明の要旨は、下記およびの合金化溶融亜鉛めっ
き鋼板の製造方法にある。The gist of the present invention resides in the following and the following methods for producing a galvannealed steel sheet.
鋼板表面に、Ｐ、ＢおよびＳの中の１種または２種
以上を合計で0.001〜30.0wt％を含有し（ただし、Ｐ単
独の場合は、その含有量が0.05g/m2を超える範囲を除
く）付着量が0.01〜10g/m2のFe系被覆を施した後、加熱
・還元および冷却処理を行って溶融亜鉛めっきを行い、
次いで熱拡散合金化処理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。The steel sheet surface contains one or more of P, B and S in a total amount of 0.001 to 30.0 wt% (however, in the case of P alone, the content exceeds 0.05 g / m 2 After applying a Fe-based coating with an adhesion amount of 0.01 to 10 g / m 2 , heating / reducing and cooling treatments are applied to hot dip galvanizing.
Then, a thermal diffusion alloying process is performed, The manufacturing method of the alloying hot-dip galvanized steel sheet.
極低炭素Ti添加鋼板を溶融亜鉛めっき後、熱拡散合
金化処理し、合金化溶融亜鉛めっき鋼板を製造するに当
たり、この鋼板表面に、Ｐ、ＢおよびＳの中の１種また
は２種以上を合計で 0.001〜30.0wt％を含有し（ただ
し、Ｐ単独の場合は、その含有量が0.05g/m2を超える範
囲を除く）付着量が0.01〜10g/m2のFe系被覆を施した
後、加熱・還元および冷却処理を行って溶融亜鉛めっき
を行い、次いで熱拡散合金化処理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。After hot dip galvanizing an ultra-low carbon Ti-added steel sheet, heat diffusion alloying treatment to produce an alloyed hot-dip galvanized steel sheet, one or more of P, B and S are applied to the surface of the steel sheet. containing 0.001～30.0Wt% in total (however, in the case of P alone, except to the extent the content exceeds 0.05 g / m 2) weight attached is subjected to Fe-based coating of 0.01 to 10 g / m 2 Then, a method for producing an alloyed hot-dip galvanized steel sheet, characterized by performing heating / reduction and cooling treatment to perform hot dip galvanizing, and then performing heat diffusion alloying treatment.
本発明の合金化溶融亜鉛めっき鋼板の製造方法におい
て、母材鋼板としては、Alキルド鋼、Siキルド鋼、絞り
用遅時効性鋼(RBH)、Si−Mn添加高張力鋼、Ti単独もし
くはTiとＢ、Nb等の１種以上を添加した極低炭素Ti添加
鋼等、各種の鋼種が使用できる。この中でも、従来の方
法では表面不均一の生じやすい極低炭素Ti添加鋼（Ti含
有ＩＦ鋼）の鋼板に対して本発明方法は極めて有効であ
って、前記の発明はこの極低炭素Ti添加鋼板を対象と
する合金化溶融亜鉛めっき鋼板の製造方法である。な
お、この場合の極低炭素Ti添加鋼板のＣ含有量は 0.008
wt％以下、Ti含有量は 0.015〜0.2 wt％である。In the method for producing an alloyed hot-dip galvanized steel sheet of the present invention, as the base material steel sheet, Al killed steel, Si killed steel, slow-aging steel for drawing (RBH), Si-Mn-added high tensile steel, Ti alone or Ti Various steel grades can be used, such as ultra-low carbon Ti-added steel with one or more additions of B, Nb, etc. Among these, the method of the present invention is extremely effective for a steel plate of an ultra-low carbon Ti-added steel (Ti-containing IF steel) which is likely to cause surface non-uniformity in the conventional method, and the above-mentioned invention is based on this ultra-low carbon Ti It is a method for manufacturing an alloyed hot-dip galvanized steel sheet for a steel sheet. In this case, the C content of the ultra low carbon Ti-added steel sheet was 0.008
The content of Ti is 0.015 to 0.2 wt% or less.
（作用） 以下、本発明の合金化溶融亜鉛めっき鋼板の製造方法に
ついて詳細に説明する。(Operation) Hereinafter, the method for producing the galvannealed steel sheet of the present invention will be described in detail.
本発明の特徴は、被めっき鋼板を加熱・還元および冷却
処理した後に溶融亜鉛めっきを行い、次いで、熱拡散合
金化処理して合金化溶融亜鉛めっき鋼板を製造するに際
し、前記加熱処理の前に被めっき鋼板表面にＰ、Ｂ及び
Ｓの中の１種又は２種以上を合計で、 0.001〜30.0wt％
を含有し、付着量が0.01〜10g/m2のFe系被覆（前記お
よびの発明のいずれにおいても、Ｐが単独で含まれる
場合は、Ｐの含有量が0.05g/m2を超える範囲を除く。以
下、特に断らない限り、「Fe系被覆」では、Ｐが単独で
含まれる場合、Ｐの含有量が0.05g/m2を超える範囲を除
く）を施すことにある。A feature of the present invention is that hot-dip galvanizing is performed after heating / reducing and cooling the steel sheet to be plated, and then, when producing an alloyed hot-dip galvanized steel sheet by thermal diffusion alloying treatment, before the heat treatment. 0.001 to 30.0 wt% in total of one or more of P, B and S on the surface of plated steel sheet
Fe-based coating containing 0.01 to 10 g / m 2 (in any of the above and above inventions, when P is contained alone, the content of P exceeds 0.05 g / m 2). Unless otherwise specified, the “Fe-based coating” hereinafter means that when P is contained alone, the P content exceeds 0.05 g / m 2 ).
Ｐ、ＢおよびＳの中の１種又は２種以上含むFe系被覆を
施すことにとり、表面に元素の濃化や介在物の偏析等の
不均一がある鋼板でも、或いはめっき操業条件に変動が
生じても、その後の合金化処理において合金化層に凹凸
模様が生じなくなる理由は、学理的には判明してはいな
いが、半金属を含有するFe系被覆層が表面への元素の濃
化に対する拡散障壁として作用するか、もしくは表面に
偏析する元素と半金属とが安定な化合物を形成すること
によるものと推測される。By applying an Fe-based coating containing one or more of P, B and S, even steel sheets with uneven elements such as element concentration and segregation of inclusions, or fluctuations in plating operating conditions Even if it occurs, the reason why the uneven pattern does not occur in the alloying layer in the subsequent alloying treatment is not theoretically known, but the Fe-based coating layer containing a semimetal concentrates elements on the surface. It is speculated that this is due to the fact that the element and the semimetal, which act as a diffusion barrier to the metal or segregate on the surface, form a stable compound.
なお、前記Ｐ、ＢおよびＳの中の１種又は２種以上を含
むFe系被覆とは、純FeもしくはFeを主成分としてZn、M
n、Mg、Ｗ、Mo、Ni、Co、Cr、Cu、Ti、Ｖ、Sn、Sb、A
s、Pb、In、Ca、Ba、Sr、Si、 Aｌ、Ge、Se、Ga、Hg、A
g、Au、Bi等の中の１種又は２種以上の元素を含むもの
である。これらの元素が１種又は２種以上含まれていて
も、その量が合計で10wt％以下であれば本発明の効果は
特に阻害されるようなことはない。The Fe-based coating containing one or more of P, B, and S means pure Fe or Zn, M containing Fe as a main component.
n, Mg, W, Mo, Ni, Co, Cr, Cu, Ti, V, Sn, Sb, A
s, Pb, In, Ca, Ba, Sr, Si, Al, Ge, Se, Ga, Hg, A
It contains one or more elements of g, Au, Bi and the like. Even if one or more of these elements are contained, the effect of the present invention is not particularly impaired as long as the total amount is 10 wt% or less.
上記Fe系被覆中のＰ、ＢおよびＳの含有量をそれらの中
の１種又は２種以上の合計で 0.001〜30.0wt％とする理
由は、 0.01wt％未満では溶融めっきラインにおける加
熱・還元および冷却処理の際に、鋼板表面における元素
の濃化や偏析等の不均一性か熱拡散により合金化層に伝
わって合金化層に凹凸模様が生成し、一方、30wt％を超
えると不均一なZn−Fe合金化の進行を防止する効果が飽
和し、製造コストが上昇して経済的でないからである。
望ましい含有量は、0.01〜10wt％である。The reason why the content of P, B and S in the Fe-based coating is 0.001 to 30.0 wt% as the total of one or more of them is 0.001 to 30.0 wt% is because heating / reduction in the hot dip coating line is less than 0.01 wt%. In addition, during cooling treatment, unevenness such as element concentration or segregation on the surface of the steel sheet or unevenness pattern is generated in the alloyed layer due to thermal diffusion and is transmitted to the alloyed layer. This is because the effect of preventing the progress of Zn-Fe alloying is saturated, the manufacturing cost rises, and it is not economical.
The desirable content is 0.01 to 10 wt%.
また、Fe系被覆の付着量を0.01〜10g/m2とする理由は、
付着量が0.01g/m2未満では被めっき鋼板表面へ均一にFe
系被覆を施すのが困難となり、合金化層に凹凸模様が生
じ易くなり、10g/m2を超えて被覆しても不均一なZn−Fe
合金化の進行を防止する効果が飽和し、めっきコストの
みが上昇して経済的に好ましくないからである。望まし
い付着量は 0.5〜５g/m2である。In addition, the reason why the amount of Fe-based coating adhered is 0.01 to 10 g / m 2 is
If the adhesion amount is less than 0.01 g / m 2 , Fe is evenly distributed on the surface of the steel sheet to be plated.
It becomes difficult to apply a system coating, uneven patterns are likely to occur in the alloyed layer, and even if the coating exceeds 10 g / m 2 , Zn-Fe is not uniform.
This is because the effect of preventing the progress of alloying is saturated and only the plating cost increases, which is economically unfavorable. A desirable deposition amount is 0.5 to 5 g / m 2 .
本発明において、前記Fe系被覆は、電気めっき法、無電
解めっき法、イオンプレーディング法、真空蒸着法、ス
パッタリング法等、様々の方法で実施することができ
る。この中でも電気めっき法および無電解めっき法は、
鋼帯全面に対して均一にめっきすることができるととも
に安定に且つ高速で処理することができるので、本発明
を実施するうえでは有利である。また、Ｐ、ＢおよびＳ
の半金属の析出効率を高めるには、パルスめっき法も有
効である。In the present invention, the Fe-based coating can be carried out by various methods such as electroplating, electroless plating, ion plating, vacuum deposition and sputtering. Among these, electroplating and electroless plating are
Since it is possible to plate the entire surface of the steel strip uniformly and to perform the processing stably and at high speed, it is advantageous in carrying out the present invention. Also, P, B and S
The pulse plating method is also effective for increasing the deposition efficiency of the semimetal.
電気めっき法および無電解めっき法で上記Fe系皮膜を施
す場合は、半金属元素およびFeイオンを含む硫酸塩浴、
塩化物浴等を使用することができる。そして、半金属元
素は次のような形でめっき浴に添加することができる。When applying the Fe-based coating by the electroplating method and the electroless plating method, a sulfate bath containing a metalloid element and Fe ions,
A chloride bath or the like can be used. Then, the metalloid element can be added to the plating bath in the following form.
半金属がＰの場合は、亜リン酸、次亜リン酸もしくはそ
の塩の形で、Ｂの場合はメタホウ酸ソーダ、ホウ素化ナ
トリウム、ジメチルアミンボラン、トリメチルアミンボ
ラン等の形で、Ｓの場合は、チオシアン酸塩の形で添加
することができる。When the semimetal is P, it is in the form of phosphorous acid, hypophosphorous acid or a salt thereof, in the case of B, it is in the form of sodium metaborate, sodium boride, dimethylamine borane, trimethylamine borane, etc. , Can be added in the form of thiocyanate.
また、Fe系被覆処理は、溶融亜鉛めっき設備の加熱前に
インラインで処理してもよく、或いは溶融めっきライン
とは別のラインで処理してもよい。インラインで処理す
る方が製造コストは安価である。Fe系被覆を施すに際し
ては、公知の脱脂処理や酸性活性化処理を施して、鋼板
表面を清浄活性化してやるのが望ましいが、鋼板表面の
清浄度に応じて適宜その洗浄のやり方を選択すればよ
い。In addition, the Fe-based coating treatment may be performed in-line before heating in the hot dip galvanizing facility, or may be performed in a line different from the hot dip galvanizing line. In-line processing is cheaper to manufacture. When applying the Fe-based coating, it is desirable to perform a known degreasing treatment or an acid activation treatment to cleanly activate the steel sheet surface, but if the cleaning method is appropriately selected according to the cleanliness of the steel sheet surface. Good.
本発明方法で製造した合金化溶融亜鉛めっき鋼板の表面
に、更にFe系、Fe−Zn系、Fe−Mn系、Fe−Sn系、Fe−Zn
−Sn系、Fe−Ni系等の上層皮膜層を設けてやれば電着塗
装欠陥を抑制することができる。またクロメート処理と
クリアー有機樹脂塗装をしてやれば耐指紋性を向上させ
ることができる。On the surface of the alloyed hot-dip galvanized steel sheet produced by the method of the present invention, further Fe-based, Fe-Zn-based, Fe-Mn-based, Fe-Sn-based, Fe-Zn
If an upper coating layer such as -Sn-based or Fe-Ni-based is provided, electrodeposition coating defects can be suppressed. Further, the anti-fingerprint property can be improved by performing chromate treatment and clear organic resin coating.
次に、実施例により本発明を更に説明する。Next, the present invention will be further described with reference to examples.
（実施例） 第１表に示す化学組成の鋼を溶製し、常法通り熱間圧延
を行って板厚４mmの熱延鋼板とした。次いで、冷間圧延
を行って板厚0.8mmの冷延鋼板を製造した。(Example) A steel having the chemical composition shown in Table 1 was melted and hot-rolled in a usual manner to obtain a hot-rolled steel sheet having a thickness of 4 mm. Then, cold rolling was performed to manufacture a cold rolled steel sheet having a sheet thickness of 0.8 mm.
この冷延鋼板を母材として、脱脂処理および酸性活性化
処理を施した後に、表面にFe系被覆を施した。Fe系被覆
は、第２表に示す(ａ浴)〜(ｅ浴)の硫酸塩浴あるいは塩
化物浴を建浴し、(ｂ浴)、(ｃ浴)および(ｅ浴)について
は電流密度１〜200A/dm2の条件で電気めっき方法によ
り、また(ａ浴)および(ｄ浴)については化学めっき方法
により行った。Using this cold-rolled steel sheet as a base material, degreasing treatment and acid activation treatment were performed, and then a Fe-based coating was applied to the surface. The Fe-based coating is prepared by forming a sulfate bath or a chloride bath of (a bath) to (e bath) shown in Table 2, and the current density for (b bath), (c bath) and (e bath). The electroplating method was performed under the condition of 1 to 200 A / dm 2 , and the chemical plating method was used for (a bath) and (d bath).
なお、Ｐ含有率は NaH2PO2の濃度で、Ｂ含有率はメタホ
ウ酸ソーダの濃度或いはDMAB（ジメチルアミンボラン）
の濃度で、Ｓ含有率はチオシアン酸カリウムの濃度で調
整した。また、付着量については化学めっき方法では浸
漬時間で、電気めっき方法では通電時間で調整した。The P content is the concentration of NaH 2 PO 2 , and the B content is the concentration of sodium metaborate or DMAB (dimethylamine borane).
The S content was adjusted by the concentration of potassium thiocyanate. Further, the amount of adhesion was adjusted by the immersion time in the chemical plating method and by the energization time in the electroplating method.
第３表に、使用した冷延鋼板の鋼種とめっき浴、及びFe
系被覆の付着量とFe系被覆中のＰ、ＢおよびＳの含有量
とを示す。Table 3 shows the type of cold-rolled steel sheet used, the plating bath, and Fe.
The adhesion amount of the system coating and the contents of P, B and S in the Fe system coating are shown.
Fe系被覆を施した鋼板に対して、引き続き下記の条件で
焼鈍処理、および溶融亜鉛めっき処理を施し、次いで熱
拡散合金化処理を行って合金化溶融亜鉛めっき鋼板を製
造した。The Fe-coated steel sheet was subsequently subjected to annealing treatment and hot dip galvanizing treatment under the following conditions, and then subjected to thermal diffusion alloying treatment to produce an alloyed hot dip galvanized steel sheet.
昇温速度：15℃／秒、加熱温度および保持時間：820℃
×30秒、炉内雰囲気ガスのH2濃度：25〜75％ 〔溶融亜鉛めっき処理条件〕 Znめっき浴中のAl濃度：0.16％、Fe濃度：0.02％、浴
温：465℃、めっき浴浸漬時間：２秒、Zn付着量：片面
で60〜70g/m2 〔熱拡散合金化処理条件〕 450〜650℃×10〜1000秒 得られた合金化合溶融亜鉛めっき鋼板について、合金化
層の外観を目視検査した。その結果を第３表に併せて示
す。Temperature rising rate: 15 ° C / sec, heating temperature and holding time: 820 ° C
× 30 seconds, H 2 concentration in furnace atmosphere gas: 25 to 75% [Conditions for hot dip galvanizing] Al concentration in Zn plating bath: 0.16%, Fe concentration: 0.02%, bath temperature: 465 ° C, plating bath immersion Time: 2 seconds, Zn adhesion amount: 60 to 70 g / m 2 on one side [thermal diffusion alloying treatment condition] 450 to 650 ° C × 10 to 1000 seconds Appearance of alloyed layer on the obtained alloyed hot-dip galvanized steel sheet Was visually inspected. The results are also shown in Table 3.
表中の×印は、従来の製造方法で得られた合金化溶融亜
鉛めっき鋼板の外観の検査結果を示し、△印は、これよ
りもやや良好、○印は、同じく良好、◎印は、同じく著
しく良好、であることを示す。X mark in the table shows the inspection result of the appearance of the alloyed hot dip galvanized steel sheet obtained by the conventional manufacturing method, Δ mark is slightly better than this, ○ mark is also good, ◎ mark is, It is also markedly good.
第３表から明らかなように、本発明方法により製造した
合金化溶融亜鉛めっき鋼板（試験No.４〜22）は、ミク
ロの凹凸や筋ムラ等の全く無い合金化層を有しており、
その外観は美麗である。 As is clear from Table 3, the galvannealed steel sheets (Test Nos. 4 to 22) produced by the method of the present invention have an alloyed layer having no micro irregularities or streaks.
Its appearance is beautiful.
これに対して、Fe系被覆処理を行わない、従来の方法で
製造した合金化溶融亜鉛めっき鋼板（試験No.１）は、
合金化層にはミクロの凹凸や筋ムラが発生し、外観は著
しく劣る。また、Ｐ含有量或いは付着量が、本発明で規
定する量より少ないFe系被覆を施して製造した合金化溶
融亜鉛めっき鋼板（No.２およびNo.３）は、従来の合金
化溶融亜鉛めっき鋼板に比べて表面外観は少し改善され
てはいるもののFe系被覆の効果が小さく、本発明方法で
得られた合金化溶融亜鉛めっき鋼板と比れば劣る。On the other hand, the alloyed hot-dip galvanized steel sheet (Test No. 1) produced by the conventional method without the Fe-based coating treatment is
The alloyed layer has micro unevenness and streak unevenness, resulting in a markedly poor appearance. Further, the alloyed hot-dip galvanized steel sheet (No. 2 and No. 3) produced by applying an Fe-based coating having a P content or an adhered amount less than the amount specified in the present invention is a conventional alloy hot-dip galvanized steel. Although the surface appearance is slightly improved as compared with the steel sheet, the effect of the Fe-based coating is small, which is inferior to the alloyed hot-dip galvanized steel sheet obtained by the method of the present invention.
なお、本発明方法により製造した合金化溶融亜鉛めっき
鋼板（試験No.４〜22）について、円筒絞り成形試験、
ビード付ハット成形試験、Ｖビードしごき試験、等の各
種試験を行ったが、いずれの変形に対しても良好な耐パ
ウダリング性を示した。In addition, for the alloyed hot-dip galvanized steel sheet (Test Nos. 4 to 22) produced by the method of the present invention, a cylindrical drawing test,
Various tests such as a beaded hat forming test and a V bead squeezing test were conducted, and good powdering resistance against any deformation was shown.
（発明の効果） 以上説明したように、本発明方法に従えば表面に Aｌ、
Si、Mn、Ti等の成分の濃化や介在物の偏析等の不均一性
を有した鋼板でも、或いはめっき操業条件等に変動が生
じても、ミクロな凹凸模様や筋ムラのない合金化層をも
つ表面が美麗な合金化溶融亜鉛めっき鋼板を安定して製
造することができる。(Effect of the Invention) As described above, according to the method of the present invention, Al is formed on the surface,
Alloying without unevenness and microscopic unevenness even on steel plates with unevenness such as concentration of components such as Si, Mn, Ti, segregation of inclusions, etc., or changes in plating operation conditions It is possible to stably manufacture a galvannealed steel sheet having a beautiful surface having layers.
フロントページの続き (72)発明者 渋谷 敦義 大阪府大阪市東区北浜５丁目15番地 住友 金属工業株式会社内 (56)参考文献 特開 昭63−312960（ＪＰ，Ａ)Front page continuation (72) Inventor Atsushi Shibuya 5-15 Kitahama, Higashi-ku, Osaka City, Osaka Prefecture Sumitomo Metal Industries, Ltd. (56) Reference JP-A-63-312960 (JP, A)
Claims (2)
たは２種以上を合計で0.001〜30.0wt％含有し（ただ
し、Ｐ単独の場合は、その含有量が0.05g/m2を超える範
囲を除く）付着量が0.01〜10g/m2のFe系被覆を施した
後、加熱・還元および冷却処理を行って溶融亜鉛めっき
を行い、次いで熱拡散合金化処理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。1. A steel sheet surface containing 0.001 to 30.0 wt% of one or more of P, B and S in total (however, in the case of P alone, the content is 0.05 g / m 2. ( Excluding the range exceeding 2 ) After applying a Fe-based coating with an adhesion amount of 0.01 to 10 g / m 2 , hot-reduction and cooling treatments are performed for hot dip galvanization, followed by thermal diffusion alloying treatment. A method for producing an alloyed hot-dip galvanized steel sheet.
熱拡散合金化処理し、合金化溶融亜鉛めっき鋼板を製造
するに当たり、この鋼板表面に、Ｐ、ＢおよびＳの中の
１種または２種以上を合計で 0.001〜30.0wt％含有し
（ただし、Ｐ単独の場合は、その含有量が0.05g/m2を超
える範囲を除く）付着量が0.01〜10g/m2のFe系被覆を施
した後、加熱・還元および冷却処理を行って溶融亜鉛め
っきを行い、次いで熱拡散合金化処理を行うことを特徴
とする合金化溶融亜鉛めっき鋼板の製造方法。2. An ultra-low carbon Ti-added steel plate is hot-dip galvanized,
In producing a hot-dip galvanized steel sheet by thermal diffusion alloying treatment, the steel sheet surface contains 0.001 to 30.0 wt% of P, B, and S in a total amount of 0.001 to 30.0 wt% (however, for P alone, except to the extent the content exceeds 0.05 g / m 2) after the amount deposited is subjected to Fe-based coating of 0.01 to 10 g / m 2, molten zinc by heating and reduction and cooling process A method for producing an alloyed hot-dip galvanized steel sheet, which comprises performing plating and then heat diffusion alloying treatment.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63186394A JPH0645853B2 (en) | 1988-07-26 | 1988-07-26 | Method for producing galvannealed steel sheet |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63186394A JPH0645853B2 (en) | 1988-07-26 | 1988-07-26 | Method for producing galvannealed steel sheet |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0238549A JPH0238549A (en) | 1990-02-07 |
| JPH0645853B2 true JPH0645853B2 (en) | 1994-06-15 |
Family
ID=16187630
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63186394A Expired - Fee Related JPH0645853B2 (en) | 1988-07-26 | 1988-07-26 | Method for producing galvannealed steel sheet |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0645853B2 (en) |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2724045B2 (en) * | 1990-12-26 | 1998-03-09 | 川崎製鉄株式会社 | Method for producing chromium-containing steel sheet plated with hot-dip zinc or zinc alloy |
| JPH04276055A (en) * | 1991-02-28 | 1992-10-01 | Nisshin Steel Co Ltd | Manufacture of differential galvannealed steel |
| JPH04301058A (en) * | 1991-03-28 | 1992-10-23 | Nisshin Steel Co Ltd | Alloyed galvanized steel |
| JPH04301059A (en) * | 1991-03-28 | 1992-10-23 | Nisshin Steel Co Ltd | Production of alloyed galvanized steel |
| WO1993020254A1 (en) * | 1992-03-30 | 1993-10-14 | Kawasaki Steel Corporation | Surface-treated steel sheet reduced in plating defects and production thereof |
| CN100368580C (en) | 2003-04-10 | 2008-02-13 | 新日本制铁株式会社 | High strength hot dip galvanized steel sheet, and its production method |
| JP4192051B2 (en) | 2003-08-19 | 2008-12-03 | 新日本製鐵株式会社 | Manufacturing method and equipment for high-strength galvannealed steel sheet |
| EP4242357A4 (en) * | 2020-11-06 | 2024-05-22 | Jfe Steel Corp | Fe-electroplated steel sheet, electrodeposition coated steel sheet, automobile component, method for manufacturing electrodeposition coated steel sheet, and method for manufacturing fe-electroplated steel sheet |
| EP4317517A1 (en) * | 2021-05-17 | 2024-02-07 | JFE Steel Corporation | Stock cold-rolled steel sheet with fe-based coating film, method for producing stock cold-rolled steel sheet with fe-based coating film, method for producing cold-rolled steel sheet with fe-based coating film, method for producing hot-dipped galvanized steel sheet, and method for producing alloyed hot-dipped galvanized steel sheet |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63312960A (en) * | 1987-06-17 | 1988-12-21 | Nippon Steel Corp | Manufacture of zinc alloy hot dip galvanized steel sheet having superior workability |
-
1988
- 1988-07-26 JP JP63186394A patent/JPH0645853B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0238549A (en) | 1990-02-07 |
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