JPH03243752A - Production of alloyed galvanized steel sheet - Google Patents
Production of alloyed galvanized steel sheetInfo
- Publication number
- JPH03243752A JPH03243752A JP3817790A JP3817790A JPH03243752A JP H03243752 A JPH03243752 A JP H03243752A JP 3817790 A JP3817790 A JP 3817790A JP 3817790 A JP3817790 A JP 3817790A JP H03243752 A JPH03243752 A JP H03243752A
- Authority
- JP
- Japan
- Prior art keywords
- steel sheet
- alloying
- galvanized steel
- alloyed
- pickling
- 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.)
- Pending
Links
- 229910001335 Galvanized steel Inorganic materials 0.000 title claims abstract description 38
- 239000008397 galvanized steel Substances 0.000 title claims abstract description 38
- 238000004519 manufacturing process Methods 0.000 title claims description 14
- 238000005554 pickling Methods 0.000 claims abstract description 30
- 229910000831 Steel Inorganic materials 0.000 claims abstract description 29
- 239000010959 steel Substances 0.000 claims abstract description 29
- 239000003112 inhibitor Substances 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 7
- 238000005275 alloying Methods 0.000 abstract description 40
- 238000005260 corrosion Methods 0.000 abstract description 3
- 230000007797 corrosion Effects 0.000 abstract description 3
- 238000000227 grinding Methods 0.000 abstract description 3
- 238000010438 heat treatment Methods 0.000 abstract description 3
- 238000007747 plating Methods 0.000 abstract description 3
- 239000000853 adhesive Substances 0.000 abstract 1
- 230000001070 adhesive effect Effects 0.000 abstract 1
- 239000007864 aqueous solution Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 9
- 230000000694 effects Effects 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 229910001209 Low-carbon steel Inorganic materials 0.000 description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 3
- 238000005097 cold rolling Methods 0.000 description 3
- 238000005246 galvanizing Methods 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- 229910001297 Zn alloy Inorganic materials 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- KFZAUHNPPZCSCR-UHFFFAOYSA-N iron zinc Chemical compound [Fe].[Zn] KFZAUHNPPZCSCR-UHFFFAOYSA-N 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000006104 solid solution Substances 0.000 description 2
- 238000004804 winding Methods 0.000 description 2
- 241000218645 Cedrus Species 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 235000011007 phosphoric acid Nutrition 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Landscapes
- Coating With Molten Metal (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は、合金化亜鉛めっき鋼板の製造方法に関するも
のである。DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a method for manufacturing an alloyed galvanized steel sheet.
（従来の技術）
Ｐを添加した亜鉛めっき鋼板の合金化速度は、例えば、
特開昭６２−１３９８８０号公報の如くめっき鋼板表面
にリンを被覆せしめ、次いで溶融亜鉛めっきを施すこと
で、めっき層密着性の優れた溶融亜鉛めっき鋼板とする
ことができるとして、Ｐによって合金化速度が遅くなり
、密着性を損なうｒ相を少なくすることができ、言い換
えれば、合金化を損なうことが開示されている。(Prior art) The alloying rate of a galvanized steel sheet added with P is, for example,
As disclosed in JP-A-62-139880, by coating the surface of a galvanized steel sheet with phosphorus and then hot-dip galvanizing, it is possible to obtain a hot-dip galvanized steel sheet with excellent adhesion of the coating layer. It is disclosed that the speed becomes slower and the r-phase, which impairs adhesion, can be reduced, in other words, it impairs alloying.
このように、Ｐを添加することで合金化が遅くなるため
に、合金化亜鉛めっき鋼板の合金化の向上が強く要求さ
れている。As described above, since the addition of P slows down alloying, there is a strong demand for improvement in alloying of galvannealed steel sheets.
（発明が解決しようとする課題）
本発明はこのような要求を有利に満足するためなされた
もので、製造時の通板速度を向上し、かつめっき密着性
、パウダリング性、加工性、耐食性をうる合金化亜鉛め
っき鋼板の製造方法を提供するものである。(Problems to be Solved by the Invention) The present invention has been made to advantageously satisfy these requirements, and it improves the threading speed during manufacturing, and improves plating adhesion, powdering property, workability, and corrosion resistance. The present invention provides a method for manufacturing an alloyed galvanized steel sheet that can obtain the following properties.
（問題点を解決するための手段）
本発明は、合金化亜鉛めっき鋼板の製造において、熱延
鋼板を巻取り後、過酸洗防止用インヒビターを添加しな
い酸洗浴で酸洗し、冷間圧延後、焼鈍し、次いで亜鉛め
っきし、合金化することを特徴とする合金化亜鉛めっき
鋼板の製造方法である。(Means for Solving the Problems) In the production of alloyed galvanized steel sheets, the present invention provides that after winding up a hot-rolled steel sheet, pickling is performed in a pickling bath that does not contain an inhibitor for preventing overpickling, and then cold rolling. This is a method for producing an alloyed galvanized steel sheet, which is characterized in that it is then annealed, then galvanized, and then alloyed.
本発明の対象とする亜鉛めっき鋼板は、Ｐを意図的に添
加した鋼を熱延、酸洗、冷延、亜鉛めっき、合金化を行
う合金化亜鉛めっき鋼板であり、その他の成分は特に規
定しない。例えば、溶融亜鉛めっき鋼板（亜鉛または亜
鉛を主体とするＮ１゜Ｐｂ、Ｃｒ等の合金めっきを施し
たものを含む）を加熱合金化した鋼板であり、合金化を
施す鉄亜鉛合金電気亜鉛めっき鋼板を加熱合金化した鋼
板、蒸着亜鉛めっき鋼板を加熱合金化した鋼板等の製造
方法である。The galvanized steel sheet that is the object of the present invention is an alloyed galvanized steel sheet that is hot-rolled, pickled, cold-rolled, galvanized, and alloyed to which P is intentionally added, and other components are not particularly specified. do not. For example, hot-dip galvanized steel sheets (including those plated with zinc or alloys such as N1°Pb and Cr based on zinc) are heated and alloyed, and iron-zinc alloy electrogalvanized steel sheets are alloyed. This is a method for manufacturing steel sheets that are heat-alloyed with evaporated galvanized steel sheets, and steel sheets that are heat-alloyed with vapor-deposited galvanized steel sheets.
本発明者らは、亜鉛めっき鋼板の種類の如何によらず、
Ｐを添加した鋼板の合金化速度を速くすることは熱延鋼
板を巻取った後、スケールを除去するとき、過酸洗防止
用インヒビターを添加しない酸洗浴で酸洗することによ
り、Ｐの鋼板表面の粒界への濃化が抑制され、合金化速
度を大幅に改善することを見出した。The present inventors believe that regardless of the type of galvanized steel sheet,
The alloying speed of P-added steel sheets can be increased by pickling them in a pickling bath that does not contain an inhibitor to prevent over-pickling when removing scale after winding a hot-rolled steel sheet. It has been found that concentration at the grain boundaries on the surface is suppressed and the alloying rate is significantly improved.
従来の上記めっき鋼板において、Ｐを含有する鋼板の合
金化速度は鋼板の通板速度を例えば、３５ｍ／ｍｌｎと
極端に遅くしないと合金化が完了せず、いわゆる生焼け
の状態となり、合金化亜鉛めっき鋼板とならないことが
ある。In the conventional plated steel sheet mentioned above, the alloying speed of the steel sheet containing P is not completed unless the steel sheet threading speed is extremely slow, for example, 35 m/mln, resulting in a so-called half-cooked state, and the alloyed zinc It may not be a plated steel sheet.
本発明者らは合金化亜鉛めっき鋼板の合金化速度を改善
するために、種々の実験を重ねた結果、たとえば少量の
Ｐ添加で高強度鋼板とすることができる（一般にはＰ
： ０．０１〜０．２％）。このような熱延鋼板のスケ
ールの酸洗前の部分的な剥離が存在するとき、酸洗され
ると、スケールの剥離部分で、過酸洗防止用インヒビタ
ーの作用で酸洗液、たとえば、ＨＣｇとの反応が抑制さ
れ、電気化学的に陰極となり、スケール残存部が陽極と
なり、局部電池が形成され、スケール残存部が局部的に
地鉄まで溶解されることが認められる。The present inventors have conducted various experiments to improve the alloying speed of alloyed galvanized steel sheets, and have found that, for example, high-strength steel sheets can be obtained by adding a small amount of P (in general, P
: 0.01-0.2%). When there is partial peeling of scale on a hot rolled steel sheet before pickling, when the hot rolled steel sheet is pickled, the pickling solution, for example, HCg It is observed that the reaction with the steel is suppressed, electrochemically becomes a cathode, the remaining scale becomes an anode, a local battery is formed, and the remaining scale is locally dissolved to the base iron.
しかも、理由は明らかではないが、溶解された部分の結
晶粒界は凸部として残存することで、Ｐが粒界に濃化し
ているためにＰの濃化した表面となり、冷延、亜鉛めっ
き、合金化することで、Ｐの合金化抑制により、合金化
不良をひきおこすことが明らかになった。Moreover, although the reason is not clear, the grain boundaries of the melted portion remain as convex parts, and P is concentrated in the grain boundaries, resulting in a P-enriched surface, which results in cold rolling and galvanizing. It has been revealed that alloying causes poor alloying due to suppression of alloying of P.
そこで、熱延鋼板のスケールの酸洗前の部分的な剥離が
存在する材料を酸洗するとき、スケールの剥離部分で、
過酸洗防止用インヒビターの作用で酸洗液、たとえば、
ＨＣｊｌとの反応が抑制され、電気化学的に陰極となり
、スケール残存部が陽極となり、局部電池が形成され、
スケール残存部が局部的に地鉄まで溶解されることを防
止するためには、過酸洗防止用インヒビターを添加しな
い酸洗液、たとえば、ＨＣＩ （２〜ｌＯ％）水溶液
で酸洗すれば、スケール剥離後の表面の凹凸はなく、Ｐ
の表面の粒界への濃化が抑制され、合金化速度が速くな
る。Therefore, when pickling a hot-rolled steel sheet with partial peeling of scale before pickling, in the peeled part of scale,
Due to the action of the inhibitor to prevent overpickling, the pickling solution, e.g.
The reaction with HCjl is suppressed, electrochemically becomes a cathode, the remaining scale becomes an anode, and a local battery is formed.
In order to prevent the remaining scale from being locally dissolved to the base metal, pickling should be carried out with a pickling solution that does not contain an inhibitor to prevent overpickling, such as an aqueous HCI (2 to 10%) solution. There is no unevenness on the surface after scale removal, and P
This suppresses the concentration of surface grains at the grain boundaries, increasing the alloying rate.
このことから、過酸洗防止用インヒビターを添加しない
酸洗液での酸洗により、合金化速度の向上刃呵能となり
、酸洗液でもＨ２ＳＯ４、Ｈ３ＰＯ４同様の効果が得ら
れる。From this, pickling with a pickling solution that does not contain an inhibitor for preventing overpickling can improve the alloying rate, and the same effects as H2SO4 and H3PO4 can be obtained with the pickling solution.
かかる合金化速度を抑制する要因として、鋼中にＰが多
く存在することにより、特に、結晶粒界に存在すること
で、合金化時のＦｅの移動を妨害し、合金化速度を遅く
すると考えられる。その他、Ｃ，Ｎ等の固溶体元素が悪
影響をおよぼすと考えられる。このように、Ｐをはじめ
とする固溶体元素を低減することが、合金化速度を向上
することに有効である。It is believed that the presence of a large amount of P in steel, especially at grain boundaries, hinders the movement of Fe during alloying and slows down the alloying rate. It will be done. In addition, solid solution elements such as C and N are thought to have an adverse effect. Thus, reducing solid solution elements such as P is effective in improving the alloying rate.
そのために、特にＰの表面の粒界への濃化を表面濃化の
過程を問わず、抑制することが合金化速度向上の鍵とい
える。Therefore, it can be said that the key to improving the alloying rate is to suppress the concentration of P on the surface grain boundaries, regardless of the process of surface concentration.
ところで、熱延鋼板の巻取り温度と合金化溶融亜鉛めっ
き鋼板の合金化速度は第１図に示すとおり、巻取温度が
高くなれば合金化速度、つまり、合金化溶融亜鉛めっき
鋼板とするための限界の通板速度は遅くなる傾向を示す
。By the way, the coiling temperature of a hot-rolled steel sheet and the alloying rate of an alloyed hot-dip galvanized steel sheet are shown in Figure 1. The limit threading speed tends to become slower.
また、そのとき酸洗浴に過酸洗防止用インヒビターを添
加したものは巻取温度を高くしたものについても、合金
化速度、つまり合金化溶融亜鉛めっき鋼板とするための
限界の通板速度は向上する。In addition, even if an inhibitor to prevent overpickling is added to the pickling bath and the coiling temperature is increased, the alloying speed, that is, the limit threading speed for producing an alloyed hot-dip galvanized steel sheet, is improved. do.
第１図の諸元は次の通りである。The specifications of FIG. 1 are as follows.
Ｐ添加量： ０．０４％
め っ き二両面ＡＳ
目 付量： ８Ｇ／８０ （ｇ ／ボ）合金化板温：４
８０℃Ｘ５ｓｅｃ
このように、合金化溶融亜鉛めっき鋼板の合金化速度は
、酸洗浴に過酸洗防止用インヒビターを添加しない酸洗
液で酸洗することにより、容易に改善することが明らか
である。Added amount of P: 0.04% Plated on both sides AS Fabric weight: 8G/80 (g/Bo) Alloyed plate temperature: 4
80°C x 5 sec Thus, it is clear that the alloying speed of alloyed hot-dip galvanized steel sheets can be easily improved by pickling with a pickling solution that does not contain an inhibitor to prevent overpickling. .
しかして、例えば前記の如き合金化亜鉛めっき鋼板の合
金化速度、つまり、合金化亜鉛めっき鋼板製造ラインの
通板速度を改善する方性としては、酸洗浴に過酸洗防止
用インヒビターを添加しない酸洗液で酸洗することによ
り、合金化溶融亜鉛めっき鋼板製造ラインの通板速度を
容易に改善することができる。Therefore, for example, as a way to improve the alloying speed of the above-mentioned alloyed galvanized steel sheet, that is, the threading speed of the alloyed galvanized steel sheet manufacturing line, it is recommended not to add an inhibitor to prevent overpickling to the pickling bath. By pickling with a pickling solution, the threading speed of the alloyed hot-dip galvanized steel sheet production line can be easily improved.
その具体的な方法としては、例えば、Ｐを０．０４％含
有した鋼板を７５０℃で巻取る熱延を行い、酸洗浴に過
酸洗防止用インヒビターを添加しない酸洗液で酸洗し、
冷延、焼鈍後亜鉛めっき、加熱合金化を行い、合金化の
板温４８０℃で５ｓｅｃとなる通板速度を９０ｍ／ｗｉ
ｎとして通板することで、合金化速度を改善することが
確実に達成できる。As a specific method, for example, a steel plate containing 0.04% P is hot-rolled at 750°C, pickled with a pickling solution that does not contain an inhibitor for preventing overpickling, and
After cold rolling and annealing, galvanizing and heating alloying are performed, and the sheet threading speed is 90 m/wi for 5 seconds at a plate temperature of 480°C during alloying.
By passing the plate as n, it is possible to reliably improve the alloying rate.
または、溶融亜鉛めっき鋼板をライン外で、合金化処理
を行うとき、鉄−亜鉛合金電気亜鉛めつき鋼板を合金化
するとき、蒸着亜鉛めっき鋼板等を加熱合金化するとき
にも適用できる。Alternatively, it can be applied when alloying a hot-dip galvanized steel sheet outside the line, when alloying an iron-zinc alloy electrogalvanized steel sheet, and when heating and alloying a vapor-deposited galvanized steel sheet.
（実 施 例） 本発明の実施例を比較例とともに第１表に挙げる。(Example) Examples of the present invention are listed in Table 1 along with comparative examples.
注１：網 種
・Ｎｂ −Ｔ１−８ＬＩＬＣ：超極低炭素鋼でＮｂ−Ｔ
ｌを添加したもの。Note 1: Net type: Nb-T1-8LILC: Nb-T ultra-low carbon steel
Added l.
・Ｔｌ−８ＵＬＣ：超極低炭素鋼でＴ１を添加したもの
。・Tl-8ULC: Ultra-low carbon steel with T1 added.
・ＡｆＪ−にニアルミキルド低炭素鋼。・AfJ- is made of near-aluminum killed low carbon steel.
注２：酸 洗 ・酸洗液：６％ＨＣ１ （比較例は、インヒビターとして杉材 化学■製 商品名ヒビロン０．０１８％添加した） ・浴 温：８５℃ ０時 間： ４０ｓｅｃ 注３：めっき鋼板の種類 ・両面ＡＳ：両面の合金化溶融亜鉛めっき鋼板。Note 2: Acid washing ・Pickling liquid: 6% HC1 (In the comparative example, cedar wood was used as an inhibitor.) Manufactured by Kagaku ■ (trade name Hibilon 0.018% added) ・Bath temperature: 85℃ 0:00: 40sec Note 3: Type of plated steel sheet ・Double-sided AS: Alloyed hot-dip galvanized steel sheet on both sides.
（６０ｇ／ｒｆ／６０ｓｒ／ｒ＋ｆ） ・片面ＡＳ：片面の合金化溶融亜鉛めっき鋼板。(60g/rf/60sr/r+f) ・Single-sided AS: Single-sided alloyed hot-dip galvanized steel sheet.
（４５ｇ／＃１０）
・電気ＡＳ：電気亜鉛めっき鋼板を合金化処理したもの
。（３０ｇ ／ ｒｒｆ／ ３０ ｇ ／ ｒｄ”）・
蒸着ＡＳ：蒸着亜鉛めっき鋼板を合金化処理したもの。(45g/#10) - Electric AS: Alloyed electrogalvanized steel sheet. (30g/rrf/30g/rd”)・
Vapor-deposited AS: Alloyed vapor-deposited galvanized steel sheet.
（３０ｇ／ボ／３０ｇ／ｒｒｒ）注４＝合金化処理温度 ・合金化処理を行うときの板温。(30g/bo/30g/rrr) Note 4 = Alloying treatment temperature ・Plate temperature during alloying treatment.
注５二合金化処理時間
・合金化処理を行うときの合金化処理温度に保持される
時間。Note 5 2. Alloying treatment time: The time to be maintained at the alloying temperature when performing alloying treatment.
注６：亜鉛めっき鋼板ラインの通板速度・合金化処理を
行う亜鉛めっき鋼板ラインの通板速度で合金化可能な限
界速度。Note 6: Threading speed of galvanized steel sheet line/Limit speed at which alloying is possible at the threading speed of galvanized steel sheet line that performs alloying treatment.
（発明の効果）
本発明により、合金化亜鉛めっき鋼板の製造において、
Ｐ添加の合金化速度つまり、合金化亜鉛めっき鋼板の製
造時の通板速度を向上することができ、かつ、合金化亜
鉛めっき鋼板に要求される緒特性、めっき密着性、パウ
ダリング性、加工性、耐蝕性等の効果が得られる。(Effects of the Invention) According to the present invention, in manufacturing an alloyed galvanized steel sheet,
P addition can improve the alloying speed, that is, the threading speed during the production of alloyed galvanized steel sheets, and improve the properties, plating adhesion, powdering properties, and processing required for alloyed galvanized steel sheets. Effects such as durability and corrosion resistance can be obtained.
第１図は熱延鋼板の巻取温度、酸洗での過酸洗防止用イ
ンヒビターの有無と合金化亜鉛めっき鋼板の合金化速度
（合金化亜鉛めっき鋼板製造時の合金化限界通板速度）
の関係を示す図表である。Figure 1 shows the coiling temperature of hot-rolled steel sheets, the presence or absence of an inhibitor to prevent over-pickling during pickling, and the alloying speed of alloyed galvanized steel sheets (alloying limit threading speed during production of alloyed galvanized steel sheets).
This is a chart showing the relationship between
Claims (1)
を巻取り後、過酸洗防止用インヒビターを添加しない酸
洗浴で酸洗し、冷間圧延後、焼鈍し、次いで亜鉛めっき
し、加熱合金化することを特徴とする合金化亜鉛めっき
鋼板の製造方法。In the production of alloyed galvanized steel sheets, a P-added hot rolled steel sheet is wound up, pickled in a pickling bath that does not contain an inhibitor to prevent overpickling, cold rolled, annealed, then galvanized, and then heated and alloyed. A method for manufacturing an alloyed galvanized steel sheet, characterized by:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3817790A JPH03243752A (en) | 1990-02-21 | 1990-02-21 | Production of alloyed galvanized steel sheet |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3817790A JPH03243752A (en) | 1990-02-21 | 1990-02-21 | Production of alloyed galvanized steel sheet |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH03243752A true JPH03243752A (en) | 1991-10-30 |
Family
ID=12518108
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3817790A Pending JPH03243752A (en) | 1990-02-21 | 1990-02-21 | Production of alloyed galvanized steel sheet |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH03243752A (en) |
-
1990
- 1990-02-21 JP JP3817790A patent/JPH03243752A/en active Pending
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