JPH0215152A - Hot dip galvanized steel sheet and its production - Google Patents
Hot dip galvanized steel sheet and its productionInfo
- Publication number
- JPH0215152A JPH0215152A JP16648188A JP16648188A JPH0215152A JP H0215152 A JPH0215152 A JP H0215152A JP 16648188 A JP16648188 A JP 16648188A JP 16648188 A JP16648188 A JP 16648188A JP H0215152 A JPH0215152 A JP H0215152A
- Authority
- JP
- Japan
- Prior art keywords
- steel sheet
- plating
- bath
- spangle
- hot
- 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 15
- 239000008397 galvanized steel Substances 0.000 title claims abstract description 15
- 238000004519 manufacturing process Methods 0.000 title claims description 10
- 239000000203 mixture Substances 0.000 claims abstract description 15
- 229910052797 bismuth Inorganic materials 0.000 claims abstract description 6
- 229910052742 iron Inorganic materials 0.000 claims abstract description 6
- 229910052745 lead Inorganic materials 0.000 claims abstract description 6
- 238000007747 plating Methods 0.000 claims description 50
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 claims description 16
- 229910000831 Steel Inorganic materials 0.000 abstract description 22
- 239000010959 steel Substances 0.000 abstract description 22
- 230000007797 corrosion Effects 0.000 abstract description 20
- 238000005260 corrosion Methods 0.000 abstract description 20
- 238000005246 galvanizing Methods 0.000 abstract description 18
- 238000000034 method Methods 0.000 abstract description 9
- 229910052725 zinc Inorganic materials 0.000 abstract description 9
- 229910052782 aluminium Inorganic materials 0.000 abstract 3
- 238000007598 dipping method Methods 0.000 abstract 2
- 239000000463 material Substances 0.000 description 27
- 239000011701 zinc Substances 0.000 description 14
- 230000000694 effects Effects 0.000 description 13
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 9
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 7
- 229910045601 alloy Inorganic materials 0.000 description 4
- 239000000956 alloy Substances 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 2
- 229910001297 Zn alloy Inorganic materials 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 241001163841 Albugo ipomoeae-panduratae Species 0.000 description 1
- 229910001020 Au alloy Inorganic materials 0.000 description 1
- 208000023514 Barrett esophagus Diseases 0.000 description 1
- 229920000298 Cellophane Polymers 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- PYRZPBDTPRQYKG-UHFFFAOYSA-N cyclopentene-1-carboxylic acid Chemical compound OC(=O)C1=CCCC1 PYRZPBDTPRQYKG-UHFFFAOYSA-N 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000005496 eutectics Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 1
- 239000003353 gold alloy Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- GVALZJMUIHGIMD-UHFFFAOYSA-H magnesium phosphate Chemical compound [Mg+2].[Mg+2].[Mg+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O GVALZJMUIHGIMD-UHFFFAOYSA-H 0.000 description 1
- 239000004137 magnesium phosphate Substances 0.000 description 1
- 229960002261 magnesium phosphate Drugs 0.000 description 1
- 229910000157 magnesium phosphate Inorganic materials 0.000 description 1
- 235000010994 magnesium phosphates Nutrition 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000009966 trimming Methods 0.000 description 1
- 230000037303 wrinkles Effects 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〉
この発明は、耐食性に優れた溶融亜鉛メッキ鋼板並びに
その製造方法に関するものである。DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to a hot-dip galvanized steel sheet with excellent corrosion resistance and a method for manufacturing the same.
〈従来技術とその課題〉
現在製造されている溶融亜鉛メッキ鋼板は、大別すると
ａ）メッキ後大気中で放冷し、溶融亜鉛層を徐々に冷却
凝固させて亜鉛結晶のスパングルを大きく発達させた“
レギュラースパングル溶融亜鉛メッキ鋼板〔以降、レギ
ュラースパングル制と略称する〕“
ｂ）メッキ後直ちに薬剤（リン酸塩を主成分とした溶液
）により熔融亜鉛層を急冷凝固させ、スパングルを殆ん
ど消失させた“ゼロスパングル（ミニマムスパングル）
溶融亜鉛メッキ鋼板〔以降、ゼロスパングル材と略称す
る〕”
とに分けられる。<Prior art and its problems> Currently manufactured hot-dip galvanized steel sheets can be roughly divided into a) those that are left to cool in the atmosphere after plating, and the molten zinc layer is gradually cooled and solidified to greatly develop spangles of zinc crystals; Ta"
Regular spangle hot-dip galvanized steel sheet [hereinafter referred to as regular spangle galvanized steel sheet] b) Immediately after plating, the molten zinc layer is rapidly cooled and solidified using a chemical (a solution containing phosphate as its main component), and most of the spangles disappear. “Zero Spangle (Minimum Spangle)
Hot-dip galvanized steel sheets (hereinafter referred to as zero-spangle materials).
このうち、ゼロスパングル材は塗装仕上り性が良好なた
め塗装材として使用されることが多く、その需要も年々
増加する傾向を示している。しかし、メッキ鋼板を採便
用する用途においては依然としてレギュラースパングル
材の需要が根強く、レギュラースパングル材の生産も重
要な地位を占めていた。Among these materials, zero spangle material is often used as a coating material because of its good paint finish, and its demand is increasing year by year. However, in applications where plated steel sheets are used, there is still a strong demand for regular spangle materials, and the production of regular spangle materials also plays an important role.
ところで、従来、レギュラースパングル材の製造に際し
ては、そのスパングル模様を効果的に発現させるため、
以下に示すような溶融亜鉛メッキ浴の使用がなされてい
た。By the way, conventionally, when manufacturing regular spangle materials, in order to effectively express the spangle pattern,
Hot-dip galvanizing baths were used as shown below.
＋ａｌ Ｐｂを０．１％（以降、成分割合を表わす％
は重量％とする）程度添加した高ｐｂ浴
（ｂｌ Ｐｂの代わりにｓｂを添加した浴（特開昭５
３１２８５３９号公報）
［ＣＩ Ｐｂとｓｂとを複合添加した浴（特開昭６１
１、１９６６３号公報）
ｄ） Ｂｉ添加浴（特開昭６１−２８８０３９号公報
）。+al Pb 0.1% (hereinafter, % representing the component ratio)
High Pb bath (bl bath with sb added instead of Pb)
Publication No. 3128539)
1, 19663) d) Bi-added bath (Japanese Unexamined Patent Publication No. 61-288039).
しかしながら、前記Ｆａ１項で示したｐｂ添加浴を使用
する方法では
）溶融亜鉛メッキ作業においては、実際上、設備的な問
題から同一メッキラインて同一浴を用いてゼロスパング
ル材の製造をも行わざるを得ない状況にあるが、高ｐｂ
浴を用いてゼロスパングル材の製造を行うと、形成され
るメッキ皮膜は粒界腐食を律し易いものとなってしまう
１１）得られたメッキ鋼板にクロメ−１・処理を施すと
、メッキ皮膜中にｐｂが高濃度（０，１％程度）で存在
することから著しい耐食性の劣化を招く等の問題を生じ
ることが指摘されていた。However, in the hot-dip galvanizing process (with the method using the PB-added bath shown in Fa1), it is practically impossible to manufacture zero-spangle material using the same bath on the same plating line due to equipment problems. Although I am in a situation where I cannot get high pb
When zero-spangle material is manufactured using a bath, the formed plating film tends to be susceptible to intergranular corrosion.11) When the resulting plated steel sheet is treated with chromate It has been pointed out that the presence of PB at a high concentration (approximately 0.1%) causes problems such as significant deterioration of corrosion resistance.
また、前記（ｂｌ及びＦｅ２項で示したｐｂ添加浴を使
用する方法におけるように、ｓｂを用いてｐｂと同程度
のスパングル模様発現効果を得るためには、ｓｂをｐｂ
の場合とほぼ同程度の量添加する必要がある。In addition, in order to obtain the same level of spangle pattern expression effect as PB using sb, as in the method using the PB addition bath shown in (bl and Fe 2), it is necessary to replace sb with PB.
It is necessary to add approximately the same amount as in the case of .
そして、この場合にはメッキ皮膜の粒界腐食性はそれほ
ど劣化しないものの、得られたメッキ鋼板にクロノート
処理を施すと、やはりｐｂ＋ｓｂを含有しないメッキ浴
を用いた場合に比べ著しい耐食性の劣化を招くものであ
った。In this case, although the intergranular corrosion of the plating film does not deteriorate significantly, when the obtained plated steel sheet is subjected to Chronaut treatment, the corrosion resistance deteriorates significantly compared to when a plating bath that does not contain PB+SB is used. It was an invitation.
一方、前記（ｄ）項で示したＢｉ添加浴を用いる方法で
は、Ｂ１は非常に少量の添加で著しいスパングルの成長
促進効果を発揮するのでｐｂやｓｂの場合のような弊害
は生しないものの、それとは別に、）メッキ浴の流動性
が低下するためメッキ表面に流れ模様が生じ易い
１１）旧は少量添加でスパングルの成長に大きな影響を
及ぼすため、逆に僅かな浴組成変動によってもメッキの
仕上がり状態が影響を受は易く、作業管理が非常に難し
い
等の問題があった。On the other hand, in the method using the Bi-added bath shown in section (d) above, B1 exhibits a remarkable spangle growth promoting effect even when added in a very small amount, so although it does not cause the adverse effects as in the case of PB and SB, Separately, the fluidity of the plating bath decreases, which tends to cause flow patterns on the plating surface. There were problems such as the finished state being easily affected and work management being extremely difficult.
勿論、従来からの低ｐｂ浴では、クロメート処理後の耐
食性は良好であるもののレギュラースパングル材の製造
が不可能であったことは言うまでもない。Of course, it goes without saying that with conventional low Pb baths, although the corrosion resistance after chromate treatment was good, it was not possible to produce regular spangle materials.
そこで、本発明の主目的は、前述の問題点を解消し、同
一メッキラインでレギュラースパングル材及びゼロスパ
ングル材を製造する必要がある場合でも、何れのメッキ
処理にも適用でき、しかもクロメート処理後の耐食性を
低ｐｂ亜鉛浴メッギに比べて劣化させることなしに高ｐ
ｂ亜鉛浴と同程度のスパングルを形成させることが可能
な溶融亜鉛メッキ鋼板の製造方法を見出し、もって耐食
性に優れた溶融亜鉛メッキ鋼板を安定して提供すること
にある。Therefore, the main purpose of the present invention is to solve the above-mentioned problems, to be applicable to any plating process even when it is necessary to manufacture regular spangle material and zero-spangle material on the same plating line, and to be able to apply it to any plating process after chromate treatment. High pb zinc bath without deteriorating corrosion resistance compared to low pb zinc bath meggi
(b) An object of the present invention is to find a method for producing a hot-dip galvanized steel sheet that can form spangles to the same extent as in a zinc bath, and thereby to stably provide a hot-dip galvanized steel sheet with excellent corrosion resistance.
〈課題を解決するだめの手段〉
本発明は、」−起用的を達成すべくなされたものであり
、
［溶融亜鉛メッキ鋼板を、皮膜の平均組成がＡｆ：０．
１〜０．７％、 旧： ０．００３〜０．０１５％Ｐ
ｂ ： ０．０１〜０．０５％、 Ｆｅ ： １．０
％以下を含み、残部が実質的にＺｎである溶融亜鉛メッ
キ皮膜を有した構成とするか、或いは、その最表層に更
にクロメート処理皮膜を有して成る構成とする点」
に特徴を有するものであり、更には、
「八ｐ：ｏ、１〜０．５％、Ｂｉ：０．００３〜０．０
１５％Ｐｂ ： ０．０１〜０．０５％
を含み、残部が実質的にＺｎである熔融亜鉛メッキ浴に
鋼板を短時間浸漬させた後、所定のＺｎ付着量にメッキ
付着量を調整してから冷却することにより、目的とする
スパングル状態の如何に係わらず、表面性状や耐食性に
優れた溶融亜鉛メッキ鋼板を作業性良く安定して製造し
得るようにした点」をも特徴とするものである。<Means for Solving the Problems> The present invention has been made to achieve the above-mentioned advantages.
1~0.7%, old: 0.003~0.015%P
b: 0.01-0.05%, Fe: 1.0
% or less and the remainder is substantially Zn, or further has a chromate-treated film on the outermost layer. And furthermore, "8p: o, 1 to 0.5%, Bi: 0.003 to 0.0
After immersing a steel plate for a short time in a hot-dip galvanizing bath containing 15% Pb: 0.01 to 0.05% and the remainder being substantially Zn, the coating amount is adjusted to a predetermined Zn coating amount. It is also characterized by the fact that, by cooling from be.
なお、ここで言うクロメ−１・処理は格別に限定される
ものではなく、亜鉛表面に適用されるものであればその
種別を問うものではない。Note that the chromium-1 treatment referred to herein is not particularly limited, and the type of treatment is not limited as long as it is applied to the zinc surface.
上述のように、本発明は、同一ラインを用いてレギュラ
ースパングル材もゼロスパングル材も製造できる特定組
成の溶融亜鉛メッキ浴を使用して鋼板のメッキ処理を行
うことにより、特定組成のメッキ皮膜を有し、クロメー
ト処理後も°゛低ｐｂ浴でのメッキに続いて同一クロメ
ート処理を施したもの”と同程度の優れた耐食性を示す
溶融亜鉛メッキ鋼板を得、更にはこれにクロメート処理
を施すことによって高耐食性溶融亜鉛メッキ鋼板を作業
性良く安定製造することに関するものであるが、以下、
本発明において、溶融亜鉛メッキ浴並びにメッキ皮膜の
化学組成を前記の如くに限定した理由を、各構成元素の
作用と共に詳述する。As mentioned above, the present invention plating a steel plate using a hot-dip galvanizing bath with a specific composition, which can produce both regular spangle material and zero-spangle material using the same line, produces a plating film with a specific composition. We obtained a hot-dip galvanized steel sheet that, even after chromate treatment, exhibits excellent corrosion resistance comparable to that of ``a plated in a low Pb bath followed by the same chromate treatment,'' and furthermore, we applied chromate treatment to this sheet. The following is related to the stable production of highly corrosion-resistant hot-dip galvanized steel sheets with good workability.
In the present invention, the reason why the chemical compositions of the hot-dip galvanizing bath and the plating film are limited as described above will be explained in detail together with the effects of each constituent element.
〈作用〉
（Δ） ＡＮ
Ａβ成分は、溶融亜鉛メッキ層の鋼素地に対する密着性
を確保するために添加されるものである。<Function> (Δ) AN The Aβ component is added to ensure the adhesion of the hot-dip galvanized layer to the steel base.
つまり、Ａｐは鋼板が溶融亜鉛メッキ浴中に浸漬されで
いるときにその表面に緻密なＦｅ−ＩＶ金合金形成させ
、鋼板−メッキ層界面でのＦｅ−Ｚｎ合金化を抑制する
ことによりメッキの密着性を確保する。In other words, Ap forms a dense Fe-IV gold alloy on the surface of a steel sheet while it is immersed in a hot-dip galvanizing bath, and suppresses Fe-Zn alloying at the interface between the steel sheet and the plating layer. Ensure adhesion.
そして、溶融亜鉛メッキ浴中の八に含有量が０．１％未
満では、上記密着性を確保するに十分なＦｅＡ１合金が
形成されないため所望の効果が得られない。一方、熔融
亜鉛メッキ浴中のＩＶ含有量が０．５％を超えると、メ
ッキ層内に遊離するＡｐ、によりメッキ層が脆化するば
かりでな（、メッキ機器類の溶食とドロスの発生が促進
されるため、設備的作業的にも問題が生しる。従って、
溶融亜鉛メッキ浴中のへβ含有量は０．１〜０．５％と
定めた。If the content of iron in the hot-dip galvanizing bath is less than 0.1%, the desired effect cannot be obtained because sufficient FeA1 alloy is not formed to ensure the above-mentioned adhesion. On the other hand, if the IV content in the molten galvanizing bath exceeds 0.5%, the plating layer will not only become brittle due to Ap liberated within the plating layer (e.g., corrosion of plating equipment and generation of dross). This causes problems in terms of equipment and work.Therefore,
The β content in the hot-dip galvanizing bath was determined to be 0.1 to 0.5%.
また、かかる溶融亜鉛メッキ浴でメッキを行った場合、
上述したように鋼板−メッキ層界面にＦｅＡＮ合金層が
形成されるため、皮膜平均でのＡｐの含有量はメッキ浴
組成のそれよりも高くなる。この界面でのＡｐの濃化量
（Ｆｅ−Ａｊ！合金の形成量）は浴中ｐｐ、９度や温度
によっても変化するが、上記メッキ浴でメッキを行った
場合はメッキ皮膜の平均へ！濃度は０．１〜０．７％と
なり、優れた密着性を示すこととなる。従って、製品メ
ッキ鋼板におけるメッキ皮膜中のＡβ含有量は、平均で
０．１〜０．７％と定めた。In addition, when plating is performed in such a hot dip galvanizing bath,
As described above, since the FeAN alloy layer is formed at the steel plate-plating layer interface, the average content of Ap in the film is higher than that in the plating bath composition. The amount of Ap concentration at this interface (the amount of Fe-Aj! alloy formed) varies depending on the pp in the bath, 9 degrees Celsius, and temperature, but when plating is performed in the above plating bath, it is the average value of the plating film! The concentration is 0.1 to 0.7%, indicating excellent adhesion. Therefore, the Aβ content in the plating film of the product plated steel sheet was determined to be 0.1 to 0.7% on average.
（Ｂ） Ｂｉ Ｐｂ
Ｂ１はスパングル形成助剤として作用する成分であるが
、これは、形成されるＢｉ −Ｚｎ合金の共晶温度が低
いために十分なスパングル径成長が促される猶予時間を
確保できることに起因すると考えられる。(B) Bi Pb B1 is a component that acts as a spangle formation aid, and this is because the eutectic temperature of the Bi-Zn alloy to be formed is low, so a grace period can be secured to promote sufficient spangle diameter growth. This is thought to be due to.
この旧のスパングル形成作用は非常に強くて少量の添加
であっても効果が認められるが、それでもＢｉ含有量が
０．００３％未満であると前記作用による所望の効果を
十分に確保することができないので、メッキ浴中の（従
って製品メッキ皮膜中の）Ｂｉ含有量は０．００３〜０
．０１５％に調整する必要がある。This old spangle-forming effect is very strong and is effective even when added in small amounts; however, if the Bi content is less than 0.003%, the desired effect due to the above effect cannot be sufficiently ensured. Therefore, the Bi content in the plating bath (and therefore in the product plating film) is 0.003 to 0.
．． It is necessary to adjust it to 0.015%.
ただ、この範囲の量であってもＢｉを単独添加したした
だけではレギュラースパングル材としてはスパングルの
大きさが不十分となるが、それにも係わらすＢｉ含有量
の上限を０．０１．５％”に定めた理由は次の通りであ
る。However, even if Bi is added in an amount within this range, the size of the spangles will be insufficient for a regular spangle material, but the upper limit of the Bi content is set at 0.01.5%. ” The reasons for this are as follows.
即ち、旧は非常に強いスパングル形成作用を有している
ものの、反面、
）旧添加はメッキ浴の流動性の観点から好ましくなくて
メッキ後の美麗な外観を得にくくなる傾向があり、その
ため、Ｂｉ添加の場合には同時にメッキ浴の流動性を改
善する生立てを講じる必要がある
１ｉ）Ｂｉのスパングル形成作用は極めて強いため、Ｂ
ｉ添加を行うと僅かな浴組成変動でスパングルの大きさ
が極端に変化して操業が困難であるので、スパングル形
成作用を緩和する生立てを講じる必要がある
１１１）メッキ浴中のＢｉを高濃度（＝０．０２０％）
とした場合には大きなスパングルが得られるが、同一メ
ッキ浴を使用してゼロスパングル材を製造しようとして
もスパングルが完全に消滅しなくなり、実際の溶融亜鉛
メッキラインへの適用が困難となる
等の問題をもたらす。そのため、これらの問題につき種
々の検討を加えた結果、Ｂｉ添加量の上限を０．０１５
％に抑えた上で０．０１〜０．０５％のｐｂとの複合添
加を実施すると、Ｂｉ添加による上記問題点が効果的に
解消されることが分かった。That is, although old has a very strong spangle-forming effect, on the other hand, adding old is undesirable from the viewpoint of fluidity of the plating bath and tends to make it difficult to obtain a beautiful appearance after plating. When adding Bi, it is necessary to take steps to improve the fluidity of the plating bath at the same time. 1i) Since the spangle-forming effect of Bi is extremely strong,
If i is added, the spangle size will change drastically with a slight change in the bath composition, making operation difficult, so it is necessary to take measures to alleviate the spangle-forming effect.111) Increase Bi in the plating bath. Concentration (=0.020%)
Although large spangles can be obtained when using the same plating bath, the spangles will not completely disappear even if a zero-spangle material is manufactured using the same plating bath, making it difficult to apply to an actual hot-dip galvanizing line. bring problems. Therefore, as a result of various studies regarding these issues, the upper limit of the amount of Bi added was set at 0.015.
It was found that the above-mentioned problems caused by the addition of Bi can be effectively solved by suppressing the Bi content to 0.01 to 0.05% by adding Pb in combination.
従って、１含有量は０．００３〜０．０１５％と定めた
。Therefore, the 1 content was determined to be 0.003 to 0.015%.
なお、Ｂｉと共に複合添加するｐｂ量が０．０１％未満
であるとＢｉ添加による前記不都合を解消できず、一方
、ｐｂ量が０．０５％を超えた場合にはメッキ皮膜の耐
食性が劣化する傾向を見せ、特にクロメート処理を施し
た場合に目立って耐食性が劣化することから、ｐｂ含有
量は０．０１〜０．０５％と限定した。Note that if the amount of Pb added in combination with Bi is less than 0.01%, the above-mentioned disadvantages due to the addition of Bi cannot be eliminated, while if the amount of Pb exceeds 0.05%, the corrosion resistance of the plating film deteriorates. The Pb content was limited to 0.01 to 0.05% because the corrosion resistance tends to deteriorate particularly when chromate treatment is applied.
（Ｃ） Ｆｅ
前述のように、本発明にかかる浴組成の熔融メッキ浴に
てメッキ処理を行うと、メッキ皮膜の鋼板との界面側に
緻密なＦｅ−Ａ２合金層が形成されて密着性が改善され
るが、皮膜中のＦｅ含有量が該皮膜の平均組成で１．０
％を超えると、皮膜中に脆弱なＦｅ −Ｚｎ合金層が認
められるようになって密着性の劣化を招くことから、メ
ッキ皮膜のＦｅ含有量を平均組成で１．０％以下と定め
た。(C) Fe As mentioned above, when plating is performed in a hot-dip plating bath having the bath composition according to the present invention, a dense Fe-A2 alloy layer is formed on the interface side of the plating film with the steel plate, and the adhesion is improved. However, the Fe content in the film is 1.0 in the average composition of the film.
%, a weak Fe--Zn alloy layer will be observed in the film, leading to deterioration of adhesion. Therefore, the Fe content of the plating film was set at 1.0% or less in average composition.
続いて、本発明の効果を実施例によって具体的に説明す
る。Next, the effects of the present invention will be specifically explained using examples.
〈実施例〉
実施例 １
まず、第１表に示される如き化学組成の溶融亜鉛メッキ
浴（浴温：４６０℃）を準備し、各メッキ浴中に０．５
ｍｍ厚Ｘ１００ｍ幅×３００顔量長の銅板試験片を１秒
間浸漬し、片面当りのメッキ目付量が６０〜１００ｇ／
ｍ＋になるように８周整した後、レギュラースパングル
材製造時における常法通りの条件で冷却し、溶融亜鉛メ
ッキ鋼板を製造した。<Example> Example 1 First, hot-dip galvanizing baths (bath temperature: 460°C) having the chemical composition shown in Table 1 were prepared, and each plating bath contained 0.5
A copper plate test piece of mm thickness x 100 m width x 300 face weight length was immersed for 1 second, and the plating weight per side was 60 to 100 g/
After trimming the steel sheet 8 times so as to obtain m+, it was cooled under the usual conditions for manufacturing regular spangle materials, and a hot-dip galvanized steel sheet was manufactured.
このようにして得られた溶融亜鉛メッキ鋼板について［
スパングル形成状態−１及び「外観（波しわの有無）」
を観察した後、一部サンプルを切り出し、「メッキ皮膜
組成」及び「メッキ密着性」の調査を実施した。なお、
メッキ皮膜組成は、１０％ＨＣ１溶液に鉄用インヒビタ
ーを０．８％添加した液で皮膜溶解を行った後、該溶解
液を分析して調査した。また、メッキ密着性は、Ｏｔ曲
げ後にセロハンテープ剥離試験を行い、その際のメッキ
剥離の有無で評価した。Regarding the hot-dip galvanized steel sheet obtained in this way [
Spangle formation status-1 and “appearance (presence or absence of wrinkles)”
After observing, some samples were cut out and the "plating film composition" and "plating adhesion" were investigated. In addition,
The composition of the plating film was investigated by dissolving the film in a 10% HCl solution with 0.8% iron inhibitor added and then analyzing the solution. Further, the plating adhesion was evaluated by performing a cellophane tape peeling test after Ot bending and checking whether or not the plating peeled off at that time.
更に、前記各メッキ鋼板にクロメート処理を施し、該メ
ッキ鋼板のクロメート処理後の耐食性をも調査した。な
お、このときのクロメート処理には、
無水クロム酸：５０ｇ／ｊ！
珪フッ化水素酸：５ｇ／ｌ
リン酸：１０ｇ／β
から成る混合液中のクロム酸をエタノールで還元してＣ
Ｃｒ”／Ｃｒ” ＝ １／１：］に調整した液を用い、
Ｃｒ付着量が２０〜２５ｍｇ／ｍとなるように塗布し乾
燥する方法を採用した。そして、クロメート処理後の耐
食性は、前記クロメート処理サンプルの５ＳＴ（ＪＩＳ
Ｚ ２３７１に規定）１００時間後の白錆発生面積に
よって評価した。Furthermore, each of the plated steel sheets was subjected to chromate treatment, and the corrosion resistance of the plated steel sheets after the chromate treatment was also investigated. In addition, for the chromate treatment at this time, chromic anhydride: 50g/j! Chromic acid in a mixture consisting of hydrosilicofluoric acid: 5 g/l and phosphoric acid: 10 g/β is reduced with ethanol to reduce C.
Using a solution adjusted to Cr"/Cr" = 1/1:],
A method of coating and drying was adopted so that the amount of Cr deposited was 20 to 25 mg/m. The corrosion resistance after chromate treatment is 5ST (JIS) of the chromate treatment sample.
Z 2371) Evaluation was made based on the area where white rust occurred after 100 hours.
これらの結果を第１表に併せて示す。These results are also shown in Table 1.
第１表に示される結果からも明らかなように、本発明に
よればメッキ密着性、外観並びにクロメト処理後耐食性
の優れた美麗なスパングル材が得られるのに対して、本
発明で規定する条件から外れた場合には、十分に満足で
きるメ、ギ鋼板を安定して得られないことが分かる。As is clear from the results shown in Table 1, according to the present invention, a beautiful spangle material with excellent plating adhesion, appearance, and corrosion resistance after chromate treatment can be obtained, whereas the conditions specified in the present invention It can be seen that if it deviates from this, it is not possible to stably obtain a fully satisfactory steel plate.
実施例 ２
八β：ｏ、＋８％、 Ｐｂ ： ０．０５％、 Ｂｉ
： ０．００５％を含み、残部が実質的にＺｎから成る
ところの、本発明に係る溶融亜鉛メッキ浴にてメッキし
た実施例１と同様の鋼板に、メッキ後直ちにリン酸マグ
ネシウム溶液を噴霧して急冷したところ、申し分のない
ゼロスパングル材を得ることができた。Example 2 Eight β: o, +8%, Pb: 0.05%, Bi
: Immediately after plating, a magnesium phosphate solution was sprayed onto a steel plate similar to that of Example 1 plated in the hot-dip galvanizing bath according to the present invention, containing 0.005% Zn and the remainder consisting essentially of Zn. When the material was quenched, a perfect zero spangle material was obtained.
そして、該ゼロスパングル材は良好な外観と十分なメッ
キ密着性を示し、クロメ−Ｉ・処理後耐食性の点でも満
足できるものであることが確認された。It was also confirmed that the zero spangle material exhibited good appearance and sufficient plating adhesion, and was also satisfactory in terms of corrosion resistance after chrome-I treatment.
なお、比較のため、八β：０．１８％、 Ｐｂ ： ０
．０５％Ｒｉ ： ０．１５％、残部が実質的にＺｎか
ら成る溶融亜鉛メッキ浴を使用した以外は上記と同様に
ゼロスパングル材の製造試みたところ、スパングルは十
分１ ら
に小さくならず、ゼロスパングル材としては不十分な外
観のメッキ鋼板となることも確認された。For comparison, 8β: 0.18%, Pb: 0
．． When an attempt was made to produce zero spangle material in the same manner as above except that a hot-dip galvanizing bath consisting of 0.15% Ri and the remainder substantially Zn was used, the spangles did not become sufficiently smaller than 1. It was also confirmed that the plated steel sheet had an appearance that was inadequate as a spangle material.
〈効果の総括〉
以上に説明した如く、この発明によれば、同一メッキ浴
でもってレギュラースパングル材とセロスパングル材の
製造が作業性良く安定して実施できる上、得られる溶融
メッキ鋼板は外観及び耐食性とも十分に優れており、特
に従来材に比して著しく優れたクロメート処理後耐食性
を示すレギュラースパングル材の安定製造が可能となる
など、産業上有用な効果がもたらされる。<Summary of Effects> As explained above, according to the present invention, regular spangle material and cello spangle material can be manufactured stably with good workability using the same plating bath, and the resulting hot-dip plated steel sheet has good appearance and It is also sufficiently excellent in corrosion resistance, and provides industrially useful effects such as making it possible to stably produce regular spangle materials that exhibit significantly superior corrosion resistance after chromate treatment compared to conventional materials.
Claims (3)
．１〜０．７％、Ｂｉ：０．００３〜０．０１５％、Ｐ
ｂ：０．０１〜０．０５％、Ｆｅ：１．０％以下を含み
、残部が実質的にＺｎである溶融亜鉛メッキ鋼板。(1) The average composition of the plating film is Al:0 in terms of weight ratio.
．． 1-0.7%, Bi: 0.003-0.015%, P
A hot-dip galvanized steel sheet containing b: 0.01 to 0.05%, Fe: 1.0% or less, and the remainder being substantially Zn.
項１に記載の溶融亜鉛メッキ鋼板。(2) The hot-dip galvanized steel sheet according to claim 1, which has a chromate treatment film on the outermost layer.
５％、Ｐｂ：０．０１〜０．０５％を含み、残部が実質
的にＺｎである溶融亜鉛メッキ浴に鋼板を浸漬すること
を特徴とする、請求項１に記載の溶融亜鉛メッキ鋼板の
製造方法。(3) Al: 0.1-0.5%, Bi: 0.003-0.01 in weight percentage
5%, Pb: 0.01 to 0.05%, and the remainder is substantially Zn. Production method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP16648188A JPH0215152A (en) | 1988-07-04 | 1988-07-04 | Hot dip galvanized steel sheet and its production |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP16648188A JPH0215152A (en) | 1988-07-04 | 1988-07-04 | Hot dip galvanized steel sheet and its production |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0215152A true JPH0215152A (en) | 1990-01-18 |
Family
ID=15832201
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP16648188A Pending JPH0215152A (en) | 1988-07-04 | 1988-07-04 | Hot dip galvanized steel sheet and its production |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0215152A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02240175A (en) * | 1989-01-28 | 1990-09-25 | Roehm Gmbh | Aueous dispersion of film-forming (meth)acrylate polymer for obtaining coating film on solid plastic surface |
| JPH0890026A (en) * | 1994-09-13 | 1996-04-09 | Sumitomo Metal Ind Ltd | Control method for tandem mill |
| JP2019501296A (en) * | 2015-12-24 | 2019-01-17 | ポスコＰｏｓｃｏ | Plating steel material excellent in friction resistance and white rust resistance and manufacturing method thereof |
-
1988
- 1988-07-04 JP JP16648188A patent/JPH0215152A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02240175A (en) * | 1989-01-28 | 1990-09-25 | Roehm Gmbh | Aueous dispersion of film-forming (meth)acrylate polymer for obtaining coating film on solid plastic surface |
| JPH0890026A (en) * | 1994-09-13 | 1996-04-09 | Sumitomo Metal Ind Ltd | Control method for tandem mill |
| JP2019501296A (en) * | 2015-12-24 | 2019-01-17 | ポスコＰｏｓｃｏ | Plating steel material excellent in friction resistance and white rust resistance and manufacturing method thereof |
| US10907243B2 (en) | 2015-12-24 | 2021-02-02 | Posco | Plated steel material having excellent friction resistance and white rust resistance and method for preparing same |
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