EP0264455B1 - Überzogener stahl mit ausgezeichneter beschichtbarkeit - Google Patents

Überzogener stahl mit ausgezeichneter beschichtbarkeit Download PDF

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Publication number
EP0264455B1
EP0264455B1 EP87902156A EP87902156A EP0264455B1 EP 0264455 B1 EP0264455 B1 EP 0264455B1 EP 87902156 A EP87902156 A EP 87902156A EP 87902156 A EP87902156 A EP 87902156A EP 0264455 B1 EP0264455 B1 EP 0264455B1
Authority
EP
European Patent Office
Prior art keywords
coating
alloy
plating
plated steel
upper layer
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
EP87902156A
Other languages
English (en)
French (fr)
Other versions
EP0264455A4 (en
EP0264455A1 (de
Inventor
Taisuke Irie
Junichi Kotegawa
Koichi Watanabe
Satoshi Hukuda
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 Nisshin Co Ltd
Original Assignee
Nisshin Steel Co Ltd
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 Nisshin Steel Co Ltd filed Critical Nisshin Steel Co Ltd
Publication of EP0264455A1 publication Critical patent/EP0264455A1/de
Publication of EP0264455A4 publication Critical patent/EP0264455A4/en
Application granted granted Critical
Publication of EP0264455B1 publication Critical patent/EP0264455B1/de
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/02—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material
    • C23C28/023—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material only coatings of metal elements only
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/02—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material
    • C23C28/023—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material only coatings of metal elements only
    • C23C28/025—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material only coatings of metal elements only with at least one zinc-based layer
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/10—Electroplating with more than one layer of the same or of different metals

Definitions

  • This invention relates to a plated steel sheet excellent in the appearance of a coating when applied in such a use that cationic electrodeposition coating is carried out as in the case of components for automobile bodies.
  • a double-layer plated steel sheet wherein an Fe coating that can achieve a good electrodeposition coating performance is further applied on a pure Zn or Zn alloy coating.
  • Conventionally known steel sheets of this type may include those wherein an upper layer comprises an Fe-Zn alloy coating having Fe content of 60 to 90 wt.%, and those wherein an upper layer comprises an Fe coating, and it is true that the application of the cationic electrodeposition coating on these double-layer plated steel sheets may result in generation of a decreased number of craterings on a coating film and can improve the coating appearance.
  • the coating weight must be made not less than 5 g/m2 (per one side), necessarily resulting in higher production cost.
  • this Fe alloy coating is so hard and brittle that an infinite number of crack may be formed when a plated steel sheet is worked into a component, with the result that the lower layer is exposed at the cracked portion. Therefore, when the electrodeposition coating is carried out, it follows that the electrodeposition coating is directly applied on the lower layer, and also that craterings are liable to be generated on the coating film.
  • the variation factor has not been made clear, this is presumably because the covering rate in the upper layer coating relative to the lower layer coating is so poor, or the purity of the upper layer coating is so high, that large crystals of phosphate may tend to be formed during phosphating which is a pre-treatment for the electrodeposition coating, and, as a result, the rate of covering by the phosphate crystals on the surface of a coating may be lowered and also the variation in the covering rate may be caused to bring about a difference in the electrolytic conduction for electrodeposition coating, between the phosphate-deposited portion and non-deposited portion. Therefore, in order to lessen the generation of craterings on a coating film by providing the Fe coating, the coating weight must be 3 g/m2 (per one side), also necessarily resulting in higher production cost.
  • this invention aims at providing a plated steel sheet that has been improved the electrodeposition coating performance and yet can achieve lower production cost.
  • This invention provides a plated steel sheet which is comprised of a plated steel sheet comprising a lower layer coating of pure Zn or a Zn alloy, provided on a steel sheet, and an upper layer coating of boron(B)-containing Fe or a boron-containing Fe-Zn alloy having an Fe percentage of 50 wt.% or more provided on said lower layer coating, said upper layer coating containing 0.001 to 3 wt.% of boron, thereby making it possibie to prevent craterings being generated on a coating film and lessen the upper layer coating weight.
  • the reason why the plated steel sheet of this invention can have an excellent electrodeposition coating performance is presumed to be that the presence of boron added to a bath at the time of the plating for the upper layer can improve the uniformity of the electrodeposition to give a uniform coating, and also that the boron contained in the upper layer can serve as a nucleus at the time of the deposition of phosphate when a phosphating is applied as a pre-treatment for the electrodeposition coating, to form a fine and dense phosphate coating, and, as a result, the electrolytic conduction on the entire surface of a steel sheet becomes uniform, whereby a coating material can be uniformly electrodeposited at the time the electrodeposition coating is carried out, and thus the generation of craterings can be stably restrained.
  • the plated steel sheet of this invention can restrain the generation of craterings in a coating film even when the coating weight is not more than 3 g/m2 per one side in the case the upper layer comprises the boron-containing Fe coating, or even when the coating weight is not more than 5 g/m2 per one side in the case the upper layer comprises the above element-containing Fe-Zn alloy coating. This is presumably because, even if the coating weight is small, the upper layer can cover the lower layer so excellently that the rate of covering of the lower layer by the upper layer can be improved.
  • the upper layer comprises the Fe-Zn alloy coating
  • Fe content is controlled to 60 to less than 100 wt.%.
  • the presence of boron contained makes it possible to lessen the generation of craterings in a coating film even if Fe content is decreased to 50 to less than 100 wt.%. This is presumably because of the above mentioned effect of improving the phosphating performance, and once the Fe content can be decreased like this, the difference in the corrosion potential between the upper layer and the lower layer becomes small, whereby the corrosion resistance of the coatings as a whole for a long period can be improved.
  • the amount of boron contained in the upper layer is controlled to 0.001 to 3 wt.%. This is because the boron amount of less than 0.001 wt.% may result in no difference from an upper layer containing no boron in respect of the generation of craterings and variation thereof in the electrodeposition coating, and the boron amount more than 3 wt.% may result in saturation of the effect so that it is meaningless to make the amount larger than that.
  • the covering weight on the upper layer may be preferably controlled to 0.5 to 10 g/m2 in the case of the boron-containing Fe coating, and 0.2 to 8 g/m2 in the case of the Fe-Zn alloy coating. This is because the weight of less than 0.5 g/m2 or 0.2 g/m2 may make it impossible to achieve perfect covering of the lower layer to bring about the generation of craterings in a coating film to be caused by the exposure of the lower layer at the time of the electrodeposition coating, and the weight more than 10 g/m2 or 8 g/m2 may result in saturation of the effect of restraining the generation of craterings in a coating film so that it is unnecessary to make the coating weight larger than that.
  • the plating may be carried out by adding one or more of boron compound(s) such as boric acid, metaboric acid, water soluble metaborate, water soluble tetraborate and tetrafluoroborate to an ordinary Fe plating bath or a plating bath of an Fe alloy such as an Fe-Zn alloy and an Fe-Ni alloy, and adjusting the pH of the bath to 1 to 3.
  • boron compound(s) such as boric acid, metaboric acid, water soluble metaborate, water soluble tetraborate and tetrafluoroborate
  • the steel sheet according to this invention can improve the performance in the electrodeposition coating of a pure Zn-plated or Zn alloy-plated steel sheet.
  • the lower layer comprises an Zn alloy coating of a Zn-Ni or Zn-Fe alloy
  • the generation of craterings can be restrained even with inclusion of a trace amount of one or more of elements such as Ni (in respect of the Zn-Fe alloy), Fe (in respect of the Zn-Ni alloy), Co, Cr, Mn, Mo and Ti.
  • the lower layer comprises a pure Zn coating, it can be also restrained even with respect to coatings obtained by carrying out electroplating, vacuum deposition or hot dipping.
  • the upper layer comprises the Zn alloy coating
  • it can be also restrained even with respect, in addition to the coatings formed by the above methods, to those which are alloyed into a Zn-Fe alloy by thermal diffusion after carrying out hot dip zinc coating or vacuum zinc deposition as in the case of an alloyed zinc-plated steel sheet.
  • the steel sheets of this invention provided with an Fe-B coating as the upper layer, show less generation of craterings and variation thereof than those in conventional double-layer plated steel sheets provided with an upper layer Zn coating and having a good electrodeposition coating performance, even with a lower layer comprising a pure Zn coating or a Zn alloy coating.
  • a cold rolled steel sheet of 0.8 mm thick was treated in the same manner as in Example 1 to make its surface clean. Thereafter, a lower layer coating comprising a Zn-Fe alloy or a Zn-Ni alloy was first provided under the conditions as shown in Table 3, and next an upper layer coating comprising a boron containing Fe-Zn alloy or a boron-free Fe-Zn alloy was provided on it.
  • a steel strip of 0.6 mm thick and 300 mm wide was reduced in a pre-treatment oven of a gas reduction system, and thereafter passed through a pressurizing chamber for preventing inflow of gas or air and a seal roll chamber in which pressure is stepwise reduced by means of a number of seal rolls, and then introduced into a first vacuum deposition chamber equipped with a vacuum deposition Zn bath of an electrical resistance heating system at a lower side of the position of the steel strip, to apply a deposition coating of pure Zn on one side of the steel strip.
  • the steel strip was guided to a second vacuum deposition chamber disposed at a lower side of the above first vacuum deposition chamber and having the same construction as the first vacuum deposition chamber to apply a deposition coating of pure Zn on the opposite side of the steel strip, and thereafter passed through a seal roll chamber and a pressurizing chamber to produce a deposited steel strip having a coating weight of 50 g/m2 (per one side).
  • the plating was carried out under the conditions of a steel strip moving speed of 15 m/min and a vacuum degree of 1.333 Pa (0.01 Torr) in both the first and second vacuum deposition chambers.
  • part of the pure Zn-plated steel strip thus produced was introduced in an oven having an atmosphere of a mixed gas (dew point: -25 o C) comprising 3 % of H2 and 97 % of N2, and heated to 280 o C to form the coating into a Zn-Fe alloy, thereby producing a steel strip provided with a coating of a Zn-Fe alloy having an Fe percentage of 10 wt.%.
  • a mixed gas dew point: -25 o C
  • this Zn-Fe alloy-plated steel strip and the pure Zn-plated steel strip were subjected to electroplating to respectively provide a Fe coating or a Fe-B coating under the same conditions as those for the upper layer coating shown in Table 1, and a boron-containing high Fe-Zn coating under the same conditions as those for the upper layer coating shown in Table 3, followed by carrying out electrodeposition coating under the same conditions as in Example 1.
  • the states of generation of craterings in the coating film are shown in Table 5 and Table 6.
  • the plated steel sheet according to this invention can achieve a good coating appearance when used not only in automobile body components but also in other components such as electrical equipment components for domestic use and construction components on which the electrodeposition coating is carried out. Since also having an excellent coating performance for coating materials other than the coating materials for the electrodeposition, the present steel sheet can be also applied in such a use for general coating.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • Electrochemistry (AREA)
  • Electroplating Methods And Accessories (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)
  • Laminated Bodies (AREA)
  • Electroplating And Plating Baths Therefor (AREA)

Claims (3)

  1. Plattiertes Stahlblech mit ausgezeichneter Elektroabscheidungsbeschichtungsfähigkeit, dadurch gekennzeichnet, daß es auf einem Stahlblech eine Beschichtung aus reinem Zn oder einer Zn-Legierung als untere Schicht und eine Beschichtung aus Bor enthaltendem Fe oder einer Bor enthaltenden Fe-Zn-Legierung mit einem Fe-Prozentgehalt von 50 Gew.-% oder mehr als obere Schicht, die auf der unteren Schicht vorgesehen ist, umfaßt, wobei die obere Schicht 0,001 bis 3 Gew.-% Bor enthält.
  2. Plattiertes Stahlblech mit ausgezeichneter Elektroabscheidungsbeschichtungsfähigkeit nach Anspruch 1, dadurch gekennzeichnet, daß das Beschichtungsgewicht der oberen Schicht 0,5 bis 10 g/m² pro einer Seite in dem Fall beträgt, wenn die obere Schicht den Bor enthaltenden Fe-Überzug umfaßt.
  3. Plattiertes Stahlblech mit ausgezeichneter Elektroabscheidungsbeschichtungsfähigkeit nach Anspruch 1, dadurch gekennzeichnet, daß das Beschichtungsgewicht der oberen Schicht 0,2 bis 8 g/m² pro einer Seite in dem Fall beträgt, in dem die obere Schicht die Bor enthaltende Fe-Zn-Legierung mit einem Fe-Prozentgehalt von 50 Gew.-% oder mehr umfaßt.
EP87902156A 1986-03-29 1987-03-27 Überzogener stahl mit ausgezeichneter beschichtbarkeit Expired - Lifetime EP0264455B1 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
JP71884/86 1986-03-29
JP61071884A JPS62228498A (ja) 1986-03-29 1986-03-29 塗装用めつき鋼板
CA000539351A CA1309055C (en) 1986-03-29 1987-06-10 Plated steel sheet having excellent coating performance

Publications (3)

Publication Number Publication Date
EP0264455A1 EP0264455A1 (de) 1988-04-27
EP0264455A4 EP0264455A4 (en) 1991-03-13
EP0264455B1 true EP0264455B1 (de) 1993-06-02

Family

ID=25671379

Family Applications (1)

Application Number Title Priority Date Filing Date
EP87902156A Expired - Lifetime EP0264455B1 (de) 1986-03-29 1987-03-27 Überzogener stahl mit ausgezeichneter beschichtbarkeit

Country Status (7)

Country Link
EP (1) EP0264455B1 (de)
JP (1) JPS62228498A (de)
KR (1) KR920009844B1 (de)
AU (1) AU589767B2 (de)
CA (1) CA1309055C (de)
DE (1) DE3786056T2 (de)
WO (1) WO1987005950A1 (de)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0610358B2 (ja) * 1986-12-06 1994-02-09 日新製鋼株式会社 複層電気めつき鋼板
DE3882769T2 (de) * 1987-03-31 1993-11-11 Nippon Steel Corp Korrosionsbeständiges plattiertes Stahlband und Verfahren zu seiner Herstellung.
JPS6428351A (en) * 1987-07-23 1989-01-30 Nisshin Steel Co Ltd Method for hot dip aluminizing hardly aluminizable steel sheet
KR910003036B1 (ko) * 1988-12-30 1991-05-17 포항종합제철 주식회사 고내식성 철-망간계 이층도금강판 및 그 제조방법
AT400040B (de) * 1993-06-02 1995-09-25 Andritz Patentverwaltung Verfahren und vorrichtung zur beschichtung von metallsubstraten, insbesondere stahl- oder aluminiumbblechen in bandform

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS56142885A (en) * 1980-04-08 1981-11-07 Nippon Steel Corp Steel material with plural plating layers
JPS59116393A (ja) * 1982-12-23 1984-07-05 Kobe Steel Ltd 塗装後の耐蝕性に優れた表面処理鋼板

Also Published As

Publication number Publication date
KR880700868A (ko) 1988-04-13
CA1309055C (en) 1992-10-20
EP0264455A4 (en) 1991-03-13
AU7208087A (en) 1987-10-20
WO1987005950A1 (en) 1987-10-08
DE3786056T2 (de) 1993-10-28
JPS62228498A (ja) 1987-10-07
KR920009844B1 (ko) 1992-10-31
EP0264455A1 (de) 1988-04-27
JPH0156159B2 (de) 1989-11-29
DE3786056D1 (de) 1993-07-08
AU589767B2 (en) 1989-10-19

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