EP0566121B1 - Procédé de production d'une feuille d'acier recouverte d'un alliage zinc-chrome d'une excellente adhérence - Google Patents

Procédé de production d'une feuille d'acier recouverte d'un alliage zinc-chrome d'une excellente adhérence Download PDF

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Publication number
EP0566121B1
EP0566121B1 EP93106155A EP93106155A EP0566121B1 EP 0566121 B1 EP0566121 B1 EP 0566121B1 EP 93106155 A EP93106155 A EP 93106155A EP 93106155 A EP93106155 A EP 93106155A EP 0566121 B1 EP0566121 B1 EP 0566121B1
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Prior art keywords
group
steel sheet
zinc
plated steel
chromium alloy
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EP93106155A
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German (de)
English (en)
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EP0566121A1 (fr
Inventor
Kazuhiro c/o Technical Research Div. Hasegawa
Hiroki c/o Technical Research Div. Nakamaru
Kazuo c/o Technical Research Div. Mochizuki
Tomokatsu c/o Technical Research Div. Katagiri
Nobuyuki c/o Technical Research Div. Morito
Shigeo c/o Technical Research Div. Kurokawa
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JFE Steel Corp
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Kawasaki Steel Corp
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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
    • C25D3/565—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of zinc

Definitions

  • the present invention relates to a method for producing a zinc-chromium alloy-plated steel sheet having excellent corrosion resistance and excellent plate adhesion.
  • Galvanized steel sheets are widely used as rust-preventive steel sheets for automobiles, household electric appliances, construction materials and the like. This is effective because since a pure zinc layer is less noble relative to iron of the steel sheet, the zinc layer has a sacrificial anticorrosion effect in that the zinc is first corroded in formation of plating defects such as pinholes or the like and portions where the matrix iron is exposed by processing and these portions are covered by corrosion products, thereby preventing rusting of the steel sheet. However, the zinc layer has a fault that because pure zinc is active, the corrosion thereof very rapidly develops in a corrosive environment such as a spray of salt water or the like.
  • the method disclosed in Japanese Patent Laid-Open No. 57-67188 uses an electroplating bath containing 70 to 370 g/l sulfate ion, 45 to 60 g/l nickel ion, 0.5 to 13 g/l chromium ion and 10 to 80 g/l boric acid, the bath being kept at a pH value of 1.4 to 2.
  • the amount of chromium contained in the plating bath used in this method is 1.0 wt% at most, and any anticorrosion effect of chromium can hardly be expected.
  • the chromium content must be further increased for improving the corrosion resistance.
  • Japanese Patent Laid-Open No. 64-55398 discloses a method of producing a zinc-chromium-plated steel sheet with excellent surface quality and corrosion resistance, wherein plating is effected with a current density of at least 50 A/dm 2 by using an acid plating bath containing zinc ions, trivalent chromium ions and 0.01 to 20 g/l of polyoxyalkylene derivative.
  • This method permits the Cr content in the plating to be increased to about 40 wt%.
  • the plated layer exhibits poor adhesion, and is thus easily peeled off from a steel sheet in both the adhesion tests below.
  • Japanese Patent Laid-Open No. 1-309998 discloses a method of producing an electroplated steel sheet with excellent corrosion resistance and surface glossiness, wherein electroplating is performed by using an acid plating bath containing Cr ions and a cation polymer and having a ratio of Cr 6+ ion/ Cr 3+ ion of 0.1 or less.
  • the specification also discloses that a quaternary amine polymer is used as the cation polymer.
  • this method is capable of producing a Zn-Cr alloy-plated steel sheet, the method has the problems that the concentration of the cation polymer cannot easily be kept constant because the cation polymer is easily entrapped in the plated layer, and that although the adhesion of the layer plated with a low current density (50 A/dm 2 ) is good, the adhesion of the plated layer obtained by plating with a current density of more than this value abruptly decreases. Further, although both Japanese Patent Laid-Open Nos. 64-55398 and 1-309998 take the amount of Cr deposition into consideration, improvements not only in corrosion resistance but also in adhesion are important problems. However, both specifications fail to describe improvement of adhesion.
  • an object of the present invention is to provide a method of producing a zinc-chromium alloy-plated steel sheet having excellent plating adhesiveness and corrosion resistance after processing.
  • a method of producing a zinc-chromium alloy-plated steel sheet having excellent plating adhesiveness by plating the surface of the steel sheet using an acid plating bath containing zinc ions (Zn 2+ ) and chromium ions (Cr 3+ ) at a molar concentration ratio of 0.1 ⁇ Cr 3+ /(Zn 2+ + Cr 3+ ) ⁇ 0.9 in a total amount of at least 0.5 mol/l within the dissolution range, and 0.1 to 30 g/l of at least one nonionic organic additive having at least a triple bond, at a bath temperature of 25 to 70°C and a pH of 1.0 to 4.0 with a current density of 50 to 200 A/dm 2 .
  • the nonionic organic additive having at least a triple bond is expressed by either of the following formulas: wherein the number of carbon atoms which form a molecule is within the range of from 10 to 800, wherein R 1 , R 2 , R 3 and R 4 each being at least one selected from a group consisting of phenyl group, naphthalene group, anthracene group, phenol group, naphthol group, anthranol group, alkyl-group adducts and/or alkylene-group adducts and/or sulphonic acid-group adducts of these groups, hydrogen, hydroxyl group, alkyl group, alkylene group, alkoxy group or its polymer, and sulphonic acid group, and wherein R is at least one selected from a group consisting of hydrogen, alkoxy group or its polymer.
  • nonionic organic additives each having at least a triple bond include acetylene alcohols, acetylene glycols and derivatives thereof.
  • a method of producing a zinc-chromium alloy-plated steel sheet of the present invention is described in further detail below.
  • the plating bath used for Zn-Cr alloy plating in the present invention comprises Zn 2+ ions and Cr 3+ ions as main metal ions, which are prepared in various known ways as by dissolving as sulfates, etc.
  • the total concentration of these Zn 2+ ions and Cr 3+ ions is at least 0.5 mol/l within the dissolution range. Namely, with a total concentration of less than 0.5 mol/l, the surface is easily burnt deposited. On the other hand, with a total concentration beyond the dissolution range, a solid is produced, and significant improvement of appearance color tone and uniform electrodeposition properties is not achieved.
  • the Zn content in the plated layer is controlled to be about 60 wt% to 95 wt%, and the molar ratio of Cr 3+ /(Zn 2+ + Cr 3+ ) in the plating bath is set to a value of 0.1 to 0.9.
  • the ratio of less than 0.1 the amount of chromium contained in the plated layer obtained cannot be increased, and thus a plated layer having excellent corrosion resistance cannot be obtained.
  • the Zn content in the plated layer cannot be easily controlled to be at least 60 wt%, thereby deteriorating the adhesion between the plated layer and the steel sheet.
  • the plating bath may contain as a conductive auxiliary at least one member selected from the group consisting of K 2 SO 4 , Na 2 SO 4 , (NH 4 ) 2 SO 4 , CaSO 4 and MgSO 4 .
  • the plating bath preferably contains at least 10 g/l of such an auxiliary.
  • the conductive auxiliary is added for improving the conductivity of the plating solution, decreasing the consumption of electric power and decreasing the burnt depositing of the surface.
  • the current density is 50 to 200 A/dm 2 , preferably 70 to 150 A/dm 2 .
  • a current density of less than 50 A/dm 2 the deposition of Cr is hardly obtained, and with a current density of more than 200 A/dm 2 , the surface is easily burnt deposited, thereby deteriorating the adhesion of the plated layer.
  • the bath temperature is preferably 25 to 70°C. At less than 25°C, the adhesion between the plated layer obtained and the steel sheet deteriorates, and at more than 70°C, the appearance tends to become black.
  • the pH value is preferably 1.0 to 4.0. With a pH value of less than 1.0, not only the efficiency of cathodic deposition is decreased, but also the apparatus used is significantly corroded. With a pH value of more than 4.0, precipitation of zinc hydroxide significantly occurs.
  • At least one nonionic organic additive having at least a triple bond is added to the plating bath in order to obtain a Zn-Cr alloy-plated layer having excellent adhesion and a uniform alloy composition.
  • the nonionic organic additive having at least a triple bond is a compound expressed by the following formulas: wherein R 1 , R 2 , R 3 and R 4 each being at least one selected from a group consisting of phenyl group, naphthalene group, anthracene group, phenol group, naphthol group, anthranol group, alkyl-group adducts and/or alkylene-group adducts and/or sulphonic acid-group adducts of these groups, hydrogen, hydroxyl group, alkyl group, alkylene group, alkoxy group or its polymer, and sulphonic acid group, and wherein R is at least one selected from a group consisting of hydrogen, alkoxy group or its polymer.
  • the number of carbon atoms which form a molecule of the nonionic organic additive is preferably within the range of 10 to 800, more preferably 10 to 250.
  • a carbon number of less than 10 the formation of a complex with the metal ions contained in the plating bath becomes unstable, and a eutectoid of both metal ions cannot be easily formed due to a large change in polarization.
  • a carbon number of more than 800 a portion near the triple bond exhibits high steric hindrance, and the adhesion on the surface of the steel sheet thus significantly deteriorates, thereby causing difficulties in obtaining a plated layer with glossiness.
  • the addition of at least one of the above compounds each having at least a triple bond causes the formation of fine crystal grains in the Zn-Cr alloy plated layer, and significantly improves the glossiness and the uniform electrodeposition property of the solution.
  • the additives have the effect of holding the plated layer on the metal surface caused by both the ⁇ -electrons of the triple bond and the hydrogen bonds, and the effect of forming a complex with Zn 2+ ions.
  • the appropriate amount of the additive added is within the range of 0.1 to 30 g/l. With an amount of less than 0.1 g/l, the deposition of Cr metal is decreased, and a plated layer having a good alloy composition cannot be easily obtained. If the amount of the additive added exceeds 30 g/l, the effects are saturated, and burnt depositing of the plated layer is caused.
  • the plated layer obtained by the above-described production method has a Zn content of 60 to 95 wt%, and exhibits a uniform color tone of a white gray to silver white and more excellent plate adhesion, without forming a stripe pattern.
  • the Zn-Cr alloy plating method of the present invention can be applied to Zn-Cr binary alloy electroplating and electroplating of an alloy mainly consisting of Zn and Cr, for example, Zn-Cr-P, Zn-Cr-Ni, Zn-Cr-Al 2 O 3 , Zn-Cr-Ti and Zn-Cr-Fe alloy plating.
  • a zinc-chromium alloy-plated steel sheet was produced by plating the same steel sheet as that used in Examples 1 to 37 under the same conditions with the exception that Fe 2+ , Ni 2+ , Co 2+ , Al 2 O 3 , SiO 2 or TiO 2 was added in an amount shown in Tables 4-1, 4-2, 5-1 and 5-2 to produce a zinc-chromium alloy-plated steel sheet with a plated layer containing one of the above substances.
  • the powdering resistance and the corrosion resistance after processing were evaluated under the above-described conditions. The results obtained are shown in Tables 4-1, 4-2, 5-1 and 5-2.
  • TMDD indicates 2,4,7,9-tetramethyl-5-decyne-4,7-diol
  • TMDDE an ethylene oxide addition product of TMDD
  • the use of the organic additive disclosed in the present invention permits the formation of a zinc-chromium alloy-plated steel sheet having excellent plate adhesion and excellent corrosion resistance.
  • the method of the present invention uses a plating bath with excellent stability, and thus permits stable production of a plated steel sheet on an industrial scale. It is very significant that the present invention enables the industrial production of a zinc-chromium alloy-plated steel sheet having excellent plate adhesion and excellent corrosion resistance.

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  • 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 (4)

  1. Procédé de production de tôles d'acier plaquées avec un alliage de zinc et de chrome ayant une excellente adhérence de placage, comprenant l'étape consistant à
    plaquer la surface desdites tôles d'acier en utilisant un bain acide de métallisation contenant
    des ions de zinc (Zn2+) et des ions de chrome (Cr3+), suivant un rapport de concentration molaire de
    0,1 ≤ Cr3+/ (Zn2+ + Cr3+) ≤ 0,9, dans une quantité totale d'au moins 0,5 mol/l comprise dans la plage de dissolution, et
    entre 0,1 g/l et 30 g/l au moins d'un additif organique non ionique ayant au moins une triple liaison,
    ledit bain ayant une température comprise entre 25°C et 70°C et un pH compris entre 1,0 et 4,0, avec une densité de courant comprise entre 50 A/dm2 et 200 A/dm2.
  2. Procédé de production de tôles d'acier plaquées avec un alliage de zinc et de chrome ayant une excellente adhérence de placage, selon la revendication 1, dans lequel ledit additif organique non ionique ayant au moins une triple liaison est exprimé par les formules suivantes :
    Figure imgb0026
        où le nombre d'atomes de carbone qui forment une molécule, est compris dans la plage variant entre 10 et 800, où R1, R2, R3 et R4 constituent, chacun, au moins un groupe sélectionné parmi un des groupes comprenant un groupe phényle, un groupe naphtyle, un groupe anthryle, un groupe hydroxyphényle, un groupe hydroxynaphtyle, un groupe hydroxyanthryle, des produits d'addition d'un groupe alkyle et/ou des produits d'addition d'un groupe alkylène et/ou des produits d'addition d'un groupe d'acide sulfonique de ces groupes, un groupe d'hydrogène, hydroxyle, un groupe alkyle, un groupe alkylène, un groupe alkoxyde ou son polymère et un groupe d'acide sulfonique, où R est au moins un groupe sélectionné parmi un groupe comprenant le groupe d'hydrogène, d'alkoxydes ou son polymère.
  3. Procédé de production de tôles d'acier plaquées avec un alliage de zinc et de chrome ayant une excellente adhérence de placage, selon la revendication 2, dans lequel ledit additif organique non ionique ayant au moins une triple liaison est sélectionné parmi le groupe des alcools acétyléniques, des glycols acétyléniques et des dérivés de ces alcools et de ces glycols.
  4. Procédé de production de tôles d'acier plaquées avec un alliage de zinc et de chrome ayant une excellente adhérence de la tôle, selon la revendication 2, dans lequel le nombre d'atomes de carbone dans ledit additif ayant au moins une triple liaison est compris entre 10 et 250.
EP93106155A 1992-04-16 1993-04-15 Procédé de production d'une feuille d'acier recouverte d'un alliage zinc-chrome d'une excellente adhérence Expired - Lifetime EP0566121B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP9633192 1992-04-16
JP96331/92 1992-04-16

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EP0566121A1 EP0566121A1 (fr) 1993-10-20
EP0566121B1 true EP0566121B1 (fr) 1997-07-02

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EP (1) EP0566121B1 (fr)
KR (1) KR960001036B1 (fr)
DE (1) DE69311833T2 (fr)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008014885A1 (fr) 2006-07-31 2008-02-07 Voestalpine Stahl Gmbh Couche de protection contre la corrosion présentant des propriétés améliorées
WO2011036306A2 (fr) 2009-09-28 2011-03-31 Voestalpine Stahl Gmbh Protection contre la corrosion à base d'alliage au zinc
DE102009045074A1 (de) 2009-09-28 2011-04-07 Voestalpine Stahl Gmbh Korrosionsschutz auf Zink-Legierungsbasis
DE102009045076A1 (de) 2009-09-28 2011-04-07 Voestalpine Stahl Gmbh Korrosionsschutz auf Zink-Legierungsbasis

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE69404781T2 (de) * 1993-08-10 1998-03-19 Nippon Kokan Kk Verfahren zur Herstellung von plattiertem Stahlblech mit Zn-Cr Legierungsplattierung
CN103225093A (zh) * 2013-04-27 2013-07-31 重庆科发表面处理有限责任公司 一种全光亮电镀锌-铬合金溶液

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS58502221A (ja) * 1981-12-28 1983-12-22 ザ　ボ−イング　コンパニ− 亜鉛―ニッケル電気メッキの製造方法
EP0285931B1 (fr) * 1987-03-31 1993-08-04 Nippon Steel Corporation Bande d'acier résistant à la corrosion et procédé de fabrication

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008014885A1 (fr) 2006-07-31 2008-02-07 Voestalpine Stahl Gmbh Couche de protection contre la corrosion présentant des propriétés améliorées
DE102006035660A1 (de) * 2006-07-31 2008-02-07 Voestalpine Stahl Gmbh Korrosionsschutzschicht mit verbesserten Eigenschaften
DE102006035660A9 (de) * 2006-07-31 2008-05-15 Voestalpine Stahl Gmbh Korrosionsschutzschicht mit verbesserten Eigenschaften
DE102006035660B4 (de) * 2006-07-31 2009-08-20 Voestalpine Stahl Gmbh Korrosionsschutzschicht mit verbesserten Eigenschaften und Verfahren zu ihrer Herstellung
WO2011036306A2 (fr) 2009-09-28 2011-03-31 Voestalpine Stahl Gmbh Protection contre la corrosion à base d'alliage au zinc
DE102009045074A1 (de) 2009-09-28 2011-04-07 Voestalpine Stahl Gmbh Korrosionsschutz auf Zink-Legierungsbasis
DE102009045076A1 (de) 2009-09-28 2011-04-07 Voestalpine Stahl Gmbh Korrosionsschutz auf Zink-Legierungsbasis
DE102009045076A9 (de) 2009-09-28 2011-07-21 Voestalpine Stahl Gmbh Korrosionsschutz auf Zink-Legierungsbasis

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Publication number Publication date
KR960001036B1 (ko) 1996-01-17
DE69311833T2 (de) 1997-11-27
KR930021828A (ko) 1993-11-23
DE69311833D1 (de) 1997-08-07
EP0566121A1 (fr) 1993-10-20

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