JPH07278873A - Method for producing high Ni-containing Zn-Ni plated steel sheet excellent in corrosion resistance and powdering resistance - Google Patents
Method for producing high Ni-containing Zn-Ni plated steel sheet excellent in corrosion resistance and powdering resistanceInfo
- Publication number
- JPH07278873A JPH07278873A JP7359994A JP7359994A JPH07278873A JP H07278873 A JPH07278873 A JP H07278873A JP 7359994 A JP7359994 A JP 7359994A JP 7359994 A JP7359994 A JP 7359994A JP H07278873 A JPH07278873 A JP H07278873A
- Authority
- JP
- Japan
- Prior art keywords
- steel sheet
- plated steel
- resistance
- corrosion resistance
- powdering
- 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
- 238000000227 grinding Methods 0.000 title claims abstract description 25
- 229910000831 Steel Inorganic materials 0.000 title claims abstract description 18
- 238000005260 corrosion Methods 0.000 title claims abstract description 18
- 230000007797 corrosion Effects 0.000 title claims abstract description 18
- 239000010959 steel Substances 0.000 title claims abstract description 18
- 229910007567 Zn-Ni Inorganic materials 0.000 title claims abstract description 16
- 229910007614 Zn—Ni Inorganic materials 0.000 title claims abstract description 16
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 12
- 238000007747 plating Methods 0.000 claims abstract description 22
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims abstract description 12
- 150000002500 ions Chemical class 0.000 claims abstract description 11
- TUOWYJFPLMIKCX-UHFFFAOYSA-N 2-ethoxynaphthalen-1-amine Chemical compound C1=CC=CC2=C(N)C(OCC)=CC=C21 TUOWYJFPLMIKCX-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000009713 electroplating Methods 0.000 claims abstract description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 4
- RUFPHBVGCFYCNW-UHFFFAOYSA-N 1-naphthylamine Chemical compound C1=CC=C2C(N)=CC=CC2=C1 RUFPHBVGCFYCNW-UHFFFAOYSA-N 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000002253 acid Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 235000002639 sodium chloride Nutrition 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 239000010960 cold rolled steel Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Landscapes
- Electroplating And Plating Baths Therefor (AREA)
- Electroplating Methods And Accessories (AREA)
Abstract
(57)【要約】
【目的】 本発明は自動車、家電用のＺｎ−Ｎｉめっき
鋼板の製造方法にかかわり、２−エトキシ−α−ナフチ
ルアミンスルホン酸をＺｎ−Ｎｉめっき浴に添加するこ
とにより、従来困難であった高Ｎｉ含有時の耐パウダリ
ング性を確保し、あわせて耐食性に優れたＺｎ−Ｎｉめ
っき鋼板の製造方法を提供するものである。これは、自
動車用途を中心に高耐食性、耐パウダリング性が要求さ
れる防錆鋼板を製造する上で極めて効果的である。
【構成】 電気Ｚｎ−Ｎｉめっき鋼板を製造するに際
し、Ｚｎ2+イオン、Ｎｉ2+イオン及び０．０１〜１．０
ｇ／ｌの２−エトキシ−α−ナフチルアミンスルホン酸
を含有するめっき浴を用いて電気めっきを行う。こうし
て得られたＺｎ−Ｎｉめっき鋼板は耐食性、耐パウダリ
ング性に優れた高Ｎｉ含有Ｚｎ−Ｎｉめっき鋼板とな
る。
(57) [Abstract] [Objective] The present invention relates to a method for producing a Zn-Ni plated steel sheet for automobiles and home appliances, which comprises adding a 2-ethoxy-α-naphthylamine sulfonic acid to a Zn-Ni plating bath. It is intended to provide a method for producing a Zn-Ni plated steel sheet which secures the powdering resistance at the time of containing a high amount of Ni, which is difficult, and also has excellent corrosion resistance. This is extremely effective for producing a rust-preventive steel plate which is required to have high corrosion resistance and powdering resistance mainly for automobiles. [Structure] When manufacturing an electric Zn-Ni plated steel sheet, Zn 2+ ions, Ni 2+ ions and 0.01 to 1.0 are used.
Electroplating is carried out using a plating bath containing g / l of 2-ethoxy-α-naphthylamine sulfonic acid. The Zn-Ni plated steel sheet thus obtained becomes a high Ni-containing Zn-Ni plated steel sheet having excellent corrosion resistance and powdering resistance.
Description
【０００１】[0001]
【産業上の利用分野】本発明は自動車、家電用の鋼板に
かかわり、耐食性、耐パウダリング性に優れた高Ｎｉ含
有Ｚｎ−Ｎｉ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 Zn-Ni plated steel sheet having a high Ni content, which relates to a steel sheet for automobiles and home appliances and which is excellent in corrosion resistance and powdering resistance.
【０００２】[0002]
【従来の技術】電気Ｚｎ−Ｎｉめっき鋼板は自動車、家
電用途を中心に幅広く使用されている。このうち自動車
用途では、寒冷地帯における冬期の道路凍結防止用の散
布岩塩による車体腐食を防止するために、より高度な耐
食性が要求されている。従来技術ではＺｎ−Ｎｉめっき
鋼板の耐食性の向上は、めっき付着量の増加あるいはＮ
ｉ含有率の増加で可能であるが、耐パウダリング性の低
下や溶接性低下の点で問題が多い。2. Description of the Related Art Electric Zn-Ni plated steel sheets are widely used mainly for automobiles and home appliances. Among them, in automobile applications, higher corrosion resistance is required in order to prevent car body corrosion due to sprayed rock salt for road freezing prevention in winter in cold regions. In the prior art, the improvement of the corrosion resistance of the Zn-Ni plated steel sheet is due to the increase of the coating amount or N
Although it is possible to increase the i content, there are many problems in that the powdering resistance and weldability are deteriorated.
【０００３】[0003]
【発明が解決しようとする課題】本発明は上記問題点を
解決するため、耐パウダリング性を確保したままＺｎ−
Ｎｉめっき中のＮｉ含有率を向上させて耐食性向上を図
ったＺｎ−Ｎｉめっき鋼板の製造方法を提供するもので
ある。SUMMARY OF THE INVENTION In order to solve the above-mentioned problems, the present invention aims to solve the problems of Zn-- while maintaining powdering resistance.
The present invention provides a method for producing a Zn-Ni plated steel sheet in which the Ni content in Ni plating is improved to improve the corrosion resistance.
【０００４】[0004]
【課題を解決するための手段】本発明の要旨は、電気Ｚ
ｎ−Ｎｉめっき鋼板を製造するに際し、Ｚｎ2+イオン、
Ｎｉ2+イオン及び０．０１〜１．０ｇ／ｌの２−エトキ
シ−α−ナフチルアミンスルホン酸を含有するめっき浴
を用いて、電気めっきを行うことを特徴とする耐食性、
耐パウダリング性に優れた高Ｎｉ含有Ｚｎ−Ｎｉめっき
鋼板の製造方法である。The gist of the present invention is to provide an electric Z
When manufacturing an n-Ni plated steel sheet, Zn 2+ ions,
Corrosion resistance characterized by performing electroplating using a plating bath containing Ni 2+ ions and 0.01 to 1.0 g / l of 2-ethoxy-α-naphthylamine sulfonic acid,
It is a method of manufacturing a high Ni-containing Zn-Ni plated steel sheet having excellent powdering resistance.
【０００５】[0005]
【作用】以下本発明について説明する。２−エトキシ−
α−ナフチルアミンスルホン酸の添加量は０．０１〜
１．０ｇ／ｌとする。０．０１ｇ／ｌ未満では耐パウダ
リング性の改善効果がなく、Ｎｉ含有量１４ｗｔ％以上
ではプレス成形性などに問題がある。また、１．０ｇ／
ｌを超えるとやはり耐パウダリング性が低下するのと、
めっき電流効率が低下し、生産性に問題を生じる。The present invention will be described below. 2-ethoxy-
The addition amount of α-naphthylamine sulfonic acid is 0.01 to
It is set to 1.0 g / l. If it is less than 0.01 g / l, there is no effect of improving the powdering resistance, and if the Ni content is 14 wt% or more, there is a problem in press formability. In addition, 1.0 g /
If it exceeds 1, the powdering resistance will decrease,
Plating current efficiency decreases, causing a problem in productivity.
【０００６】図１に２−エトキシ−α−ナフチルアミン
スルホン酸の添加量と耐パウダリング性の関係を示す。
めっき中のＮｉ％が１１％，１４％，１７％の３水準に
なるようめっき条件を調整している。他のめっき浴組成
は同じである。２−エトキシ−α−ナフチルアミンスル
ホン酸０．０１ｇ／ｌ未満では耐パウダリング性の評点
は６以下であるが、０．０１〜１．０ｇ／ｌの範囲では
評点７以上となり、１．０を超えると、また評点６以下
に低下する。FIG. 1 shows the relationship between the amount of 2-ethoxy-α-naphthylamine sulfonic acid added and the powdering resistance.
The plating conditions are adjusted so that the Ni% in the plating becomes three levels of 11%, 14%, and 17%. Other plating bath compositions are the same. When 2-ethoxy-α-naphthylaminesulfonic acid is less than 0.01 g / l, the powdering resistance has a rating of 6 or less, but in the range of 0.01 to 1.0 g / l, the rating is 7 or more. If it exceeds, the score will drop to 6 or less.
【０００７】めっき浴としては、硫酸浴、塩化物浴、こ
れらの混合浴のいずれも適用できる。金属イオン濃度に
ついては、Ｚｎ2+イオン、Ｎｉ2+イオンの合計で３０〜
２００ｇ／ｌが好ましい。３０ｇ／ｌ未満では高電流密
度でイオンの供給不足となりやすく、結果としてめっき
焼けを生じやすい。２００ｇ／ｌを超えると、ドラッグ
アウトによるイオンの浪費が無視できなくなるととも
に、液温が低くなった場合の結晶化の懸念を生じる。そ
の他のめっき条件については、特に制約されるものでは
ないが、ｐＨ＝０．５〜３．０、浴温４０〜７０℃、液
流速１ｍ／ｍｉｎ以上、電流密度２０Ａ／ｄｍ2 以上が
好ましい範囲であり、目的とするめっき組成、電流効率
を考慮して最適な条件を採用することができる。めっき
浴中には、Ｎａ+ 、ＮＨ4 + イオンなどの電導度助剤を
添加してもよく、本発明の製造方法に本質的な支障はな
い。めっき層中Ｎｉ含有量は１０〜１７％が好ましい。
１０％未満では耐食性に劣り、１７％を超えると耐パウ
ダリング性が低下してくる。As the plating bath, any of a sulfuric acid bath, a chloride bath and a mixed bath thereof can be applied. Regarding the metal ion concentration, the total of Zn 2+ ions and Ni 2+ ions is 30 to
200 g / l is preferred. If it is less than 30 g / l, the supply of ions tends to be insufficient at a high current density, and as a result, plating burn is likely to occur. If it exceeds 200 g / l, the waste of ions due to dragout cannot be ignored, and there is a concern of crystallization when the liquid temperature becomes low. Other plating conditions are not particularly limited, but preferable ranges are pH = 0.5 to 3.0, bath temperature 40 to 70 ° C., liquid flow rate 1 m / min or more, and current density 20 A / dm 2 or more. Therefore, the optimum conditions can be adopted in consideration of the intended plating composition and current efficiency. A conductivity auxiliary agent such as Na + and NH 4 + ions may be added to the plating bath, and there is no essential obstacle to the production method of the present invention. The Ni content in the plating layer is preferably 10 to 17%.
If it is less than 10%, the corrosion resistance is poor, and if it exceeds 17%, the powdering resistance is deteriorated.
【０００８】[0008]
【実施例】冷延鋼板をアルカリ脱脂し、５％硫酸で酸洗
した後、表１および表２に示す条件で電気めっきを行っ
た。めっき浴としては硫酸浴を用い、めっき付着量は３
０ｇ／ｍ2 とした。こうして得られためっき組成と耐食
性、耐パウダリングの評価を表２に示す。耐食性は塩水
噴霧試験（ＪＩＳ Ｚ２３７１に準拠）を５００時間行
い以下の要領で判定した。◎：赤錆１％以下，〇：赤錆
10％以下，△：赤錆50％以下，×：赤錆50％超耐パウダ
リング性に関しては、ＯＴ折り曲げ後のテープ剥離を行
い、テープに付着しためっき量にて１０段階の評点をつ
け、７点以上を合格レベルとした。EXAMPLE A cold rolled steel sheet was degreased with alkali, pickled with 5% sulfuric acid, and then electroplated under the conditions shown in Tables 1 and 2. A sulfuric acid bath is used as the plating bath, and the coating weight is 3
It was set to 0 g / m 2 . Table 2 shows the evaluation of the plating composition, corrosion resistance, and powdering resistance thus obtained. The corrosion resistance was evaluated by a salt spray test (according to JIS Z2371) for 500 hours and the following procedure. ◎: Red rust 1% or less, ◯: Red rust
10% or less, △: Red rust 50% or less, ×: Red rust 50% For powdering resistance, peel the tape after OT bending and give a 10-point rating according to the amount of plating adhered to the tape, and score 7 points. The above is the passing level.
【０００９】[0009]
【表１】 [Table 1]
【００１０】[0010]
【表２】 [Table 2]
【００１１】表１及び表２において、比較例１は２−エ
トキシ−α−ナフチルアミンスルホン酸の添加がないた
め、耐パウダリング性を確保するとＮｉ含有量が低い領
域のものしか得られず耐食性が低下している。また、比
較例２は２−エトキシ−α−ナフチルアミンスルホン酸
の添加なしにＮｉ含有量を高めた結果、耐パウダリング
性を確保できていない。比較例３は、２−エトキシ−α
−ナフチルアミンスルホン酸を適量添加しているが、め
っき層中のＮｉ含有量を上げすぎたため、耐パウダリン
グ性が低下している。In Tables 1 and 2, Comparative Example 1 does not contain 2-ethoxy-α-naphthylamine sulfonic acid, so that if powdering resistance is secured, only Ni content in the low region is obtained and corrosion resistance is improved. It is falling. Further, in Comparative Example 2, as a result of increasing the Ni content without adding 2-ethoxy-α-naphthylamine sulfonic acid, the powdering resistance cannot be secured. Comparative Example 3 is 2-ethoxy-α.
-Although a proper amount of naphthylamine sulfonic acid was added, the powdering resistance was lowered because the Ni content in the plating layer was too high.
【００１２】比較例４は２−エトキシ−α−ナフチルア
ミンスルホン酸の添加が少ないためめっき中のＮｉ含有
量を増やすと耐パウダリング性が低下している。また、
比較例５は２−エトキシ−α−ナフチルアミンスルホン
酸の添加量が多すぎるため効果がなく、めっき中のＮｉ
含有量を増やすと耐パウダリング性が低下している。こ
れに対し本発明例は、いずれの場合も１４％以上の高Ｎ
ｉ含有量となり耐食性が良好である上に、耐パウダリン
グ性も良好であるのがわかる。In Comparative Example 4, since the addition of 2-ethoxy-α-naphthylamine sulfonic acid was small, the powdering resistance was lowered when the Ni content in the plating was increased. Also,
Comparative Example 5 had no effect because the amount of 2-ethoxy-α-naphthylaminesulfonic acid added was too large, and Ni during plating was
When the content is increased, the powdering resistance is lowered. On the other hand, in all the cases of the present invention, high N of 14% or more was obtained.
It can be seen that the content is i and the corrosion resistance is good, and the powdering resistance is also good.
【００１３】[0013]
【発明の効果】以上説明したように、本発明は２−エト
キシ−α−ナフチルアミンスルホン酸をＺｎ−Ｎｉめっ
き浴に添加することにより、従来困難であった高Ｎｉ含
有時の耐パウダリング性を確保し、あわせて耐食性に優
れたＺｎ−Ｎｉめっき鋼板の製造方法を提供するもので
ある。これは、自動車用途を中心に高耐食性、耐パウダ
リング性が要求される防錆鋼板を製造する上で極めて効
果的である。As described above, according to the present invention, by adding 2-ethoxy-α-naphthylamine sulfonic acid to the Zn-Ni plating bath, the powdering resistance at the time of containing high Ni, which has been difficult in the past, can be obtained. It is intended to provide a method for manufacturing a Zn-Ni plated steel sheet which is secured and also has excellent corrosion resistance. This is extremely effective for producing a rust-preventive steel plate which is required to have high corrosion resistance and powdering resistance mainly for automobiles.
【図１】２−エトキシ−α−ナフチルアミンスルホン酸
の添加量と耐パウダリング性との関係を示す図である。FIG. 1 is a graph showing the relationship between the amount of 2-ethoxy-α-naphthylamine sulfonic acid added and powdering resistance.
Claims (1)
際し、Ｚｎ2+イオン、Ｎｉ2+イオン及び０．０１〜１．
０ｇ／ｌの２−エトキシ−α−ナフチルアミンスルホン
酸を含有するめっき浴を用いて電気めっきを行うことを
特徴とする耐食性、耐パウダリング性に優れた高Ｎｉ含
有Ｚｎ−Ｎｉめっき鋼板の製造方法。1. When manufacturing an electric Zn-Ni plated steel sheet, Zn 2+ ions, Ni 2+ ions and 0.01-1.
Electrolytic plating is performed using a plating bath containing 0 g / l 2-ethoxy-α-naphthylamine sulfonic acid, and a method for producing a high Ni-containing Zn-Ni plated steel sheet having excellent corrosion resistance and powdering resistance. .
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6073599A JP3032112B2 (en) | 1994-04-12 | 1994-04-12 | Method for producing high Ni-containing Zn-Ni plated steel sheet excellent in corrosion resistance and powdering resistance |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6073599A JP3032112B2 (en) | 1994-04-12 | 1994-04-12 | Method for producing high Ni-containing Zn-Ni plated steel sheet excellent in corrosion resistance and powdering resistance |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH07278873A true JPH07278873A (en) | 1995-10-24 |
| JP3032112B2 JP3032112B2 (en) | 2000-04-10 |
Family
ID=13522953
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP6073599A Expired - Fee Related JP3032112B2 (en) | 1994-04-12 | 1994-04-12 | Method for producing high Ni-containing Zn-Ni plated steel sheet excellent in corrosion resistance and powdering resistance |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3032112B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NL1018972C2 (en) | 2001-09-18 | 2003-03-19 | Antonie Herman De Leeuw | Delivery box for goods unable to fit through letterbox, has flexible depth and is accessible via delivery flap and security flaps |
| KR100419659B1 (en) * | 1999-12-20 | 2004-02-25 | 주식회사 포스코 | A plating solution for blackening zinc-nickel alloy coated steel sheet and electroplating method for zinc-nickel steel sheet |
| KR100506394B1 (en) * | 2000-12-22 | 2005-08-10 | 주식회사 포스코 | Zn-Ni alloy electrolyte for good surface roughness, whiteness and suppression of edge burning |
-
1994
- 1994-04-12 JP JP6073599A patent/JP3032112B2/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100419659B1 (en) * | 1999-12-20 | 2004-02-25 | 주식회사 포스코 | A plating solution for blackening zinc-nickel alloy coated steel sheet and electroplating method for zinc-nickel steel sheet |
| KR100506394B1 (en) * | 2000-12-22 | 2005-08-10 | 주식회사 포스코 | Zn-Ni alloy electrolyte for good surface roughness, whiteness and suppression of edge burning |
| NL1018972C2 (en) | 2001-09-18 | 2003-03-19 | Antonie Herman De Leeuw | Delivery box for goods unable to fit through letterbox, has flexible depth and is accessible via delivery flap and security flaps |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3032112B2 (en) | 2000-04-10 |
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