EP0364596B1 - METHODS FOR PRODUCING Zn-Ni ALLOY-PLATED STEEL SHEET HAVING EXCELLENT PRESS MOLDABILITY - Google Patents

METHODS FOR PRODUCING Zn-Ni ALLOY-PLATED STEEL SHEET HAVING EXCELLENT PRESS MOLDABILITY Download PDF

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Publication number
EP0364596B1
EP0364596B1 EP89903215A EP89903215A EP0364596B1 EP 0364596 B1 EP0364596 B1 EP 0364596B1 EP 89903215 A EP89903215 A EP 89903215A EP 89903215 A EP89903215 A EP 89903215A EP 0364596 B1 EP0364596 B1 EP 0364596B1
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EP
European Patent Office
Prior art keywords
plated
alloy
steel plate
plated steel
plate
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
EP89903215A
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German (de)
English (en)
French (fr)
Other versions
EP0364596A4 (en
EP0364596A1 (en
Inventor
Ryoichi Muko
Kazuo Mochizuki
Hajime Kimura
Toshio Ichida
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.)
JFE Steel Corp
Original Assignee
Kawasaki Steel Corp
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Filing date
Publication date
Application filed by Kawasaki Steel Corp filed Critical Kawasaki Steel Corp
Publication of EP0364596A1 publication Critical patent/EP0364596A1/en
Publication of EP0364596A4 publication Critical patent/EP0364596A4/en
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Publication of EP0364596B1 publication Critical patent/EP0364596B1/en
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02—Anodisation
    • C25D11/34—Anodisation of metals or alloys not provided for in groups C25D11/04 - C25D11/32
    • 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
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/07—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing phosphates
    • C23C22/08—Orthophosphates
    • 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
    • C25D5/48—After-treatment of electroplated surfaces

Definitions

  • This invention relates to methods for producing a Zn-Ni alloy plated steel plate having superior press formability.
  • the Zn-Ni alloy plated steel sheet, strip or plate exhibits corrosion resistance about five to ten times that of the Zn-plated steel plate having the same deposited amount of the plated metal. For this reason, it is used in an increasing amount as a steel plate for coping with the problem recently presented of early corrosion of vehicle bodies caused by road freezing preventive agents employed in winter, and is used at various portions from the front fender to a bonnet and trunk lid outer.
  • the present-day trend is to use a double side plated steel plate on the outer surface of the vehicle body with the aim of improving the corrosion resistance after peel-off of the coating by the stones or pebbles striking on the outer surface, to replace the one side plated steel plate during the time of early usage of the plated steel plates which was aimed at preventing rusting at the portions where coating may be insufficient, such as the inner surface of the vehicle body.
  • the plated surface turns out to be the protruding surface at the time of press working, and the friction of the plated surface itself presents problems.
  • the press working may naturally be facilitated with the use of the highly viscous press oil at the time of press working, the customary practice is to apply the rust preventive oil of low viscosity to the plated steel plate and to perform the press working with the rust preventive oil resting on the plate surface to facilitate the degreasing and coating at the user.
  • the plated plate is required to have satisfactory workability with the rust preventive oil applied thereto.
  • This method utilizes the so-called powdering of the upper Zn-Ni plating layer to improve the press workability, the peeled-off powders are placed and heaped on the press mold surface, in case of continuous stamping of a large number of samples, thus causing the problem of pimples.
  • a method comprising plating a steel sheet with a Zn-Ni layer and subjecting the plated surface to an anodic treatment in order to blacken said surface.
  • the charge values in said anodic treatment are 100 to 300 C/dm.
  • the present invention contemplates to eliminate the lowering of the press formability caused by the frictional resistance of the plated surface of the Zn-Ni alloy plated steel plate, and is aimed to improve the press formability without accompanying powdering of the plated layer, such as is encountered in the prior art.
  • a method for producing a Zn-Ni alloy plated steel plate having superior press formability comprising the steps as defined in claim 1.
  • a method for producing a Zn-Ni alloy plated steel plate having superior press formability comprising the steps as defined in claim 2.
  • Fig.1 is a chart showing the limiting drawing ratio (LDR) for illustrating the effect of the present invention following the dipping treatment.
  • Fig.2 is a chart showing changes of the limiting drawing ratio (LDR) after the dipping treatment.
  • Fig.3 is a chart showing the result of comparison between the LDR of the Zn-Ni alloy plated plate and that of the cold rolled plate.
  • Fig.4 is a diagrammatic view showing a cylindrical deep drawing tester.
  • Fig.5 is a diagrammatic view showing a friction measurement tester.
  • Fig.6 shows the difference in the friction between the Zn-Ni alloy plated plate and the cold rolled plate.
  • Fig.3 shows the relative ease with which the cold rolled plate, the single-side Zn-Ni alloy plated steel plate and the double-side Zn-Ni alloy plated steel plate are expressed in terms of the limiting drawing ratio (LDR) in a cylindrical deep drawing testing.
  • LDR limiting drawing ratio
  • the limiting drawing ratio was measured by taking the ratio of the punch diameter to the blank diameter when a test plate is broken as the blank diameter is changed between the values of 60 and 80 mm using a cylindrical deep drawing tester shown in Fig.4. The testing was performed so that the cold rolled surface of the single-side Zn-Ni alloy plated steel plate turned out to be the protruding surface.
  • the rust preventive oil manufactured by the Idemitsu Kosan Co. Ltd.
  • the double-side plated plate is low in LDR and markedly inferior in press formability as compared with the cold rolled plate. Since the plated steel plate is a substitute material for cold rolled plate, it is pressed on a press mold designed for use with cold rolled plates. It was found that the tested plate was broken on a press mold designed for use exclusively with ultra deep drawing steel plate.
  • the cold rolled plate differs from the plated plate in surface friction, and this difference possibly affects the formability.
  • Fig.1 shows the changes in LDR when the Zn-Ni alloy plated plate was dipped for four seconds in the following solution.
  • the amount of deposition on one side of the plated plate was 30 g/m, the Ni contents were 12.5 % and the type of the steel used was SPCC.
  • the solution employed in the dipping treatment may contain one or both of H2PO 4 - ions and HPO 4 2- ions.
  • the concentration or temperature of the solution since some time may be involved due to the dipping treatment until the effect is displayed, it is preferred that the temperature and the concentration be elevated for more prompt effects. For short time treatment of less than 10 seconds, suited for industrial production, it is preferred that the dipping temperature be not lower than 40 °C and the concentration in the dipping solution of the H2PO 4 - and HPO 4 2- summed together be not less than 100 g/l.
  • the Ni contents in the plated plate employed are 10 to 17 wt.% and preferably 11 to 15 wt.%.
  • the contents lower than 10 wt.% are not effective in the case of the present method, while the contents in excess of 17 wt.% tend to cause powdering in the Zn-Ni plated layer. It is for this reason that the Ni contents of the Zn-Ni alloy plated steel plate of the present invention are limited to the range of 10 to 17 wt.%.
  • addition of Co, Fe, Cr, Cu, Mn, Al etc. in an amount of not more than several percent for further improving the corrosion resistance may be made without departing from the purport of the present invention.
  • the pH of the solution is 4 to 10. With the pH lower than 4, Zn, above all, of the plated layer is dissolved severely thus decreasing the amount of deposition of the plated material. On the other hand, with the pH above 10, the effect in improving the press formability is annulled. It is for this reason that the pH of the solution is limited to 4 to 10.
  • the positive ions of K+, Na+, Mg+, Ca+ or Al3+ etc. in the employed solution should be electro-chemically less noble than Zn and Ni. It is because metals electro-chemically less noble than Zn and Ni undergo a substitution reaction with Zn or Ni to be precipitated on the plated surface to degrade the appearance when the plated plate is dipped in a solution containing metal ions.
  • the amount of P on the plated surface when reckoned as P, is 0.1 to 5 mg/m. With the amount lower than 0.1 mg/m, the effect is annulled. On the other hand, with the amount in excess of 5 mg/m, phosphatability is deteriorated.
  • the treatment by the solution containing HPO 4 2- and/or H2PO 4 - may also be made by spraying by the above solution, in place of the above described dipping.
  • the operating conditions at this time may be approximately the same as those obtained in the dipping treatment.
  • anodic treatment in the above solution may also be performed in place of the dipping and spraying methods.
  • the conditions for anodic treatment include electric charges of up to 100 c(coulomb)/dm since the plated layer, above all Zn tends to be dissolved in excess of 100 c/dm.
  • Example 1 For Example 1 and Comparative Examples 1 and 2, the LDR values are shown in Fig.2 for more clear demonstration of the effects of the present invention.
  • the plated surface of a Zn-Ni alloy plated steel plate is treated by dipping, spraying or by anodic treatment by a solution containing HPO 4 2- and/or H2PO 4 - , whereby

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Electroplating Methods And Accessories (AREA)
  • Shaping Metal By Deep-Drawing, Or The Like (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)
EP89903215A 1988-03-16 1989-03-15 METHODS FOR PRODUCING Zn-Ni ALLOY-PLATED STEEL SHEET HAVING EXCELLENT PRESS MOLDABILITY Expired - Lifetime EP0364596B1 (en)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP60575/88 1988-03-16
JP63060575A JPH01234592A (ja) 1988-03-16 1988-03-16 プレス成形性の優れたＺｎ−Ｎｉ合金めっき鋼板の製造方法
PCT/JP1989/000276 WO1989008730A1 (en) 1988-03-16 1989-03-15 PROCESS FOR PRODUCING Zn-Ni ALLOY-PLATED STEEL SHEET HAVING EXCELLENT PRESS MOLDABILITY
CA 601174 CA1338621C (en) 1988-03-16 1989-05-30 Method for producing zn-ni alloy plated steel plate having superior press formability

Publications (3)

Publication Number Publication Date
EP0364596A1 EP0364596A1 (en) 1990-04-25
EP0364596A4 EP0364596A4 (en) 1990-07-03
EP0364596B1 true EP0364596B1 (en) 1996-03-06

Family

ID=25672767

Family Applications (1)

Application Number Title Priority Date Filing Date
EP89903215A Expired - Lifetime EP0364596B1 (en) 1988-03-16 1989-03-15 METHODS FOR PRODUCING Zn-Ni ALLOY-PLATED STEEL SHEET HAVING EXCELLENT PRESS MOLDABILITY

Country Status (5)

Country Link
EP (1) EP0364596B1 (ko)
JP (1) JPH01234592A (ko)
CA (1) CA1338621C (ko)
DE (1) DE68925858T2 (ko)
WO (1) WO1989008730A1 (ko)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102015118869A1 (de) 2014-11-04 2016-05-04 Voestalpine Stahl Gmbh Verfahren zum Herstellen einer Korrosionsschutzbeschichtung für härtbare Stahlbleche und Korrosionsschutzschicht für härtbare Stahlbleche

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2002046494A1 (fr) * 2000-12-04 2002-06-13 Jfe Steel Corporation Tôle d'acier zinguée et son procédé de production

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1229932A (ko) * 1967-07-24 1971-04-28
JPS56130477A (en) * 1980-03-13 1981-10-13 Sumitomo Metal Ind Ltd Surface treated steel plate
JPS61288098A (ja) * 1985-06-14 1986-12-18 Nippon Steel Corp 着色Ｚｎ−Ｎｉ系合金めつき鋼板及びその製造方法
JPH06164884A (ja) * 1992-11-20 1994-06-10 Mitsubishi Electric Corp ファクシミリ装置

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
Encyclopedia of Chemical Technology, Kirk-Othmer, 3rd Edn. Vol.15, pages 304 to 307 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102015118869A1 (de) 2014-11-04 2016-05-04 Voestalpine Stahl Gmbh Verfahren zum Herstellen einer Korrosionsschutzbeschichtung für härtbare Stahlbleche und Korrosionsschutzschicht für härtbare Stahlbleche

Also Published As

Publication number Publication date
JPH01234592A (ja) 1989-09-19
EP0364596A4 (en) 1990-07-03
JPH0535234B2 (ko) 1993-05-26
CA1338621C (en) 1996-10-01
EP0364596A1 (en) 1990-04-25
WO1989008730A1 (en) 1989-09-21
DE68925858D1 (de) 1996-04-11
DE68925858T2 (de) 1996-08-01

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