EP0546914B1 - Bad und elektrolytisches Verfahren zur Aufbringung einer dünnen Beschichtung aus einer Eisen-Zink-Legierung mit einem hohen Eisengehalt auf ein galvanisiertes Legierungsubstrat - Google Patents

Bad und elektrolytisches Verfahren zur Aufbringung einer dünnen Beschichtung aus einer Eisen-Zink-Legierung mit einem hohen Eisengehalt auf ein galvanisiertes Legierungsubstrat Download PDF

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Publication number
EP0546914B1
EP0546914B1 EP92403307A EP92403307A EP0546914B1 EP 0546914 B1 EP0546914 B1 EP 0546914B1 EP 92403307 A EP92403307 A EP 92403307A EP 92403307 A EP92403307 A EP 92403307A EP 0546914 B1 EP0546914 B1 EP 0546914B1
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EP
European Patent Office
Prior art keywords
iron
bath
approximately
zinc alloy
galvanised
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
Application number
EP92403307A
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English (en)
French (fr)
Other versions
EP0546914A1 (de
Inventor
Franco Delfrate
Régis Doucet
Jacques Keller
Alain Popadenec
Isabelle Souedet
Sylviane Wajda
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.)
Sollac SA
Original Assignee
Sollac SA
Lorraine de Laminage Continu SA SOLLAC
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Publication date
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Publication of EP0546914A1 publication Critical patent/EP0546914A1/de
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/56—Electroplating: Baths therefor from solutions of alloys
    • C25D3/562—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of iron or nickel or cobalt

Definitions

  • the invention relates to a bath as well as to a method for depositing a flash coating of iron-zinc alloy on a substrate of alloyed galvanized steel, in particular a sheet of alloyed galvanized steel, known as "galvannealed" sheet.
  • “Galvanized-alloyed” sheets are coated steel sheets obtained by immersing the sheet in a pot of molten zinc and heat treatment of the coated sheet. Following the heat treatment, part of the iron in the substrate diffuses into the zinc coating layer so that it contains, after treatment, around 10% of iron.
  • These sheets however have several drawbacks, the most important being the production of a craterization phenomenon during the cataphoresis operation which makes the sheet unsuitable for certain uses such as the automotive industry where it tends to have an irregular surface after application. paint.
  • the means currently used to remedy these drawbacks consists in applying a coating of an iron-zinc alloy with a thickness of less than 1 ⁇ m, called a flash coating.
  • flash coatings are deposited industrially by means of baths containing Fe+ and Zn+ ions in sulfate medium, in a system with an insoluble anode.
  • JP-57/31504 describes an iron-zinc electroplating bath having the following composition: ZnSO4, 7H2: 150 g / l FeSO4, 7H2O: 300 g / l (NH4) 2 SO4: 30 g / l the pH of this bath being 1, 2.
  • the concentration of Fe3+ ions is controlled by passing the bath through a bed lined with zinc or iron particles.
  • the present invention aims to provide an electrolytic coating bath of an iron-zinc alloy intended to provide on a galvanized-alloy steel substrate, a flash coating having a high iron content and providing a high yield.
  • This bath is characterized in that it consists of an aqueous medium which comprises from 60 to 120 g / l of Fe+ ions in the form of chlorides, from 20 to 60 g / l of Zn+ ions in the as chlorides, 200 to 280 g / l KCl, 0.5 to 10 g / l ascorbic acid and 0 to 2 g / l KOH and has a pH of about 1.5 to about 2 , 5, and preferably about 2.
  • KCl also promotes the conductivity of the electrolytic bath and therefore makes it possible to reduce the energy cost of depositing the iron-zinc flash coating.
  • the presence of KOH has the effect of decreasing the aggressiveness of the bath by increasing the pH, thereby limiting the aggression of the galvanized-alloy steel sheet during the coating operation.
  • the Fe+ / Fe+ + Zn+ ratio is between 60 and 80%, by weight.
  • the subject of the invention is also a process for the electrolytic deposition of a flash coating of an iron-zinc alloy on a galvanized-alloy steel substrate, in particular a galvanized-alloy sheet, consisting in bringing the substrate forming cathode into contact. with an electrolytic bath according to the invention, with a current density between 20 and 200 A / dm, at a temperature between 55 and 65 ° C, in a system with soluble anode, to obtain an iron-zinc coating, having an iron content greater than 60% by weight, preferably about 80% by weight.
  • the galvanized-alloy steel sheets have an iron-zinc flash coating with a thickness of between 0.1 and 1 ⁇ m, and preferably equal to 0.5 ⁇ m.
  • the current density is around 100 A / dm.
  • the galvanized-alloy steel substrate is for example a galvanized-alloy steel sheet, called "galvannealed" sheet, the speed of travel in the electrolytic bath is advantageously from about 20 to about 200 m / min, preferably 100 m / min.
  • the soluble anode preferably consists of iron, but can also consist of zinc, for example in the form of ingot, sheet, particles or powder, or any other suitable form.
  • ascorbic acid is to control the amount of Fe3+ ions that form, by reducing Fe3+ ions to Fe+ ions according to the equation 2 Fe3+ + C6H8O6 ⁇ 2Fe+ + C6H6O6 + 2H+
  • the pH of the bath is around 2.
  • a flash-coating of an iron-zinc alloy is deposited on a "galvannealed" sheet comprising a zinc-iron coating containing 10% iron with a layer weight of 50 g / m.
  • the flash coating according to the invention is produced with an iron anode, the sheet to be coated forming a cathode.
  • the temperature of the bath is 60 ° C.
  • the current density is 100 A / dm.
  • the running speed of the steel strip is 100 m / min.
  • the flash coating obtained has a thickness of 0.5 ⁇ m with an iron percentage of 80%.
  • the yield of the deposit is 90%.
  • the Applicant has surprisingly and unexpectedly shown in the tests which follow that the method of the invention using a particular electrolytic bath to deposit an iron-zinc flash coating on a galvanized-alloy steel sheet provided the galvanized-alloy steel sheet thus coated, on the one hand a great ease of implementation shape, and on the other hand an improvement in its appearance after painting by eliminating the phenomenon of craterization at the cataphoresis tensions commonly used.
  • This test aims to illustrate, through a friction test, the ease of implementation of a galvanized-alloy steel sheet coated with an iron-zinc flash coating according to the method of the invention.
  • the test is carried out on two samples of galvanized-alloy steel sheet marked 1 and 2, the coating of which is made of iron-zinc alloy is obtained in a conventional manner by immersion of said sheet in a pot of molten zinc and by heat treatment of the sheet thus coated.
  • the coating thus formed of iron-zinc alloy has an iron content close to 10% and has for the two samples a thickness of the order of 8 ⁇ m, the thickness of the metallic substrate constituted by galvanized steel sheet- ally having a thickness of the order of 0.7 mm.
  • Each sample measures 40 cm long by 4 cm wide.
  • the sample 2 is brought into contact with an electrolytic coating bath according to the present invention and the composition of which is as follows:
  • the pH of the bath is around 2.
  • the friction test consists in placing each of the samples vertically between a tool and a cylinder, for example hydraulic, which applies to the sample a variable pressure corresponding to the drawing pressure usually used, while the sample is drawn vertically towards the top at constant speed equal to 0.1 m / min and with a force proportional to the drawing pressure.
  • Figure 2 clearly shows that a galvanized-alloy steel sheet coated with an iron-zinc flash is perfectly suited to shaping, given that for a drawing pressure of 700 bars, the coefficient friction is only 0.1083.
  • the purpose of this test is to show the resistance to craterization of galvanized-alloy steel sheets coated with an iron-zinc flash according to the invention during the cataphoresis operation.
  • test is carried out on two samples of galvanized-alloy steel sheet marked 1 and 2 as described in test 1.
  • Each of the samples is subjected to a cataphoresis of the PPG CORONA BLACK ED 3002 type, making it possible to apply a first layer of paint with a thickness of approximately 15 ⁇ m, which is subsequently fired.
  • the test consists in applying different electrical voltages to the electrolyte during the cataphoresis operation and recording for each voltage applied to the two samples the number of punctures per cm of surface.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Electroplating And Plating Baths Therefor (AREA)
  • Electroplating Methods And Accessories (AREA)

Claims (10)

  1. Galvanisches Bad zur Abscheidung einer Anschlaggalvanisierbeschichtung aus einer Eisen-Zink-Legierung auf einem Ausgangsmaterial aus galvanisiertem legiertem Stahl, dadurch gekennzeichnet, daß es aus einem wäßrigen Medium besteht, das 60 bis 120 g/l Fe⁺-Ionen in der Form von Chlorid, 20 bis 60 g/l Zn⁺-Ionen in der Form von Chlorid, 200 bis 280 g/l KCl, 0,5 bis 10 g/l Ascorbinsäure und 0 bis 2 g/l KOH umfaßt und einen pH-Wert von ungefähr 1,5 bis ungefähr 2,5 hat.
  2. Galvanisches Bad nach Anspruch 1, dadurch gekennzeichnet, daß der pH-Wert ungefähr 2 ist.
  3. Galvanisches Bad nach Anspruch 1, dadurch gekennzeichnet, daß das Verhältnis der Fe⁺-Ionen zur Summe der Fe⁺- und Zn⁺-Ionen, bezogen auf Gewicht, zwischen 60 und 80% liegt.
  4. Galvanisches Bad nach irgendeinem der Ansprüche 1 bis 3, dadurch gekennzeichnet, daß es die folgende Zusammensetzung hat:
    - Fe⁺ (in der Form von FeCl₂) : 84 g/l
    - Zn⁺ (in der Form von ZnCl₂) : 36 g/l
    - KCl : 250 g/l
    - Ascorbinsäure : 5 g/l
    - KOH : 0,5 g/l
    - H₂O : zum Auffüllen,
    wobei der pH-Wert des Bades ungefähr 2 ist.
  5. Verfahren zur galvanischen Abscheidung einer Beschichtung aus einer Eisen-Zink-Legierung auf einem Ausgangsmaterial aus galvanisiertem legiertem Stahl, gekennzeichnet durch In-Kontakt-bringen des die Kathode bildenden Ausgangsmaterials mit einen Bad zur galvanischen Beschichtung, wie in einem der Ansrüche 1 bis 4 definiert, mit einer Stromdichte zwischen 20 und 200 A/dm, bei einer Temperatur, die zwischen 55 und 65°C liegt, in einem löslichen Anodensystem, um eine Eisen-Zink-Beschichtung zu erhalten, die einen Eisengehalt von mehr als 60 Gew.-%, bevorzugt von ungefähr 80 Gew.-%, hat.
  6. Verfahren nach Anspruch 5, dadurch gekennzeichnet, daß eine Beschichtung aus einer Eisen-Zink-Legierung abgeschieden wird, die einen Eisengehalt von ungefähr 80 Gew.-% umfaßt.
  7. Verfahren nach Anspruch 5 oder 6, dadurch gekennzeichnet, daß die Stromdichte ungefähr 100 A/dm ist.
  8. Verfahren nach Anspruch 7, dadurch gekennzeichnet, daß das Ausgangsmaterial ein Blech aus galvanisiertem legiertem Stahl ist, und dadurch, daß die Durchlaufgeschwindigkeit des Blechs in dem Bad ungefähr 20 bis ungefähr 200 m/Min., bevorzugt 100 m/Min. , ist.
  9. Blech aus galvanisiertem legiertem Stahl, beschichtet durch das Verfahren nach einem der Ansprüche 5 bis 8, dadurch gekennzeichnet, daß die Anschlaggalvanisierbeschichtung aus Eisen-Zink-Legierung einen Eisengehalt von mehr als 60 Gew.-% und bevorzugt gleich 80 Gew.-% hat.
  10. Blech aus galvanisiertem legiertem Stahl, beschichtet nach Anspruch 9, dadurch gekennzeichnet, daß die Anschlaggalvanisierbeschichtung aus Eisen-Zink-Legierung eine Stärke zwischen 0,1 bis 1 µm und bevorzugt gleich 0,5 µm hat.
EP92403307A 1991-12-13 1992-12-07 Bad und elektrolytisches Verfahren zur Aufbringung einer dünnen Beschichtung aus einer Eisen-Zink-Legierung mit einem hohen Eisengehalt auf ein galvanisiertes Legierungsubstrat Expired - Lifetime EP0546914B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR9115535 1991-12-13
FR9115535A FR2685013A1 (fr) 1991-12-13 1991-12-13 Bain et procede electrolytique de depot d'un revetement-flash d'un alliage fer-zinc a haut pourcentage en fer sur un substrat galvanise-allie.

Publications (2)

Publication Number Publication Date
EP0546914A1 EP0546914A1 (de) 1993-06-16
EP0546914B1 true EP0546914B1 (de) 1996-05-15

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EP92403307A Expired - Lifetime EP0546914B1 (de) 1991-12-13 1992-12-07 Bad und elektrolytisches Verfahren zur Aufbringung einer dünnen Beschichtung aus einer Eisen-Zink-Legierung mit einem hohen Eisengehalt auf ein galvanisiertes Legierungsubstrat

Country Status (6)

Country Link
EP (1) EP0546914B1 (de)
JP (1) JPH05247681A (de)
AT (1) ATE138115T1 (de)
DE (1) DE69210775T2 (de)
ES (1) ES2089460T3 (de)
FR (1) FR2685013A1 (de)

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100417616B1 (ko) * 1999-12-22 2004-02-05 주식회사 포스코 인산염처리성 및 도장후 내식성이 우수한 아연-코발트-비스무스 합금 전기도금 강판의 제조방법
KR101288085B1 (ko) * 2012-10-11 2013-08-07 남동화학(주) 전기아연 도금용 복합아연 플래쉬 도금용액, 이를 이용한 전기아연 도금방법 및 이에 의해 제조된 전기아연도금강판
EP2784189A1 (de) 2013-03-28 2014-10-01 Coventya SAS Elektroplattierungsbad für Zink-Eisen-Legierungen, Verfahren zur Ablagerung von Zink-Eisen-Legierung auf einer Vorrichtung sowie solche Vorrichtung
CN107923056B (zh) * 2015-08-11 2020-11-10 Posco公司 利用闪镀锌溶液制造的电镀锌钢板及其制造方法
CN107805830A (zh) * 2017-10-11 2018-03-16 武汉钢铁有限公司 闪镀铁镀液及闪镀方法
CN111270276A (zh) * 2020-03-28 2020-06-12 武汉钢铁有限公司 闪镀锌镀液及其制备方法与闪镀方法

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4444629A (en) * 1982-05-24 1984-04-24 Omi International Corporation Zinc-iron alloy electroplating baths and process

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
CHEMICAL ABSTRACTS, vol. 104, no. 22, 1986, Columbus, Ohio, US; abstract no. 195509u, KIYONO 'manufacture of zinc-iron type alloy electroplated steel sheets having excellent adherence' page 597 ; & JP-A-6130696 *

Also Published As

Publication number Publication date
ES2089460T3 (es) 1996-10-01
DE69210775D1 (de) 1996-06-20
ATE138115T1 (de) 1996-06-15
FR2685013B1 (de) 1994-12-16
DE69210775T2 (de) 1996-10-02
JPH05247681A (ja) 1993-09-24
EP0546914A1 (de) 1993-06-16
FR2685013A1 (fr) 1993-06-18

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