JPH01162795A - Zinc-chromium double-electroplated steel sheet - Google Patents

Zinc-chromium double-electroplated steel sheet

Info

Publication number
JPH01162795A
JPH01162795A JP31983187A JP31983187A JPH01162795A JP H01162795 A JPH01162795 A JP H01162795A JP 31983187 A JP31983187 A JP 31983187A JP 31983187 A JP31983187 A JP 31983187A JP H01162795 A JPH01162795 A JP H01162795A
Authority
JP
Japan
Prior art keywords
steel sheet
layer
corrosion resistance
plating
electroplated steel
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
Application number
JP31983187A
Other languages
Japanese (ja)
Other versions
JPH0715153B2 (en
Inventor
Tatsuya Kanamaru
金丸 辰也
Motohiro Nakayama
元宏 中山
Katsutoshi Arai
新井 勝利
Shinichi Suzuki
眞一 鈴木
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nippon Steel Corp
Original Assignee
Nippon Steel Corp
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Nippon Steel Corp filed Critical Nippon Steel Corp
Priority to JP62319831A priority Critical patent/JPH0715153B2/en
Priority to DE88104874T priority patent/DE3882769T2/en
Priority to EP88104874A priority patent/EP0285931B1/en
Priority to US07/174,830 priority patent/US4897317A/en
Priority to AU13897/88A priority patent/AU597163B2/en
Priority to CA000562971A priority patent/CA1336698C/en
Priority to KR1019880003622A priority patent/KR910002186B1/en
Priority to US07/320,071 priority patent/US4877494A/en
Publication of JPH01162795A publication Critical patent/JPH01162795A/en
Priority to CA000616731A priority patent/CA1336699C/en
Priority to CA000616732A priority patent/CA1336700C/en
Priority to CA000616830A priority patent/CA1337054C/en
Publication of JPH0715153B2 publication Critical patent/JPH0715153B2/en
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

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  • Electroplating Methods And Accessories (AREA)

Abstract

PURPOSE:To produce a Zn-Cr double electroplated steel sheet having superior corrosion resistance and suitability to coating by forming a Zn-Cr plating layer contg. a specified amt. of Cr as an inner layer and a Zn or Zn alloy plating layer as an outer layer on a steel sheet by electroplating. CONSTITUTION:A Zr-Cr plating layer contg. 5-40% Cr as an inner layer is formed on a steel sheet by electroplating at >= about 50A/dm<2> current density in an acidic plating bath contg. Zn ions, tervalent Cr ions and a Cr deposition accelerator. A Zn or Zn alloy plating layer as an outer layer is then formed by electroplating by about 1-1.5g/m<2>. In case of the Zn alloy, the Zn content is regulated to >= about 60%. A double-electroplated steel sheet for rust prevention having high corrosion resistance and also having superior corrosion resistance after coating is obtd.

Description

【発明の詳細な説明】 (産業上の利用分野) 本発明は、自動車、家電、建材等に使用される耐食性お
よび塗装適合性に優れた防錆用の複層電気めっき鋼板に
関する。
DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a multilayer electroplated steel sheet for rust prevention, which is used in automobiles, home appliances, building materials, etc. and has excellent corrosion resistance and paint compatibility.

(従来の技術) ZnないしZn系合金めっき中にCrを含有せしめた電
気めっき鋼板としては、例えば特公昭61−36078
号、特公昭5B−56039号2特開昭61−2703
98号等が公知であるが、Crの共析率が0.005〜
5%までの極めて微量であって、耐食性にとってCrの
効果は付随的でしかあり得ない。従って耐食性を改善す
る目的からは更に高含量のCrを共析させることが強く
望まれるところである。
(Prior art) As an electroplated steel sheet containing Cr in Zn or Zn-based alloy plating, for example, Japanese Patent Publication No. 61-36078
No., JP 5B-56039 No. 2, JP 61-2703
No. 98 etc. are known, but the eutectoid rate of Cr is 0.005 to
In extremely small amounts of up to 5%, the effect of Cr on corrosion resistance can only be incidental. Therefore, for the purpose of improving corrosion resistance, it is strongly desired to eutectoid a higher content of Cr.

(発明が解決しようとする問題点) しかしながら、従来Cr共析率を高め得るZn−Cr電
気めっき技術がなかった。即ち、単にめっき浴中の3価
Crイオン濃度を高めても、密着性のある正常なめっき
が得られず、電流効率も急減する等の障害があって、工
業的にCr共析率を高めることは極めて困難であった。
(Problems to be Solved by the Invention) However, conventionally there has been no Zn-Cr electroplating technology capable of increasing the Cr eutectoid rate. That is, even if the concentration of trivalent Cr ions in the plating bath is simply increased, normal plating with adhesion cannot be obtained, and there are problems such as a sudden decrease in current efficiency, and it is difficult to increase the Cr eutectoid rate industrially. This was extremely difficult.

本発明者らはCr含有率の高いZn−Cr系電るにつれ
、塗装前処理として常用される化成処理において、リン
酸塩皮膜が不完全にしか形成されないため、塗装後の耐
食性がめつき層自身の効果によって若干改善されるもの
の、それほど大巾な改善は期待できなかった。
The present inventors discovered that as Zn-Cr systems with high Cr content are developed, the phosphate film is only incompletely formed in the chemical conversion treatment commonly used as a pre-painting treatment. Although there was some improvement due to the effects of

本発明は上記問題点に鑑みなされたもので、塗装後の耐
食性を大巾に改善させた電気めっき鋼板を提供する。
The present invention was made in view of the above problems, and provides an electroplated steel sheet whose corrosion resistance after painting is greatly improved.

(問題点を解決するための手段) 本発明は、Cr5〜40%を含有するZn−Cr系電気
めっき層を内層とし、外層をZnまたはZnを主体とす
る合金めっき層から構成される亜鉛−クロム系複層電気
めっき鋼板である。
(Means for Solving the Problems) The present invention has a zinc-Cr electroplated layer containing 5 to 40% Cr as an inner layer, and an outer layer consisting of Zn or an alloy plating layer mainly composed of Zn. It is a chromium-based multilayer electroplated steel sheet.

(作 用) 本復層めっき鋼板の耐食性は、主としてZn−Cr系電
気めっき層の作用である。Zn−Cr系めっき層中のC
rの含有量は、5%以上が好ましい。5%未満では耐食
性効果は顕著ではない。例えば塩水噴霧試験によれば、
Cr含有量5%以上になると赤錆発生が大巾に抑制され
、7%以上になると、1ケ月間の試験で赤錆がほとんど
発生しない程度の驚くべき耐食性が認められる。
(Function) The corrosion resistance of the present double-layer plated steel sheet is mainly a function of the Zn-Cr electroplated layer. C in Zn-Cr based plating layer
The content of r is preferably 5% or more. If it is less than 5%, the corrosion resistance effect is not significant. For example, according to the salt spray test,
When the Cr content is 5% or more, the occurrence of red rust is greatly suppressed, and when the Cr content is 7% or more, surprising corrosion resistance is observed to the extent that almost no red rust occurs during a one-month test.

このような高耐食性は、従来公知のZnめっき、あるい
はZn−Fe、Zn−Ni等の合金めっきでは到底達成
することはできない。
Such high corrosion resistance cannot be achieved by conventionally known Zn plating or alloy plating such as Zn-Fe or Zn-Ni.

CrはZnとの共存下では不働態化せず、Znとともに
犠牲防食作用に加担し、しかもCrの腐食生成物が難溶
性の保護皮膜として腐食部に沈積することにより腐食を
抑制していることが、高耐食性を発揮する理由であろう
と考えられる。
Cr does not passivate when coexisting with Zn, but participates in the sacrificial anticorrosion effect together with Zn, and furthermore, corrosion products of Cr deposit in the corroded areas as a poorly soluble protective film, thereby suppressing corrosion. This is thought to be the reason why it exhibits high corrosion resistance.

Cr含有量が40%を越えると、耐食性はあるものの、
プレス加工等の加工時にめっき層が剥離する所謂ゆるパ
ウダリング性が劣化するため、実用上は適用が難しい。
When the Cr content exceeds 40%, although it has corrosion resistance,
It is difficult to apply it practically because the so-called powdering property, in which the plating layer peels off during processing such as press working, deteriorates.

外層のZnまたはZnを主体とする合金めっき層は、化
成処理において健全なリン酸塩皮膜を形成する作用をも
つ。その結果、塗装後の耐食性を向上させる効果をもつ
。内層のZn−Crめっき層が化成処理中に表面に露出
しなければ良いのであって、そのためには外層の目付量
は1〜15g/rrfあることが好ましい。Znを主体
とする合金めっき層としては、Zn−Fe、Zn−Ni
The outer Zn or Zn-based alloy plating layer has the effect of forming a healthy phosphate film during chemical conversion treatment. As a result, it has the effect of improving corrosion resistance after painting. It is sufficient that the inner Zn-Cr plating layer is not exposed to the surface during the chemical conversion treatment, and for this purpose, the outer layer preferably has a basis weight of 1 to 15 g/rrf. As the alloy plating layer mainly composed of Zn, Zn-Fe, Zn-Ni
.

Zn−Mn、Zn−Co等であり、Znは60%以上で
よく、これらはいづれもZnめっきと同様に、スプレー
型あるいは浸漬型リン酸塩処理において、健全で性能の
良いリン酸塩皮膜を形成でき、それはクロレートあるい
はフッ化物等の促進剤の種類を問わない。
These include Zn-Mn, Zn-Co, etc., and the Zn content may be 60% or more, and all of these can produce a healthy and high-performance phosphate film in spray-type or immersion-type phosphate treatment, similar to Zn plating. can be formed regardless of the type of promoter such as chlorate or fluoride.

該外層には、上記金属の他少量のSn、Cd。The outer layer contains small amounts of Sn and Cd in addition to the above metals.

Al2.Pb、Cu、Ag、P、C,O,Sb。Al2. Pb, Cu, Ag, P, C, O, Sb.

Ti等を含んでもよく、Crでさえ、約1%程度なら許
容できる。また必要なら、酸化物等の共析も許容できる
It may contain Ti, etc., and even Cr is permissible in an amount of about 1%. Furthermore, if necessary, eutectoid deposition of oxides etc. is also acceptable.

次に製造態様について説明する。Next, the manufacturing mode will be explained.

Zn−Cr系内層のめっき法は、Znイオン。The plating method for the Zn-Cr inner layer is Zn ion.

3価CrイオンおよびCr析出促進剤を含む酸性めっき
浴から、電流密度50A/drd以上でCr5〜40%
含有するZn−Crめっきを電析させることができる。
From an acidic plating bath containing trivalent Cr ions and a Cr precipitation promoter, 5 to 40% Cr is removed at a current density of 50 A/drd or more.
The contained Zn-Cr plating can be electrodeposited.

Cr析出促進剤としては、例えばポリエチレングリコー
ル、アルキルポリエチレンエーテル、ポリオキシメチレ
ン誘導体、α−エトキシレーテッドナフトールおよびあ
るいはそのスルフォン酸誘導体等のポリオキシアルキレ
ン誘導体類を0.01〜20g/(2添加使用する。他
の態様としては、Si。
As a Cr precipitation accelerator, for example, polyoxyalkylene derivatives such as polyethylene glycol, alkyl polyethylene ether, polyoxymethylene derivatives, α-ethoxylated naphthol and/or its sulfonic acid derivative can be added at 0.01 to 20 g/(2). In another embodiment, Si.

Al、Zr、Ti、Sb、Sn、Cr、Mo、Ce等の
酸化物コロイド類を2〜200g/j2添加使用するこ
とができる。まためっき層中にこれらを析出させても良
い。
Oxide colloids such as Al, Zr, Ti, Sb, Sn, Cr, Mo, Ce, etc. can be added in an amount of 2 to 200 g/j2. Moreover, these may be precipitated in the plating layer.

他に電導度付与剤としてNa” 、に’ 、NH4”等
のアルカリ金属イオンを添加することもできる。陰イオ
ンとしては硫酸浴、塩化浴いずれも適用でき、pHは0
.5〜3が適当である。
In addition, alkali metal ions such as Na'', Ni'', NH4'', etc. may be added as conductivity imparting agents. Both a sulfuric acid bath and a chloride bath can be used as anions, and the pH is 0.
.. 5 to 3 is appropriate.

他に6価クロムイオン、鉄2価、3価イオン等不可避的
に共存するイオンはもちろん、Ni。
There are other ions that inevitably coexist, such as hexavalent chromium ions, divalent iron, and trivalent iron ions, as well as Ni.

Co、Mn、Cu、Ag、Sn、Sb、Cd。Co, Mn, Cu, Ag, Sn, Sb, Cd.

Pb、Mo、A/2.Mg等のイオンを必要あれば添加
し、まためっき層中に析出させてもよい。
Pb, Mo, A/2. If necessary, ions such as Mg may be added and precipitated into the plating layer.

めっき液の流速は、鋼帯との相対速度として30〜20
0 m/min 、めっき温度は40〜70’Cが適当
である。
The flow rate of the plating solution is 30 to 20% relative to the steel strip.
0 m/min and a plating temperature of 40 to 70'C are appropriate.

外層の亜鉛または亜鉛を主体とする合金めっきは、周知
の電気めっき法を適用することができる。
A well-known electroplating method can be applied to the outer layer of zinc or zinc-based alloy plating.

その場合、内層めっきから持ち出されるCrイオンドラ
グアウドを十分水洗除去することが好ましい。外層は比
較的薄いめっきの場合には、ドライめっき法等を適用す
ることも可能である。
In that case, it is preferable to thoroughly wash away the Cr ion dragaud taken out from the inner layer plating. If the outer layer is plated relatively thinly, it is also possible to apply a dry plating method or the like.

(実施例) 次に本発明の実施例を比較例とともに第1表に挙げる。(Example) Next, Examples of the present invention are listed in Table 1 along with comparative examples.

第  1  表 注1) ′内層めっき条件は、Z n 2 +  イオン56g
/l。
Table 1 Note 1) 'Inner layer plating conditions are Z n 2 + ion 56g
/l.

Cr”″ イオン44g/j2.Na”イオン15g/
lを硫酸塩として建浴、ポリエチレングリコール(分子
量=1500)を1gノ!添加したpH=2.0+ 5
0°Cのめっき浴を用いて、冷延鋼板(0,7m厚)に
めっき液流速60m/分、電流密度100 A/dI1
12で実施例9の内層めっきを施こした。他の実施例及
び比較例2はそれぞれ条件を変えて製造した。
Cr"" ion 44g/j2. Na” ion 15g/
Prepare a bath with 1 sulfate and 1 g of polyethylene glycol (molecular weight = 1500)! Added pH=2.0+5
Using a 0°C plating bath, a plating solution flow rate of 60 m/min and a current density of 100 A/dI1 were applied to a cold rolled steel plate (0.7 m thick).
In No. 12, the inner layer plating of Example 9 was applied. Other Examples and Comparative Example 2 were manufactured under different conditions.

注2) 外層めっき条件は周知の条件でめっきを施こした。Note 2) The outer layer was plated under well-known conditions.

このようにして製造した複層めっき鋼板を第2第2表 注、3)裸めっき鋼板の耐食性 塩水の噴霧試験(JIS Z2371に準拠)により7
20hr後の赤錆発生面積%をあられす。
The multi-layer plated steel sheet produced in this manner was tested in Table 2, Note 3) Corrosion resistance of bare plated steel sheet Salt water spray test (according to JIS Z2371).
Check the area percentage of red rust after 20 hours.

注4)リン酸塩処理性 浸漬型リン酸塩処理での皮膜結晶状態を評価する。Note 4) Phosphate treatability Evaluate the crystalline state of the film after immersion phosphate treatment.

O: 緻密な結晶 Δ: 粗大結晶 注5)塗装板の耐食性 浸漬型リン酸塩処理、カチオン電着塗装20μmを施こ
し、中塗り、水研ぎ、上塗り塗装をして総合塗膜厚80
μmとし、クロスカットを入れた試験片を屋外に曝露し
た。曝露期間中−週間に1回の割にて5%食塩水をサン
プル上に撒布し、10週間後のクロスカット部の錆巾で
評価した(mm)。
O: Dense crystals Δ: Coarse crystals Note 5) Corrosion resistance of the painted plate Apply dipped phosphate treatment, cationic electrodeposition coating of 20 μm, intermediate coating, water sanding, and top coating to achieve a total coating thickness of 80
A test piece with cross-cuts made in micrometers was exposed outdoors. During the exposure period - 5% saline was sprinkled on the sample once a week, and the rust width at the cross-cut portion was evaluated after 10 weeks (mm).

(発明の効果) 以上述べたように本発明によれば、高耐食性で、かつ塗
装後の耐食性にも優れた防錆用の複層電気めっき鋼板が
得られる。
(Effects of the Invention) As described above, according to the present invention, a multilayer electroplated steel sheet for rust prevention that has high corrosion resistance and excellent corrosion resistance after coating can be obtained.

Claims (1)

【特許請求の範囲】[Claims] (1)Cr5〜40%を含有するZn−Cr系電気めっ
き層を内層とし、外層をZnまたはZnを主体とする合
金めっき層から構成される亜鉛−クロム系複層電気めっ
き鋼板。
(1) A zinc-chromium multilayer electroplated steel sheet comprising an inner layer of a Zn-Cr electroplated layer containing 5 to 40% of Cr, and an outer layer of Zn or an alloy plating layer mainly composed of Zn.
JP62319831A 1987-03-31 1987-12-17 Zinc-chromium multi-layer electroplated steel sheet Expired - Fee Related JPH0715153B2 (en)

Priority Applications (11)

Application Number Priority Date Filing Date Title
JP62319831A JPH0715153B2 (en) 1987-12-17 1987-12-17 Zinc-chromium multi-layer electroplated steel sheet
DE88104874T DE3882769T2 (en) 1987-03-31 1988-03-25 Corrosion-resistant plated steel strip and process for its manufacture.
EP88104874A EP0285931B1 (en) 1987-03-31 1988-03-25 Corrosion resistant plated steel strip and method for producing same
US07/174,830 US4897317A (en) 1987-03-31 1988-03-29 Corrosion resistant Zn-Cr plated steel strip
AU13897/88A AU597163B2 (en) 1987-03-31 1988-03-30 Corrosion resistant plated steel strip and method for producing same
CA000562971A CA1336698C (en) 1987-03-31 1988-03-30 Corrosion resistant plated steel strip and method for producing same
KR1019880003622A KR910002186B1 (en) 1987-03-31 1988-03-31 Corrosion resistant zn-cr plated steel strip
US07/320,071 US4877494A (en) 1987-03-31 1989-03-07 Corrosion resistant plated steel strip and method for producing same
CA000616731A CA1336699C (en) 1987-03-31 1993-09-21 Corrosion resistant plated steel strip and method for producing same
CA000616732A CA1336700C (en) 1987-03-31 1993-09-21 Corrosion resistant plated steel strip and method for producing same
CA000616830A CA1337054C (en) 1987-03-31 1994-03-07 Corrosion resistant plated steel strip and method for producing same

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP62319831A JPH0715153B2 (en) 1987-12-17 1987-12-17 Zinc-chromium multi-layer electroplated steel sheet

Publications (2)

Publication Number Publication Date
JPH01162795A true JPH01162795A (en) 1989-06-27
JPH0715153B2 JPH0715153B2 (en) 1995-02-22

Family

ID=18114699

Family Applications (1)

Application Number Title Priority Date Filing Date
JP62319831A Expired - Fee Related JPH0715153B2 (en) 1987-03-31 1987-12-17 Zinc-chromium multi-layer electroplated steel sheet

Country Status (1)

Country Link
JP (1) JPH0715153B2 (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH03166396A (en) * 1989-11-24 1991-07-18 Nippon Steel Corp Highly corrosion resistant composite electroplated steel sheet excellent in chemical conversion treating property and its production
JPH03166397A (en) * 1989-11-24 1991-07-18 Nippon Steel Corp Highly corrosion resistant composite electroplated steel sheet excellent in chemical conversion treating property and weldability and its production

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5891163A (en) * 1981-11-24 1983-05-31 Kobe Steel Ltd Manufacture of composite zinc plated steel plate with superior suitability to coating
JPS6082691A (en) * 1983-10-12 1985-05-10 Nippon Kokan Kk <Nkk> Multilayer plated steel sheet

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5891163A (en) * 1981-11-24 1983-05-31 Kobe Steel Ltd Manufacture of composite zinc plated steel plate with superior suitability to coating
JPS6082691A (en) * 1983-10-12 1985-05-10 Nippon Kokan Kk <Nkk> Multilayer plated steel sheet

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH03166396A (en) * 1989-11-24 1991-07-18 Nippon Steel Corp Highly corrosion resistant composite electroplated steel sheet excellent in chemical conversion treating property and its production
JPH03166397A (en) * 1989-11-24 1991-07-18 Nippon Steel Corp Highly corrosion resistant composite electroplated steel sheet excellent in chemical conversion treating property and weldability and its production

Also Published As

Publication number Publication date
JPH0715153B2 (en) 1995-02-22

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