JPH036235B2 - - Google Patents
Info
- Publication number
- JPH036235B2 JPH036235B2 JP58234299A JP23429983A JPH036235B2 JP H036235 B2 JPH036235 B2 JP H036235B2 JP 58234299 A JP58234299 A JP 58234299A JP 23429983 A JP23429983 A JP 23429983A JP H036235 B2 JPH036235 B2 JP H036235B2
- Authority
- JP
- Japan
- Prior art keywords
- plating
- coated
- lower layer
- steel plate
- present
- 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 - Lifetime
Links
- 229910000831 Steel Inorganic materials 0.000 claims description 19
- 239000010959 steel Substances 0.000 claims description 19
- 229910018605 Ni—Zn Inorganic materials 0.000 claims description 13
- 229910045601 alloy Inorganic materials 0.000 claims description 4
- 239000000956 alloy Substances 0.000 claims description 4
- 229910001297 Zn alloy Inorganic materials 0.000 claims description 3
- 238000007747 plating Methods 0.000 description 29
- 239000011701 zinc Substances 0.000 description 21
- 239000010410 layer Substances 0.000 description 14
- 239000011248 coating agent Substances 0.000 description 10
- 238000000576 coating method Methods 0.000 description 10
- 230000007797 corrosion Effects 0.000 description 8
- 238000005260 corrosion Methods 0.000 description 8
- 229910000765 intermetallic Inorganic materials 0.000 description 6
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 6
- 229910052725 zinc Inorganic materials 0.000 description 6
- 229910001335 Galvanized steel Inorganic materials 0.000 description 5
- 239000008397 galvanized steel Substances 0.000 description 5
- 239000003973 paint Substances 0.000 description 5
- 230000002265 prevention Effects 0.000 description 5
- 239000000463 material Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 238000005452 bending Methods 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910007570 Zn-Al Inorganic materials 0.000 description 2
- 239000010953 base metal Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000009863 impact test Methods 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 238000010008 shearing Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910002482 Cu–Ni Inorganic materials 0.000 description 1
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical group ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 1
- 230000005856 abnormality Effects 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 1
- 239000010960 cold rolled steel Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- POWFTOSLLWLEBN-UHFFFAOYSA-N tetrasodium;silicate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-][Si]([O-])([O-])[O-] POWFTOSLLWLEBN-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 description 1
- 229910000165 zinc phosphate Inorganic materials 0.000 description 1
- 229910000859 α-Fe Inorganic materials 0.000 description 1
Landscapes
- Electroplating Methods And Accessories (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
Description
（産業上の利用分野）
本発明は、あらかじめ塗装されて需要家に供給
されるいわゆる「プレコート鋼板」に関するもの
で、特に、耐食性と高速加工性に秀れ、自動車用
鋼板として好適なめつき鋼板に係るものである。
（従来技術）
近年、鋼板需要家の要望として、あらかじめコ
イルコーター等で鉄鋼メーカー又はその関連メー
カーで塗装されたプレコート鋼板が普及しつつあ
り、これが需要家における合理化に寄与している
と考えられる。
耐食性が要求されるプレコート鋼板としては、
Zn又はZn合金めつき鋼板が採用されることが多
いが、従来のこの種のめつき鋼板には下記の２点
において問題があつた。即ち、第１点は剪断加工
等により無塗装端面の露出が必ず生じ端面部から
の塗膜ブリスターが生長し、終局的には塗膜の剥
離を生じ、防錆上のネツクとなる点で、特にZn
めつきやZn−Al合金めつきは、この防錆上の欠
陥において耐食プレコート材としては不利であ
る。第２点は、高速もしくは衝撃的な曲げ変形等
において、過大な界面剪断応力がめつき−鋼板界
面もしくは塗膜−めつき界面に発生する点であ
る。特に、界面剪断応力に対する耐性に関して脆
性的である金属間化合物のめつきは不利であつ
て、例えば、Fe−Zn、Ni−Zn等のめつきは、剪
断、打抜、衝撃曲げ等の加工により、多くの場
合、めつき−鋼板界面で少なからず剥離を生じ
る。これは、電析めつきでも、溶融めつきでも本
質的に変らない。ZnめつきやZn−Alめつき等、
非金属間化合物系のめつきでは、この剥離は生じ
にくいが、塗膜厚が過大になると、塗膜−めつき
界面で剥離する場合が認められる。
以上要するに、防錆機能と加工機能の前記２点
を共に満足する安価なプレコート用めつき鋼板
は、従来公知のZn系めつき鋼板の中には見当ら
ないのが現状である。
（発明の目的）
本発明は、従来のプレコート用めつき鋼板の上
記問題点を改善したもので、端面からの塗膜フク
レを発生することのない、高度の高速加工性（即
ち、打ち抜き性、剪断性）と美麗な光沢を有する
積層めつき鋼板を提供するにある。
（発明の構成）
本発明の骨子は、鋼板表面上に、下層として、
Feを1.5〜50ｇ／m2被覆し、更に、その上にNi含
有量９〜20％（以下、すべて重量％を示す）の
Ni−Zn合金もしくはFe含有率７〜40％のFe−Zn
合金を２〜80ｇ／m2被覆してなる積層構造を有す
るめつき鋼板にある。
ここで下層とする被覆は、例えば、Cu−Ni等
の金属結晶の固溶体やその混相、あるいはCd、
Fe、Pb等とZnの混合物であつても良いが、金属
間化合物であつてはならない。その理由は、金属
間化合物は脆性的であり、鋼板の高速もしくは衝
撃的な曲げ変形に追従し得ないからである。
本発明において、下層としてFeは最も好適な
金属である。何故ならば、下層にFeを冠するこ
とによつて、従来公知のFe−Znめつきもしくは
Ni−Znめつきとの電気化学的な異質性は殆ど無
く、Ni−ZnもしくはFe−Znめつきの防錆機能が
そのまま発揮されるし、更にコストが低いからで
ある。本発明における数値限定の理由は、次のと
おりである。
下層の被覆量が1.5ｇ／m2未満では、全体を被
覆するに不充分であり、塗装後の耐衝撃性の向上
が期待できない。
Fe量が20ｇ／m2をこえても効果が飽和すると
共に経済的でなくなるので、上限を20ｇ／m2とし
た。
上層に冠するめつきは、Ni−Zn又はFe−Znが
好適である。その理由は、これらのめつきは、端
面の塗膜フクレが小さい、即ちここで言う防食性
が大きいからである。
Ni−ZnめつきのNi含有率が９％未満では、Zn
相が共存して防食性が低下する。また、20％をこ
えると、Ni相が共存して、化成処理性、防食性
が低下する。
Fe−Znめつきの場合、Fe含有率が７％未満で
は、η相が共電析して塗装後耐食性が低下し、40
％をこえると、フエライト相が共析して、カツト
部等の赤錆を誘発する。
上層に冠するめつき層の付着量は、２ｇ／m2以
上80ｇ／m2以下である必要がある。２ｇ／m2未満
では、端面防錆を含め耐食性の点で不充分である
し、80ｇ／m2をこえると、付着量過剰となり、特
に、曲げ加工、プレス成形性等が低下する。
本発明によるめつき鋼板は、一般の化成処理を
経て、塗料、特に高硬度塗料を塗布された状態に
おいて、従来のめつき鋼板に比して、秀れた性能
を発揮する。
以下、本発明を実施例によつて、更に説明す
る。
（実施例）
SPCCグレードの軟綱冷延鋼板（板厚0.50mm）
を、150×100mmに裁断し、トリクロルエチレンに
よる蒸気洗浄を行つた後、オルソ珪酸ソーダ溶液
中で電解脱脂し、次いで、表１に示す電解条件
で、Zn、Fe、の電気めつきを行つた。電解面積
は1dm2である。
次に、下層めつきを行つた鋼板を水洗後、表２
に示す電解条件で、Ni−Zn又はFe−Znの合金電
気めつきを施した。別に、単層のZn、Ni−Zn、
Fe−Zn等の電気めつき試料を、表１、表２の条
件によつて作成した。なお、付着量はトータルで
40ｇ／m2とした。各試料は、通常のリン酸亜鉛処
理（日本パーカー(株)ボンデライト＃3300）を経
て、クロメートシーリング（日本パーカー(株)パー
コレン＃62）を施した後、アクリル系焼付塗料
（プイマー6μｍ、トツプコート18μｍ）をバーコ
ーターにより塗布した。
次に、各試料は、25℃で、12φ−１Kgｆ−50cm
の条件でデユポン衝撃試験、クリアランス0.06mm
の電動シヤーによる剪断試験を実施し、高速加工
性を評価した。更に、該試料の四辺を剪断し、四
辺の端面を露出したまま、JISZ2371による塩水
噴霧試験に供し、480hrの端面部の塗膜フクレ巾
を測定した。これらの結果を、添付図面および表
３に示す。
添付図面は、上層にNi−Znめつき、下層にFe
又はZnを施した場合における、下層めつきと各
種性能の関係を示す。図において、衝撃テスト評
点は、めつき剥離を０、塗膜異常なしを５として
評価した。図に示すように、少くとも２ｇ／m2の
下層金属体（金属間化合物を除く）の存在によつ
て、高速加工性が極めて改善できる。しかし、
Znのような卑な金属を採用した時は、端面耐食
性を著しく損なうことが分る。
表３は、各種金属下地に、Fe−Znめつき（Fe
含有率22％）をめつきしたプレコート材の各種性
能をまとめたものである。表３に見られるよう
に、下地金属によつて若干の差異はあるが、本発
明の範囲においては、比較例に比して特に秀れた
性能を有することが分る。
これらの結果から、脆性な化合物系めつき層と
鋼の間に、延性を有する金属体Feを介在させる
ことによつて、何等かの応力緩和機構が働き、
Ni−Zn、Fe−Zn等のプレコート材の高速加工性
が改善できることが明らかである。なお、この手
段は、Fe−Zn、Ni−Znに限らず、脆性的な金属
間化合物系めつきの加工性の改善に応用し得る有
効な手段であると推測できる。
(Field of Industrial Application) The present invention relates to so-called "pre-coated steel sheets" which are coated in advance and supplied to customers. This is related. (Prior art) In recent years, pre-painted steel sheets that have been coated in advance by a steel manufacturer or related manufacturer using a coil coater, etc. have become popular as a request from steel sheet customers, and this is thought to be contributing to rationalization among customers. As a pre-painted steel sheet that requires corrosion resistance,
Zn or Zn alloy plated steel sheets are often used, but conventional plated steel sheets of this type have had the following two problems. That is, the first point is that uncoated end faces are inevitably exposed due to shearing, etc., and paint blisters grow from the end faces, eventually causing peeling of the paint film, which becomes a problem in rust prevention. Especially Zn
Plating or Zn-Al alloy plating is disadvantageous as a corrosion-resistant precoat material due to this defect in rust prevention. The second point is that excessive interfacial shear stress is generated at the plating-steel plate interface or the coating film-plating interface during high-speed or impactful bending deformation. In particular, plating of brittle intermetallic compounds is disadvantageous in terms of resistance to interfacial shear stress. For example, plating of Fe-Zn, Ni-Zn, etc. In many cases, considerable peeling occurs at the plating-steel plate interface. This essentially remains the same whether it is electrodeposition plating or melt plating. Zn plating, Zn-Al plating, etc.
This peeling is less likely to occur with non-intermetallic compound plating, but if the coating film thickness becomes too thick, peeling may occur at the coating film-plating interface. In summary, the present situation is that an inexpensive pre-coated plated steel plate that satisfies both the above-mentioned two points of rust prevention function and processing function cannot be found among the conventionally known Zn-based plated steel plates. (Object of the Invention) The present invention improves the above-mentioned problems of conventional pre-coated galvanized steel sheets, and has high high-speed workability (i.e., punchability, The purpose of the present invention is to provide a laminated galvanized steel sheet having excellent shearability and beautiful luster. (Structure of the invention) The gist of the present invention is that on the surface of a steel plate, as a lower layer,
Coated with Fe at 1.5 to 50 g/ m2 , and further coated with Ni content of 9 to 20% (hereinafter, all weight percentages are shown).
Ni-Zn alloy or Fe-Zn with Fe content of 7-40%
It is a plated steel plate having a laminated structure coated with 2 to 80 g/m 2 of alloy. The underlying coating is, for example, a solid solution of metal crystals such as Cu-Ni, a mixed phase thereof, or Cd,
It may be a mixture of Fe, Pb, etc. and Zn, but it must not be an intermetallic compound. The reason is that intermetallic compounds are brittle and cannot follow high-speed or impactful bending deformation of the steel sheet. In the present invention, Fe is the most suitable metal for the lower layer. This is because by adding Fe to the lower layer, conventionally known Fe-Zn plating or
This is because there is almost no electrochemical difference with Ni-Zn plating, the rust prevention function of Ni-Zn or Fe-Zn plating is exhibited as is, and the cost is low. The reason for the numerical limitation in the present invention is as follows. If the coating amount of the lower layer is less than 1.5 g/m 2 , it is insufficient to cover the entire surface, and no improvement in impact resistance after coating can be expected. If the amount of Fe exceeds 20 g/m 2 , the effect will be saturated and it will become uneconomical, so the upper limit was set at 20 g/m 2 . The plating on the upper layer is preferably Ni-Zn or Fe-Zn. The reason for this is that these platings have less blistering of the coating film on the end face, that is, they have greater corrosion resistance as referred to here. If the Ni content in Ni-Zn plating is less than 9%, Zn
Corrosion resistance decreases due to coexistence of phases. Moreover, when it exceeds 20%, Ni phase coexists, and chemical conversion properties and anticorrosion properties decrease. In the case of Fe-Zn plating, if the Fe content is less than 7%, the η phase will be co-electrodeposited and the corrosion resistance will decrease after coating.
%, the ferrite phase eutectoids and induces red rust on cut parts, etc. The amount of adhesion of the plating layer covering the upper layer must be 2 g/m 2 or more and 80 g/m 2 or less. If it is less than 2 g/m 2 , corrosion resistance including edge rust prevention is insufficient, and if it exceeds 80 g/m 2 , the amount of adhesion will be excessive, and in particular, bending workability, press formability, etc. will be deteriorated. The galvanized steel sheet according to the present invention exhibits superior performance compared to conventional galvanized steel sheets when coated with a paint, particularly a high-hardness paint, after a general chemical conversion treatment. The present invention will be further explained below with reference to Examples. (Example) SPCC grade soft rolled cold rolled steel plate (thickness 0.50mm)
was cut to 150 x 100 mm, steam-cleaned with trichlorethylene, electrolytically degreased in a sodium orthosilicate solution, and then electroplated with Zn and Fe under the electrolytic conditions shown in Table 1. . The electrolytic area is 1dm 2 . Next, after washing the steel plate with the lower layer plated, Table 2
Ni-Zn or Fe-Zn alloy electroplating was performed under the electrolytic conditions shown below. Separately, single layer Zn, Ni−Zn,
Electroplated samples such as Fe-Zn were prepared under the conditions shown in Tables 1 and 2. In addition, the total amount of adhesion is
It was set to 40g/ m2 . Each sample was subjected to the usual zinc phosphate treatment (Bonderite #3300, manufactured by Nippon Parker Co., Ltd.), then chromate sealing (Percolene #62, manufactured by Nippon Parker Co., Ltd.), and then acrylic baking paint (Primer 6μm, Topcoat 18μm). ) was applied using a bar coater. Next, each sample was heated to 12φ-1Kgf-50cm at 25℃.
Dupont impact test under the conditions of, clearance 0.06mm
A shearing test using an electric shear was conducted to evaluate high-speed processability. Furthermore, the four sides of the sample were sheared, and while the end faces of the four sides were exposed, they were subjected to a salt spray test according to JIS Z2371, and the blistering width of the coating film at the end face was measured after 480 hours. These results are shown in the accompanying drawings and Table 3. The attached drawing shows Ni-Zn plating on the upper layer and Fe plating on the lower layer.
It also shows the relationship between lower layer plating and various performances when Zn is applied. In the figure, the impact test score was 0 for plating peeling and 5 for no coating abnormality. As shown in the figure, the presence of at least 2 g/m 2 of the underlying metal body (excluding intermetallic compounds) can significantly improve high-speed processability. but,
It can be seen that when a base metal such as Zn is used, the end face corrosion resistance is significantly impaired. Table 3 shows Fe-Zn plating (Fe
This is a summary of various performances of pre-coated materials plated with 22% content. As seen in Table 3, although there are some differences depending on the base metal, within the scope of the present invention, it can be seen that the performance is particularly excellent compared to the comparative example. These results indicate that by interposing a ductile metal Fe between the brittle compound-based plating layer and the steel, some kind of stress relaxation mechanism is activated.
It is clear that the high-speed processability of precoated materials such as Ni-Zn and Fe-Zn can be improved. It is assumed that this method is an effective method that can be applied to improve the workability of brittle intermetallic compound plating, not only Fe-Zn and Ni-Zn.
【表】【table】
【表】【table】
【表】【table】
【表】
（発明の効果）
本発明は、従来課題のあつた金属間化合物系め
つき鋼板の加工性の改善に極めて大きな効果を有
し、耐食性と加工性に、共に秀れたプレコート材
を供給する有用な発明である。[Table] (Effects of the invention) The present invention has an extremely large effect on improving the workability of intermetallic compound-plated steel sheets, which has been a problem in the past, and provides a pre-coated material with excellent corrosion resistance and workability. This is a useful invention.
添付図面は、上層にNi−Znめつき、下層にFe
又はZnめつきを施した積層めつき鋼板の性能を
示す図である。
The attached drawing shows Ni-Zn plating on the upper layer and Fe plating on the lower layer.
Or, it is a figure showing the performance of the laminated galvanized steel plate which gave Zn plating.
Claims (1)
m2被覆し、更に上層としてNi含有率９〜20％の
Ni−Zn合金又はFe含有率７〜40％のFe−Zn合金
を２〜80ｇ／m2被覆したことを特徴とする積層め
つき鋼板。1 1.5 to 20 g of Fe is added as a lower layer on the surface of the steel plate.
m 2 coated with a Ni content of 9 to 20% as an upper layer.
A laminated plated steel sheet characterized by being coated with 2 to 80 g/m 2 of Ni-Zn alloy or Fe-Zn alloy with an Fe content of 7 to 40%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP23429983A JPS60128286A (en) | 1983-12-14 | 1983-12-14 | Double plated steel sheet |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP23429983A JPS60128286A (en) | 1983-12-14 | 1983-12-14 | Double plated steel sheet |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS60128286A JPS60128286A (en) | 1985-07-09 |
| JPH036235B2 true JPH036235B2 (en) | 1991-01-29 |
Family
ID=16968815
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP23429983A Granted JPS60128286A (en) | 1983-12-14 | 1983-12-14 | Double plated steel sheet |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS60128286A (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH075971B2 (en) * | 1987-12-31 | 1995-01-25 | 株式会社神戸製鋼所 | Method for producing alloy electroplated steel sheet for deep drawing with excellent impact peel resistance after painting |
| JP2532999B2 (en) * | 1991-01-29 | 1996-09-11 | 新日本製鐵株式会社 | Highly corrosion resistant surface treated steel sheet |
| JP2533000B2 (en) * | 1991-01-30 | 1996-09-11 | 新日本製鐵株式会社 | Highly corrosion resistant surface treated steel sheet |
| GB2345918B (en) | 1999-01-25 | 2003-03-12 | San O Ind Co | Steel product with plating layers |
| KR101879116B1 (en) * | 2014-04-08 | 2018-07-16 | 신닛테츠스미킨 카부시키카이샤 | Plated steel sheet |
| JP6468059B2 (en) * | 2015-05-01 | 2019-02-13 | 新日鐵住金株式会社 | Sn-plated steel sheet and method for producing Sn-plated steel sheet |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5635790A (en) * | 1979-08-29 | 1981-04-08 | Sumitomo Metal Ind Ltd | Surface treated steel sheet |
| JPS56166389A (en) * | 1980-05-28 | 1981-12-21 | Nippon Steel Corp | Zn type alloy coated steel plate of superior corrossion resistant phosphating property having two-layer coating layers |
| JPS58117890A (en) * | 1982-01-06 | 1983-07-13 | Kawasaki Steel Corp | Highly corrosion resistant surface treated steel plate |
-
1983
- 1983-12-14 JP JP23429983A patent/JPS60128286A/en active Granted
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5635790A (en) * | 1979-08-29 | 1981-04-08 | Sumitomo Metal Ind Ltd | Surface treated steel sheet |
| JPS56166389A (en) * | 1980-05-28 | 1981-12-21 | Nippon Steel Corp | Zn type alloy coated steel plate of superior corrossion resistant phosphating property having two-layer coating layers |
| JPS58117890A (en) * | 1982-01-06 | 1983-07-13 | Kawasaki Steel Corp | Highly corrosion resistant surface treated steel plate |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS60128286A (en) | 1985-07-09 |
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