JP2562607B2 - Method for producing zinc-chromium composite electroplated steel sheet - Google Patents
Method for producing zinc-chromium composite electroplated steel sheetInfo
- Publication number
- JP2562607B2 JP2562607B2 JP62195344A JP19534487A JP2562607B2 JP 2562607 B2 JP2562607 B2 JP 2562607B2 JP 62195344 A JP62195344 A JP 62195344A JP 19534487 A JP19534487 A JP 19534487A JP 2562607 B2 JP2562607 B2 JP 2562607B2
- Authority
- JP
- Japan
- Prior art keywords
- zinc
- steel sheet
- electroplated steel
- plating
- chromium composite
- 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
Landscapes
- Electroplating And Plating Baths Therefor (AREA)
- Electroplating Methods And Accessories (AREA)
Description
【発明の詳細な説明】 （産業上の利用分野） 本発明は耐食性の優れた亜鉛−クロム系複合電気めっ
き鋼板の製造方法に関する。TECHNICAL FIELD The present invention relates to a method for producing a zinc-chromium composite electroplated steel sheet having excellent corrosion resistance.
（従来技術、発明の解決しようとする問題点） 亜鉛−３価クロム電気めっき法に関しては例えば特公
昭61−36078、特公昭58−56039、特開昭61−270398に見
られる如く、Crの共析率が0.005〜５％までの極めて微
量の範囲が開示されているのみである。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が、単に３価クロムイオン濃度を高
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、工業的には極めて困難
であった。(Prior Art, Problems to be Solved by the Invention) Regarding the zinc-trivalent chromium electroplating method, as shown in, for example, Japanese Patent Publication No. 61-36078, Japanese Patent Publication No. 58-56039, and Japanese Patent Publication No. Only the extremely minute range of the deposition rate of 0.005 to 5% is disclosed. For the purpose of improving the corrosion resistance, it is strongly desired to co-deposit a higher content of Cr, but even if the trivalent chromium ion concentration is simply increased, normal plating with good adhesion cannot be obtained, and current efficiency is increased. However, there were obstacles such as a sharp decrease, and it was extremely difficult industrially.
一方、SiO2、Al2O3コロイド等を亜鉛系合金めっきに
複合共析させる方法も知られている。（例えば特開昭61
−127900、61−270398、61−235600、61−266599等。） しかしながら、このような酸化物コロイド自身を共析
させることを開示しているのみで、金属析出に対する作
用を示唆しているものではない。On the other hand, there is also known a method in which SiO 2 , Al 2 O 3 colloid, etc. are subjected to complex codeposition on a zinc alloy plating. (For example, JP-A-61
-127900, 61-270398, 61-235600, 61-266599, etc. However, it only discloses that such an oxide colloid itself is co-deposited, and does not suggest any action on metal precipitation.
本発明は耐食性に対する要求を有利に解決するため、
更に高いCr含有率まで容易に製造できる技術を提供しよ
うとするものである。The present invention advantageously solves the requirement for corrosion resistance,
It is an object of the present invention to provide a technique capable of easily producing a higher Cr content.
（問題点を解決するための手段） 本発明の特徴とするところは、亜鉛イオン20〜70g/
、３価クロムイオン10〜70g/からなり、更にSi,Zr,
Ti,Sb,Sn,Cr,Mo,Ceの１種以上からなる酸化物コロイド
２〜200g/、Na+9〜18g/からなる酸性めっき浴で、
電流密度120超〜250A/dm2で電着せしめ、めっき層組成
を金属Cr（Cr:7〜40％）、酸化物微粒子、残部Znとした
ことを特徴とする亜鉛−クロム系複合電気めっき鋼板の
製造方法に関するものである。(Means for Solving Problems) The feature of the present invention is that zinc ion is 20 to 70 g /
Consisting of trivalent chromium ions 10-70g /, Si, Zr,
An acid plating bath consisting of 2 to 200 g / of oxide colloid consisting of one or more of Ti, Sb, Sn, Cr, Mo and Ce, and Na + 9 to 18 g /
A zinc-chromium composite electroplated steel sheet characterized by being electrodeposited at a current density of over 120 to 250 A / dm 2 and having a plating layer composition of metallic Cr (Cr: 7 to 40%), oxide fine particles, and the balance Zn. The present invention relates to a manufacturing method of.
（作 用） 元来、亜鉛−３価クロムめっき系は、相合わないめっ
き系である。即ち、めっき浴中の亜鉛イオン比率を高め
ると、Znは析出するが、Crはほとんど析出しない。一方
３価クロムイオン比率を高めると、亜鉛の析出が著しく
抑制され、クロムも正常に析出しなくなる。(Working) Originally, the zinc-trivalent chromium plating system is a plating system that does not match. That is, when the proportion of zinc ions in the plating bath is increased, Zn is deposited but Cr is hardly deposited. On the other hand, when the ratio of trivalent chromium ions is increased, the precipitation of zinc is remarkably suppressed, and chromium also does not precipitate normally.
ところが、この系に例えばSi,Zr,Ti,Sb,Sn,Cr,Mo,Ce
の１種以上の酸化物コロイドを添加すると、ZnもCrも電
析されてくるのである。この理由は定かではない。しか
し次のように考えられる。即ち、亜鉛は水酸化物境膜を
介して電析するとされている。一方３価クロムを水和物
ないし水酸化物境膜を形成し、それを介して電析すると
考えられる。両者が形成する水和物ないしは水酸化物境
膜が互いに相手の電析を妨害するので、Zn−Cr系の共析
が困難になっていると考えられる。However, in this system, for example, Si, Zr, Ti, Sb, Sn, Cr, Mo, Ce
When one or more kinds of oxide colloids are added, both Zn and Cr are electrodeposited. The reason for this is unclear. However, it can be considered as follows. That is, zinc is said to be electrodeposited through the hydroxide boundary film. On the other hand, it is considered that trivalent chromium forms a hydrate or hydroxide boundary film, and is electrodeposited through the film. Since the hydrate or hydroxide boundary film formed by both interferes with the electrodeposition of the other, it is considered difficult to co-deposit the Zn-Cr system.
上記酸化物コロイドはめっき境膜に吸着することによ
り、前２者の境膜を乱し、コロイド粒子表面を介して金
属の析出する通路を作るものと考えられる。以上は仮説
にすぎないが、これに従えば少くとも現像は良く理解で
きる。It is considered that the above oxide colloid adsorbs to the plating film to disturb the former film and to form a path for metal precipitation through the surface of the colloidal particles. Although the above is only a hypothesis, development can be understood at least well if this is followed.
上記酸化物コロイドは粒径１μｍ以下のものを使用す
るのが、めっきの均一性の点で好ましい。酸化物コロイ
ドのめっき浴中添加量は２〜200g/、より好ましくは1
0〜100g/が適当である。2g/未満であれば、酸化物
コロイドの添加効果はほとんどなく、2g/以上で共析
させることができ、特に10g/以上添加すれば、Crを共
析できる適正電流密度がより低い領域まで広い範囲にわ
たって操業できるので有利である。It is preferable to use an oxide colloid having a particle size of 1 μm or less from the viewpoint of plating uniformity. The amount of oxide colloid added in the plating bath is 2-200 g /, more preferably 1
0-100 g / is suitable. If it is less than 2 g /, there is almost no effect of adding the oxide colloid, and it can be co-deposited at 2 g / or more. Especially, if it is added at 10 g / or more, the appropriate current density where Cr can be co-deposited is wide to a lower region. It is advantageous because it can operate over a range.
酸化物コロイドを複合共析させ、より耐食性を高める
目的では酸化物コロイドの添加量をより高めることが有
利である。しかしながら、コロイド濃度が高くなるにつ
れ、コロイド粒子が凝集する確率が増えることになり、
100g/を越えるとややコロイドの安定性が劣化する傾
向が現われ、200g/が上限である。It is advantageous to increase the addition amount of the oxide colloid for the purpose of complex eutectoid oxide colloid and further enhancing the corrosion resistance. However, as the colloid concentration increases, the probability of colloidal particles aggregating increases,
If it exceeds 100 g /, the stability of the colloid tends to deteriorate, and 200 g / is the upper limit.
２種以上の酸化物コロイドを添加する場合は共凝集し
ない組合せを用いるべきである。When adding two or more oxide colloids, a combination that does not coaggregate should be used.
３価クロムイオン濃度は、10〜70g/が好ましく、10
g/未満では、亜鉛イオンとの比率を調整してもCr含有
率の高いめっき層を得ることが困難であり、又70g/超
になると亜鉛イオン濃度を調整しても亜鉛の電析が抑制
され、従って電流効率が急減して工業的に実施するに
は、極めて不利である。亜鉛イオン濃度は、目的とする
めつき組成に応じて調整することができるが、20〜70g/
の範囲で好ましく実施例できる。The trivalent chromium ion concentration is preferably 10 to 70 g /
If it is less than g /, it is difficult to obtain a plating layer with a high Cr content even if the ratio with zinc ions is adjusted, and if it exceeds 70 g /, zinc electrodeposition is suppressed even if the zinc ion concentration is adjusted. Therefore, the current efficiency is drastically reduced, which is extremely disadvantageous for industrial implementation. The zinc ion concentration can be adjusted according to the intended plating composition, but is 20 to 70 g /
The preferred embodiment can be carried out within the range.
めっき浴の陰イオンに関しては硫酸浴、塩化浴ともに
適用可能である。めっき浴のpH3〜１の範囲が好まし
い。Regarding the anion of the plating bath, both a sulfuric acid bath and a chloride bath can be applied. The pH of the plating bath is preferably in the range of 3 to 1.
更に、Na+イオンの無関係塩を添加することは、浴の
電導度を高め、酸化物コロイドの析出調整効果を補助す
るため有効である。Furthermore, the addition of an irrelevant salt of Na + ions is effective in increasing the conductivity of the bath and assisting the effect of controlling the precipitation of the oxide colloid.
なお、目的に応じては、Fe,Mn,Cu,Sn,Cd,Pbのイオン
を少量添加しても本発明の効果は本質的には変らない。Depending on the purpose, even if a small amount of Fe, Mn, Cu, Sn, Cd, and Pb ions are added, the effect of the present invention is essentially unchanged.
次にめっき条件について説明する。 Next, the plating conditions will be described.
電流密度は120A/dm2超ではCrを７％以上と高Crの共析
が確実にでき、250A/dm2を超えると、Crの析出は飽和
し、実用上は電圧が上昇するので好ましくない。When the current density exceeds 120 A / dm 2, it is possible to reliably deposit Cr with high Cr of 7% or more, and when it exceeds 250 A / dm 2 , precipitation of Cr is saturated and the voltage rises in practice, which is not preferable. .
電流密度を高めれば酸化物コロイドもまた共析し易く
なる。しかしながら、浴成分を調整することにより、酸
化物コロイドをほとんど共析させないでCrを共析させる
ことも可能である。If the current density is increased, the oxide colloid will also be easily codeposited. However, by adjusting the bath components, it is also possible to co-deposit Cr without almost co-depositing the oxide colloid.
流速は相対速流（めっき液流速と鋼帯速度の差）とし
て10〜200m/minが適当である。めっき温度は40〜70℃が
適当である。The appropriate flow velocity is 10 to 200 m / min as a relative velocity (difference between plating solution velocity and steel strip velocity). A suitable plating temperature is 40 to 70 ° C.
かくすることにより、得られるめっき層の組成はCr:7
〜40％、酸化物微粒子：痕跡〜20％、残部Znからなる耐
食性に極めて優れた電気めっき鋼板を製造することがで
きる。By doing so, the composition of the plating layer obtained is Cr: 7
It is possible to manufacture an electroplated steel sheet having excellent corrosion resistance consisting of -40%, oxide fine particles: traces-20%, and balance Zn.
（実施例） 次に本発明の実施例を比較例とともに表に挙げる。(Examples) Next, examples of the present invention are listed in a table together with comparative examples.
（発明の効果） かくすることにより、耐食性に優れた高クロム含有率
の亜鉛−クロム系複合電気めっき鋼板を工業的に容易に
製造することができる。 (Effect of the Invention) By doing so, a zinc-chromium composite electroplated steel sheet having a high chromium content and excellent corrosion resistance can be industrially easily manufactured.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 鈴木 真一 愛知県東海市東海町５―３ 新日本製鐵 株式会社名古屋製鐵所内 (56)参考文献 特開 昭64−39398（ＪＰ，Ａ) 特開 昭60−125395（ＪＰ，Ａ) 特開 昭62−54099（ＪＰ，Ａ) 特開 昭61−270398（ＪＰ，Ａ) 特開 昭62−48539（ＪＰ，Ａ) ─────────────────────────────────────────────────── --- Continuation of front page (72) Inventor Shinichi Suzuki 5-3 Tokai-cho, Tokai City, Aichi Pref. Nippon Steel Co., Ltd. Nagoya Works (56) Reference Japanese Patent Laid-Open No. 64-39398 (JP, A) Kai 60-125395 (JP, A) JP 62-54099 (JP, A) JP 61-270398 (JP, A) JP 62-48539 (JP, A)
Claims (1)
10〜70g/からなり、更にSi,Zr,Ti,Sb,Sn,Cr,Mo,Ceの
１種以上からなる酸化物コロイド２〜200g/、Na+9〜1
8g/からなる酸性めっき浴で、電流密度120超〜250A/d
m2で電着せしめ、めっき層組成を金属Cr（Cr:7〜40
％）、酸化物微粒子、残部Znとしたことを特徴とする亜
鉛−クロム系複合電気めっき鋼板の製造方法。1. Zinc ion 20 to 70 g / trivalent chromium ion
Oxide colloid consisting of 10-70 g /, and more than one kind of Si, Zr, Ti, Sb, Sn, Cr, Mo, Ce 2-200 g /, Na + 9-1
8g / acid plating bath, current density over 120 ~ 250A / d
Electroplated with m 2 and plated layer composition is metallic Cr (Cr: 7 ~ 40
%), Oxide fine particles, and the balance Zn, and a method for producing a zinc-chromium composite electroplated steel sheet.
Priority Applications (11)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62195344A JP2562607B2 (en) | 1987-08-06 | 1987-08-06 | Method for producing zinc-chromium composite electroplated steel sheet |
| EP88104874A EP0285931B1 (en) | 1987-03-31 | 1988-03-25 | Corrosion resistant plated steel strip and method for producing same |
| DE88104874T DE3882769T2 (en) | 1987-03-31 | 1988-03-25 | Corrosion-resistant plated steel strip and process for its manufacture. |
| US07/174,830 US4897317A (en) | 1987-03-31 | 1988-03-29 | Corrosion resistant Zn-Cr plated steel strip |
| CA000562971A CA1336698C (en) | 1987-03-31 | 1988-03-30 | Corrosion resistant plated steel strip and method for producing same |
| AU13897/88A AU597163B2 (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 |
| CA000616732A CA1336700C (en) | 1987-03-31 | 1993-09-21 | 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 |
| 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 |
|---|---|---|---|
| JP62195344A JP2562607B2 (en) | 1987-08-06 | 1987-08-06 | Method for producing zinc-chromium composite electroplated steel sheet |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6439399A JPS6439399A (en) | 1989-02-09 |
| JP2562607B2 true JP2562607B2 (en) | 1996-12-11 |
Family
ID=16339608
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62195344A Expired - Lifetime JP2562607B2 (en) | 1987-03-31 | 1987-08-06 | Method for producing zinc-chromium composite electroplated steel sheet |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2562607B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2707085B2 (en) | 1987-08-06 | 1998-01-28 | 新日本製鐵株式会社 | Zinc-chromium composite electroplated steel sheet |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5100563A (en) * | 1991-01-28 | 1992-03-31 | Hirotsugu Suzuki | Method for introducing pure hot-spring water directly transported from a spa into a spa house bath and for maintaining the purity and freshness of the introduced water |
| KR100370472B1 (en) * | 1998-12-02 | 2003-04-10 | 주식회사 포스코 | Cr Solution for Coating Steel Sheets |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60125395A (en) * | 1983-12-09 | 1985-07-04 | Kawasaki Steel Corp | Zn-alumina composite electroplated steel sheet having high corrosion resistance |
| JPS61270398A (en) * | 1985-05-25 | 1986-11-29 | Kawasaki Steel Corp | Composite plated steel sheet having high corrosion resistance and its manufacture |
| JPH0228464B2 (en) * | 1985-08-28 | 1990-06-25 | Nippon Steel Corp | KOTAISHOKUSEIYOSETSUKANOTOSOKOHAN |
| JPH0718040B2 (en) * | 1985-09-02 | 1995-03-01 | 川崎製鉄株式会社 | Composite plated steel sheet excellent in spot weldability and corrosion resistance and method for producing the same |
-
1987
- 1987-08-06 JP JP62195344A patent/JP2562607B2/en not_active Expired - Lifetime
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2707085B2 (en) | 1987-08-06 | 1998-01-28 | 新日本製鐵株式会社 | Zinc-chromium composite electroplated steel sheet |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6439399A (en) | 1989-02-09 |
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