EP0546914B1 - Bain et procédé électrolytique de dépot d'un revetement-flash d'un alliage fer-zinc à haut pourcentage en fer sur un substrat galvanisé-allié - Google Patents

Bain et procédé électrolytique de dépot d'un revetement-flash d'un alliage fer-zinc à haut pourcentage en fer sur un substrat galvanisé-allié Download PDF

Info

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
Authority
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
Other languages
German (de)
English (en)
French (fr)
Other versions
EP0546914A1 (fr
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
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 Sollac SA, Lorraine de Laminage Continu SA SOLLAC filed Critical Sollac SA
Publication of EP0546914A1 publication Critical patent/EP0546914A1/fr
Application granted granted Critical
Publication of EP0546914B1 publication Critical patent/EP0546914B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

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)
EP92403307A 1991-12-13 1992-12-07 Bain et procédé électrolytique de dépot d'un revetement-flash d'un alliage fer-zinc à haut pourcentage en fer sur un substrat galvanisé-allié Expired - Lifetime EP0546914B1 (fr)

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 (fr) 1993-06-16
EP0546914B1 true EP0546914B1 (fr) 1996-05-15

Family

ID=9420052

Family Applications (1)

Application Number Title Priority Date Filing Date
EP92403307A Expired - Lifetime EP0546914B1 (fr) 1991-12-13 1992-12-07 Bain et procédé électrolytique de dépot d'un revetement-flash d'un alliage fer-zinc à haut pourcentage en fer sur un substrat galvanisé-allié

Country Status (6)

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

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 (en) 2013-03-28 2014-10-01 Coventya SAS Electroplating bath for zinc-iron alloys, method for depositing zinc-iron alloy on a device and such a device
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
JPH05247681A (ja) 1993-09-24
DE69210775T2 (de) 1996-10-02
FR2685013A1 (fr) 1993-06-18
FR2685013B1 (enrdf_load_stackoverflow) 1994-12-16
ES2089460T3 (es) 1996-10-01
DE69210775D1 (de) 1996-06-20
EP0546914A1 (fr) 1993-06-16
ATE138115T1 (de) 1996-06-15

Similar Documents

Publication Publication Date Title
JP2002510749A (ja) 選択された単体添加剤を配合した被覆
EP2450470A1 (fr) Traitement de surface par hydroxysultate
EP2947180B1 (en) Manufacturing method for zinc-plated steel sheet
EP0546914B1 (fr) Bain et procédé électrolytique de dépot d'un revetement-flash d'un alliage fer-zinc à haut pourcentage en fer sur un substrat galvanisé-allié
CA2348924A1 (en) Battery sheath made of a formed cold-rolled sheet and method for producing battery sheaths
EP0025396B1 (fr) Procédé d'élaboration d'un matériau pour la fabrication d'emballages métalliques, notamment boîtes à conserves, constitué d'une tôle d'acier protégée
CA2343016C (fr) Toles d'acier zingue revetues d'une couche prelubrifiante d'hydroxysulfate et procedes d'obtention de cette tole
JP4864493B2 (ja) 缶用めっき鋼板
FR2594855A1 (fr) Feuille d'acier traitee en surface pour boites soudees et son procede de production
FR2460346A1 (fr) Procede pour preparer des toles d'acier revetues par galvanoplastie, ayant une excellente adherence des peintures
KR100234452B1 (ko) 아연계 도금 강판 및 그 제조방법
US3959099A (en) Electrolytic method of producing one-side-only coated steel
US3383293A (en) Processes for drawing and coating metal substrates
US3838024A (en) Method of improving the corrosion resistance of substrates
JP2004027263A (ja) 表面外観に優れた溶融亜鉛めっき鋼板とその製造方法
US3364057A (en) Metal hydroxide intermediate coating for metal
JPH0689472B2 (ja) 製缶用薄Ｓｎメツキ鋼板及びその製造方法
US5316652A (en) Method for manufacturing iron-zinc alloy plated steel sheet having two plating layers and excellent in electropaintability and pressformability
EP0704558B1 (fr) Cellule d'électrodéposition en continu d'alliages métalliques
JP3097472B2 (ja) プレス成形性に優れた合金化溶融亜鉛メッキ鋼板およびその製造方法
JPS58151490A (ja) 着色電気亜鉛めつき金属板の製造法
EP0890655B1 (fr) Procédé de traitement de surface de tôles d'acier galvanisé allié et tôle obtenue.
EP0111039A1 (fr) Procédé de galvanisation et de recuit en continu à grande vitesse d'un fil métallique
JPH0431039B2 (enrdf_load_stackoverflow)
CN115928164A (zh) 钝化马口铁表面的方法以及用于实施该方法的电解系统

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE CH DE DK ES FR GB GR IT LI LU NL PT SE

17P Request for examination filed

Effective date: 19930521

17Q First examination report despatched

Effective date: 19950504

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AT BE CH DE DK ES FR GB GR IT LI LU NL PT SE

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 19960515

Ref country code: DK

Effective date: 19960515

REF Corresponds to:

Ref document number: 138115

Country of ref document: AT

Date of ref document: 19960615

Kind code of ref document: T

ITF It: translation for a ep patent filed
REF Corresponds to:

Ref document number: 69210775

Country of ref document: DE

Date of ref document: 19960620

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SE

Effective date: 19960815

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: PT

Effective date: 19960816

GBT Gb: translation of ep patent filed (gb section 77(6)(a)/1977)

Effective date: 19960816

REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2089460

Country of ref document: ES

Kind code of ref document: T3

REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2089460

Country of ref document: ES

Kind code of ref document: T3

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LI

Effective date: 19961231

Ref country code: CH

Effective date: 19961231

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

26N No opposition filed
REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

K2C3 Correction of patent specification (complete document) published

Effective date: 19960515

REG Reference to a national code

Ref country code: GB

Ref legal event code: IF02

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: AT

Payment date: 20021121

Year of fee payment: 11

Ref country code: NL

Payment date: 20021121

Year of fee payment: 11

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 20021129

Year of fee payment: 11

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: ES

Payment date: 20021209

Year of fee payment: 11

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20021211

Year of fee payment: 11

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: LU

Payment date: 20021216

Year of fee payment: 11

Ref country code: FR

Payment date: 20021216

Year of fee payment: 11

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: BE

Payment date: 20030102

Year of fee payment: 11

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20031207

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20031207

Ref country code: AT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20031207

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: ES

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20031209

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20031231

BERE Be: lapsed

Owner name: *SOLLAC

Effective date: 20031231

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20040701

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20040701

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20031207

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20040831

NLV4 Nl: lapsed or anulled due to non-payment of the annual fee

Effective date: 20040701

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

REG Reference to a national code

Ref country code: ES

Ref legal event code: FD2A

Effective date: 20031209

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES;WARNING: LAPSES OF ITALIAN PATENTS WITH EFFECTIVE DATE BEFORE 2007 MAY HAVE OCCURRED AT ANY TIME BEFORE 2007. THE CORRECT EFFECTIVE DATE MAY BE DIFFERENT FROM THE ONE RECORDED.

Effective date: 20051207