JPH05125515A - Manufacture of hot-dip zn-al plated steel sheet excellent in appearance, secular blackening resistance and corrosion resistance - Google Patents
Manufacture of hot-dip zn-al plated steel sheet excellent in appearance, secular blackening resistance and corrosion resistanceInfo
- Publication number
- JPH05125515A JPH05125515A JP31736691A JP31736691A JPH05125515A JP H05125515 A JPH05125515 A JP H05125515A JP 31736691 A JP31736691 A JP 31736691A JP 31736691 A JP31736691 A JP 31736691A JP H05125515 A JPH05125515 A JP H05125515A
- Authority
- JP
- Japan
- Prior art keywords
- steel sheet
- appearance
- dip
- hot
- corrosion resistance
- 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.)
- Granted
Links
Landscapes
- Coating With Molten Metal (AREA)
Abstract
Description
【0001】[0001]
【産業上の利用分野】本発明は、主として建材及び家電
用途で使用される外観、耐経時黒変性、耐食性に優れる
溶融Zn−Alめっき鋼板の製造方法に関するものであ
る。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a hot-dip Zn-Al plated steel sheet having excellent appearance, blackening resistance over time, and corrosion resistance, which are mainly used for building materials and home appliances.
【0002】[0002]
【従来の技術】溶融Zn−Alめっき鋼板は、溶融Zn
めっき鋼板に比較して裸耐食性、塗装後耐食性が優れて
いることから、最近主として建材、家電用途での使用量
が増加している。しかしながら、溶融Zn−Alめっき
鋼板は亀甲模様と称する外観不良の問題及び高温度、高
湿度環境化にさらされると表面が黒変する経時黒変の問
題がありその改善が必要である。また、耐食性について
も更に向上の要求がある。これらの課題に対し、例えば
特公昭63−11420号公報にてZn−Al合金にT
iまたはZrの1種または2種、Mn,Ni,Coまた
はFeの内1種または2種、TiAl3またはZrAl3
の1種または2種を添加した合金を用いた耐食性に優れ
るめっき鋼板を製造する技術、特開平2−274851
号公報にて、同じくZn−Al合金にTi,B及びS
i,Mg,MnまたはCuの1種または2種を添加した
合金を用いた耐食性に優れるめっき鋼板を製造する技術
が開示されている。2. Description of the Related Art Hot-dip Zn-Al plated steel sheets are
Compared with galvanized steel sheet, it has more excellent bare corrosion resistance and post-painting corrosion resistance, so the amount of its use mainly in building materials and home appliances has been increasing recently. However, the hot-dip Zn-Al plated steel sheet has a problem of poor appearance called a hexagonal pattern and a problem of blackening over time when its surface is blackened when exposed to high temperature and high humidity environment, and its improvement is necessary. There is also a demand for further improvement in corrosion resistance. To solve these problems, for example, in Japanese Patent Publication No. 63-11420, Zn-Al alloys with T
i or Zr, one or two, Mn, Ni, Co, or Fe, one or two, TiAl 3 or ZrAl 3
Of producing a plated steel sheet having excellent corrosion resistance using an alloy containing one or two of the above, Japanese Patent Application Laid-Open No. 2-274851
In the publication, the same Zn-Al alloy is added to Ti, B and S.
A technique for producing a plated steel sheet having excellent corrosion resistance using an alloy containing one or two of i, Mg, Mn, or Cu is disclosed.
【0003】しかし、これらの技術は耐食性向上効果は
得られるものの、外観及び耐経時黒変性については性能
改善が得られなかった。また、めっき浴に多種類の元素
を添加する方法は、実操業において浴成分の管理が困難
である問題を生じた。また、耐経時黒変性改善について
は、溶融めっき後鋼板表面をCo,Ni等の金属を電気
めっきもしくは置換めっきにて析出させる方法等が適用
されている。しかし、この方法はZnに対して電位的に
貴である金属をめっき表面に析出させるため耐食性の低
下の原因となる、また溶融めっき後に処理する必要があ
るため製造コストが増加する等の問題があった。However, although these techniques can improve the corrosion resistance, they cannot improve the appearance and the blackening resistance with time. Further, the method of adding various kinds of elements to the plating bath causes a problem that it is difficult to control the bath components in the actual operation. Further, with respect to the improvement in blackening resistance over time, a method of depositing a metal such as Co or Ni by electroplating or displacement plating on the surface of a steel sheet after hot dipping is applied. However, this method causes a reduction in corrosion resistance because it deposits a metal, which is more noble to Zn, on the plating surface, and there is a problem that the manufacturing cost increases because it needs to be treated after hot dipping. there were.
【0004】[0004]
【発明が解決しようとする課題】以上述べた、従来技術
を用いることで耐食性、耐経時黒変性を個々に改善する
ことが可能であるが、外観、耐経時黒変性及び耐食性を
共に改善させることはできなかった。また、これら従来
技術を組み合わせる方法を用いた場合、製造コストが大
幅に増加する問題が生じた。Although it is possible to individually improve the corrosion resistance and the blackening resistance over time by using the above-mentioned conventional techniques, it is necessary to improve both the appearance, the blackening resistance over time and the corrosion resistance. I couldn't. Further, when the method of combining these conventional techniques is used, there is a problem that the manufacturing cost is significantly increased.
【0005】[0005]
【課題を解決するための手段】そこで、本発明者は外
観、耐経時黒変性及び耐食性に優れる溶融Zn−Alめ
っき鋼板の製造方法として以下の解決手段を見いだし
た。連続式溶融Znめっきラインにおいて被めっき鋼板
をめっき浴組成Al:3〜10重量%、Ti:0.01
〜1重量%、残部Zn及び不可避的不純物からなり、か
つめっき浴温度が410〜470℃のめっき浴を用いて
めっきした後、該めっき鋼板を冷却する際、板温が40
0℃から380℃に低下する間で冷却速度を15〜10
0℃/秒とすることを特徴とする外観、耐経時黒変性、
耐食性に優れる溶融Zn−Alめっき鋼板の製造方法。Therefore, the present inventor has found the following solution as a method for producing a hot-dip Zn-Al plated steel sheet having excellent appearance, blackening resistance over time, and corrosion resistance. In a continuous hot dip Zn plating line, a steel sheet to be plated is plated with a bath composition of Al: 3 to 10% by weight, Ti: 0.01
After plating using a plating bath having a plating bath temperature of 410 to 470 ° C., the plate temperature is 40% when cooled.
Cooling rate is 15 to 10 while decreasing from 0 ° C to 380 ° C.
Appearance characterized by 0 ° C / sec, blackening resistance over time,
A method for producing a hot-dip Zn-Al plated steel sheet having excellent corrosion resistance.
【0006】[0006]
【作用】めっき浴組成においてAl 3〜10重量%、
Ti 0.01〜1重量%、残部Znを用いる。Al
は、Znと共晶組織を形成し優れた耐食性を発揮する。
この効果を得るためにはAl 3〜10重量%とする。
Alが3重量%未満では共晶組織形成による耐食性向上
作用が得られなくなる。また10重量%超ではめっき層
の硬度が増し鋼板を折り曲げて使用する部位ではめっき
が剥がれる等の問題を生じやすくなる。Tiは、めっき
層の表面にTi酸化皮膜層形成による耐食性向上及び耐
経時黒変性の改善効果が得られる。また、めっき層のス
パングルを微細化する作用を有することから、スパング
ル粗大化に起因して生じる亀甲模様を低減させめっき表
面外観を改善する効果が得られる。この効果を得るため
にはTi0.01〜1重量%とする。Ti 0.01重
量%未満では上記効果が得られず、また1重量%超で
は、めっき浴の粘性が増大しめっき付着量制御が困難と
なる問題が生じる。めっき浴温度は410〜470℃に
て行なう。410℃未満では、めっきワイピング時にさ
ざ波模様状の外観不良が生じめっき表面の平滑性が失わ
れる。470℃超ではめっき層と素地鋼板界面にFe−
Al系の合金層が発達し、めっき層の加工性が低下する
問題を生じる。[Function] In the plating bath composition, Al 3 to 10% by weight,
0.01 to 1% by weight of Ti and the balance Zn are used. Al
Forms a eutectic structure with Zn and exhibits excellent corrosion resistance.
In order to obtain this effect, Al 3 to 10% by weight is used.
If Al is less than 3% by weight, the effect of improving the corrosion resistance due to the formation of a eutectic structure cannot be obtained. On the other hand, if it exceeds 10% by weight, the hardness of the plating layer increases, and problems such as peeling of the plating are likely to occur at the site where the steel sheet is bent and used. Ti has the effects of improving corrosion resistance and blackening resistance over time by forming a Ti oxide film layer on the surface of the plating layer. Further, since it has the effect of making the spangle of the plating layer fine, it is possible to reduce the hexagonal pattern caused by the coarsening of the spangle and improve the appearance of the plated surface. To obtain this effect, Ti is 0.01 to 1% by weight. If the Ti content is less than 0.01% by weight, the above effect cannot be obtained. If the Ti content exceeds 1% by weight, the viscosity of the plating bath increases, which makes it difficult to control the coating amount. The plating bath temperature is 410 to 470 ° C. If the temperature is lower than 410 ° C., a ripple-like appearance defect will occur during the wiping of the plating, and the smoothness of the plating surface will be lost. If the temperature exceeds 470 ° C, Fe-
This causes a problem that the Al-based alloy layer develops and the workability of the plated layer decreases.
【0007】めっき後、めっき鋼板を冷却する際400
℃から380℃に移行する間で冷却速度を15〜100
℃/秒とする。すなわち、本発明の浴組成で得られため
っき層は凝固する際、400℃付近で初晶β−Zn相も
しくはα−Alリッチ相が析出して凝固が開始し、38
0℃付近でZn−Al−Tiの3元共晶温度となり凝固
が終了する。このめっき層の凝固開始から終了迄の間の
冷却速度を15〜100℃/秒とすることで前述しため
っき層のスパングルを微細化することによりめっき表面
外観を改善する効果と、初晶β−Zn相もしくはα−A
lリッチ相の析出サイズを微細化することによる耐食性
の向上効果が得られる。冷却速度15℃/秒未満では上
記効果が得られず、また100℃/秒超では鋼板の形状
崩れ等の問題が生じる。冷却速度をこの範囲に制御する
方法としては、めっきワイピング部の後に例えばガス吹
付け式強制冷却装置またはミストスプレーまたはフォグ
式強制冷却装置を用いることができる。When the plated steel sheet is cooled after plating, 400
The cooling rate is 15 to 100 during the transition from ℃ to 380 ℃.
C / sec. That is, when the plating layer obtained by the bath composition of the present invention is solidified, the primary crystal β-Zn phase or the α-Al rich phase is precipitated at around 400 ° C. to start solidification.
The ternary eutectic temperature of Zn-Al-Ti is reached near 0 ° C, and solidification is completed. By setting the cooling rate from the start of solidification of the plating layer to the end to 15 to 100 ° C./sec, the effect of improving the appearance of the plating surface by refining the spangle of the plating layer and the primary crystal β- Zn phase or α-A
The effect of improving the corrosion resistance can be obtained by refining the precipitation size of the l-rich phase. If the cooling rate is less than 15 ° C./sec, the above effect cannot be obtained, and if it exceeds 100 ° C./sec, problems such as shape collapse of the steel sheet occur. As a method of controlling the cooling rate within this range, for example, a gas spray type forced cooling device or a mist spray or fog type forced cooling device can be used after the plating wiping portion.
【0008】[0008]
【実施例】次に、実施例を説明する。ゼンジマー方式連
続溶融亜鉛めっきラインにて、板厚0.4mmのAl−
Killed鋼板を表1に示すめっき浴及び冷却条件に
て通板し、溶融Zn−Alめっき鋼板を製造した。得ら
れためっき鋼板の表面外観、耐経時黒変性及び耐食性を
下記に示す方法で評価した結果を同じく表1に示す。本
発明例1〜4はめっき浴のAl組成の影響、本発明例
5,6はTi組成の影響、本発明例7,8はめっき浴温
度の影響、本発明例9,10はめっき後の冷却速度の影
響を調べたものでいづれも表面外観、耐経時黒変性及び
耐食性が良好である。実施例に対し比較例1はTiが添
加されていない場合で、表面外観、耐経時黒変性及び耐
食性がやや劣る。比較例2はAl組成が低い場合で、耐
食性が著しく低下する。比較例3はめっき後に急冷しな
かった場合で表面外観が劣る。比較例4,5は現在市販
されているZn−Al系の溶融めっき鋼板を評価したも
ので、比較例4は耐経時黒変性が著しく劣り、比較例5
は表面外観及び耐食性が劣る。EXAMPLES Next, examples will be described. In the Zenzimer system continuous hot dip galvanizing line, the thickness of Al-0.4mm
The killed steel sheet was passed through the plating bath and cooling conditions shown in Table 1 to produce a hot dip Zn-Al plated steel sheet. Table 1 also shows the results of evaluation of the surface appearance, blackening resistance over time, and corrosion resistance of the obtained plated steel sheet by the methods described below. Inventive examples 1 to 4 are influenced by the Al composition of the plating bath, inventive examples 5 and 6 are influenced by the Ti composition, inventive examples 7 and 8 are influenced by the plating bath temperature, and inventive examples 9 and 10 are after the plating. The effects of the cooling rate were examined, and the surface appearance, blackening resistance over time, and corrosion resistance were all good. Comparative Example 1 is a case where Ti was not added to the Examples, and the surface appearance, blackening resistance over time, and corrosion resistance were slightly inferior. In Comparative Example 2, the Al composition is low, and the corrosion resistance is significantly reduced. Comparative Example 3 is inferior in surface appearance when it is not quenched after plating. Comparative Examples 4 and 5 are evaluations of Zn-Al-based hot-dip galvanized steel sheets that are currently on the market, and Comparative Example 4 is significantly inferior in blackening resistance over time.
Has poor surface appearance and corrosion resistance.
【0009】[0009]
【表1】 [Table 1]
【0010】表面外観評価方法 目視観察により下記基準で評価した。 ○:亀甲模様なし。 △:亀甲模様わずかに認められる。 ×:亀甲模様が目立つ。 耐経時黒変性評価方法 サンプル表面にクロメート処理を施した後、温度50
℃、RH95%の恒温恒湿槽にて梱包スタック試験を1
4日間行ない、試験前後の鋼板表面の明度の変化量(Δ
L値)を測定し下記基準で評価した。 〔使用測定機器:スガ試験機(株)製 カラーコンピュー
ター Model SM-4〕 ○: 3未満 △: 3以上 10未満 ×:10以上 耐食性 JIS・Z2371にもとづく塩水噴霧試験を3日間行
ない、腐食生成物をクロム酸を用いて洗浄除去し試験前
後のめっき腐食減量(g/m2・日)を重量法にて測定
し、下記基準で評点付けした。 5: 5g/m2・日未満 4: 5g/m2・日以上 10g/m2・日未満 3:10g/m2・日以上 20g/m2・日未満 2:20g/m2・日以上 40g/m2・日未満 1:40g/m2・日以上Surface Appearance Evaluation Method The surface appearance was evaluated by the following criteria. ○: No turtle shell pattern. Δ: A slight glaze pattern is observed. X: A tortoiseshell pattern is conspicuous. Black aging resistance evaluation method After the chromate treatment was applied to the sample surface, the temperature was set to 50.
1 in a packing stack test in a constant temperature and humidity chamber at ℃ and RH 95%
The amount of change in lightness of the steel sheet surface before and after the test (Δ
The L value) was measured and evaluated according to the following criteria. [Measurement equipment used: Color Computer Model SM-4 manufactured by Suga Test Instruments Co., Ltd.] ○: Less than 3 △: 3 or more and less than 10 ×: 10 or more Corrosion resistance A salt spray test based on JIS / Z2371 was performed for 3 days to obtain a corrosion product. Was washed and removed with chromic acid, and the amount of plating corrosion loss (g / m 2 · day) before and after the test was measured by a gravimetric method and rated according to the following criteria. 5: 5 g / m less than 2 · day 4: 5 g / m 2 · day or more 10 g / m less than 2 · day 3: 10 g / m 2 · day or more 20 g / m 2 · day less than 2: 20 g / m 2 · day or more Less than 40 g / m 2 · day 1: 40 g / m 2 · day or more
【0011】[0011]
【発明の効果】以上説明したごとく、本発明を用いるこ
とにより溶融Zn−Alめっき鋼板の外観、耐経時黒変
性及び耐食性の大幅な性能改善が得られ、建材及び家電
を中心とした溶融Zn−Alめっき鋼板の用途を拡大
し、工業的に大きな効果を奏するものである。As described above, by using the present invention, the performance of the hot-dip Zn-Al plated steel sheet can be greatly improved in appearance, blackening resistance and corrosion resistance. The application of the Al-plated steel sheet is expanded and a great industrial effect is achieved.
Claims (1)
めっき鋼板をめっき浴組成Al:3〜10重量%、T
i:0.01〜1重量%、残部Zn及び不可避的不純物
からなり、かつめっき浴温度が410〜470℃のめっ
き浴を用いてめっきした後、該めっき鋼板を冷却する
際、板温が400℃から380℃に低下する間で冷却速
度を15〜100℃/秒とすることを特徴とする外観、
耐経時黒変性、耐食性に優れる溶融Zn−Alめっき鋼
板の製造方法。1. A steel sheet to be plated in a continuous hot dip Zn plating line has a plating bath composition of Al: 3 to 10% by weight, T
i: 0.01 to 1% by weight, the balance consisting of Zn and unavoidable impurities, and after plating using a plating bath having a plating bath temperature of 410 to 470 ° C., when the plated steel sheet is cooled, the plate temperature is 400. Appearance characterized by a cooling rate of 15 to 100 ° C./sec while the temperature falls from ℃ to 380 ° C.,
A method for producing a hot-dip Zn-Al plated steel sheet which is excellent in blackening resistance over time and corrosion resistance.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP31736691A JP2821827B2 (en) | 1991-11-06 | 1991-11-06 | Method for producing hot-dip Zn-Al-plated steel sheet with excellent appearance, blackening resistance over time and corrosion resistance |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP31736691A JP2821827B2 (en) | 1991-11-06 | 1991-11-06 | Method for producing hot-dip Zn-Al-plated steel sheet with excellent appearance, blackening resistance over time and corrosion resistance |
Publications (2)
Publication Number | Publication Date |
---|---|
JPH05125515A true JPH05125515A (en) | 1993-05-21 |
JP2821827B2 JP2821827B2 (en) | 1998-11-05 |
Family
ID=18087444
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP31736691A Expired - Fee Related JP2821827B2 (en) | 1991-11-06 | 1991-11-06 | Method for producing hot-dip Zn-Al-plated steel sheet with excellent appearance, blackening resistance over time and corrosion resistance |
Country Status (1)
Country | Link |
---|---|
JP (1) | JP2821827B2 (en) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR100543286B1 (en) * | 2001-12-20 | 2006-01-20 | 주식회사 포스코 | Manufacturing method of galvanized steel sheets with excellent corrosion resistance |
US7998533B2 (en) | 2002-10-28 | 2011-08-16 | Nippon Steel Corporation | Highly corrosion-resistant hot-dip galvanized steel product excellent in surface smoothness and formability and process for producing same |
CN103422041A (en) * | 2013-07-08 | 2013-12-04 | 常州大学 | Ti-contained ZAM hot-dip galvanized zinc alloy and preparation method thereof |
CN103600526A (en) * | 2013-10-31 | 2014-02-26 | 苏州扬子江新型材料股份有限公司 | Wear-resistant fire-resistant color coating steel plate |
-
1991
- 1991-11-06 JP JP31736691A patent/JP2821827B2/en not_active Expired - Fee Related
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR100543286B1 (en) * | 2001-12-20 | 2006-01-20 | 주식회사 포스코 | Manufacturing method of galvanized steel sheets with excellent corrosion resistance |
US7998533B2 (en) | 2002-10-28 | 2011-08-16 | Nippon Steel Corporation | Highly corrosion-resistant hot-dip galvanized steel product excellent in surface smoothness and formability and process for producing same |
US8029915B2 (en) | 2002-10-28 | 2011-10-04 | Nippon Steel Corporation | Highly corrosion-resistant hot-dip galvanized steel product excellent in surface smoothness and formability and process for producing same |
CN103422041A (en) * | 2013-07-08 | 2013-12-04 | 常州大学 | Ti-contained ZAM hot-dip galvanized zinc alloy and preparation method thereof |
CN103600526A (en) * | 2013-10-31 | 2014-02-26 | 苏州扬子江新型材料股份有限公司 | Wear-resistant fire-resistant color coating steel plate |
Also Published As
Publication number | Publication date |
---|---|
JP2821827B2 (en) | 1998-11-05 |
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