EP0510224A1 - Plated steel sheet having two plating layers and excellent in antifriction, corrosion resistance and painting adaptability - Google Patents

Plated steel sheet having two plating layers and excellent in antifriction, corrosion resistance and painting adaptability Download PDF

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Publication number
EP0510224A1
EP0510224A1 EP91106540A EP91106540A EP0510224A1 EP 0510224 A1 EP0510224 A1 EP 0510224A1 EP 91106540 A EP91106540 A EP 91106540A EP 91106540 A EP91106540 A EP 91106540A EP 0510224 A1 EP0510224 A1 EP 0510224A1
Authority
EP
European Patent Office
Prior art keywords
steel sheet
plated steel
zinc
layer
electroplating 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.)
Withdrawn
Application number
EP91106540A
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German (de)
English (en)
French (fr)
Inventor
Masaru C/O Nkk Corporation Sagiyama
Masafumi c/o NKK Corporation Yoshida
Masaki c/o NKK Corporation Kawabe
Satoru c/o NKK Corporation Ando
Tadashi C/O Nkk Corporation Ono
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 Engineering Corp
Original Assignee
NKK Corp
Nippon Kokan 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 NKK Corp, Nippon Kokan Ltd filed Critical NKK Corp
Publication of EP0510224A1 publication Critical patent/EP0510224A1/en
Withdrawn legal-status Critical Current

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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
    • 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
    • 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
    • C25D5/60—Electroplating characterised by the structure or texture of the layers
    • C25D5/615—Microstructure of the layers, e.g. mixed structure
    • C25D5/617—Crystalline layers

Definitions

  • the present invention relates to a plated steel sheet having two plating layers and excellent in antifriction upon press-forming, corrosion resistance and painting adaptability.
  • the body of an automobile is exposed to a corrosive environment, and particularly to a severe corrosive environment in a coastal area or a cold area where an automobile tends to come into contact with a substance containing chlorine ions having a violent corrosivity.
  • a zinc plated steel sheet or a zinc alloy plated steel sheet is conventionally widely used as a steel sheet for an automobile body having an excellent corrosion resistance even in such a severe corrosive environment.
  • the conventional zinc plated steel sheet has however the following problems:
  • the zinc electroplated steel sheet applied with the high-viscosity lubricant oil on the surface thereof has a small frictional coefficient of 0.11. If the orientation of the crystals of the zinc electroplating layer along the ⁇ 10 1 ⁇ X ⁇ plane (where, X is 1, 2, 3 or 4) as taught by the prior art can be maintained, an antifriction of the same order as in the application of the high-viscosity lubricant oil would be available by the application of the conventional anticorrosive oil which is easy to remove, onto the surface of the zinc electroplated steel sheet.
  • the crystal orientation of the zinc electroplating layer of the zinc electroplated steel sheet depends upon electroplating conditions, and among others, upon an electric current density. As a result, it is inevitable to alter the plating conditions in response to the width, for example, of the steel sheet to be electroplated. In the manufacture of the zinc electroplated steel sheet in an industrial scale, it is practically impossible to maintain the orientation of the crystals of the zinc electroplating layer along the ⁇ 10 1 ⁇ X ⁇ plane (where, X is 1, 2, 3 or 4).
  • An object of the present invention is therefore to provide a plated steel sheet having two electroplating layers and excellent in antifriction, corrosion resistance and painting adaptability.
  • a plated steel sheet having two plating layers and excellent in antifriction, corrosion resistance and painting adaptability characterized by comprising; a steel sheet; a zinc plating layer formed on at least one surface of said steel sheet, said zinc plating layer having a plating weight within a range of from 25 to 150 g/m2 per surface of said steel sheet; and an electroplating layer formed on said zinc plating layer, said electroplating layer comprising at least one element selected from the group consisting of chromium, manganese, iron, cobalt and nickel, and said electroplating layer having a plating weight within a range of from 1 to 10 g/m2 per surface of said steel sheet.
  • a plated steel sheet having two plating layers and excellent in antifriction, corrosion resistance and painting adaptability is available by the following steps:
  • the present invention was made on the basis of the above-mentioned findings.
  • the plated steel sheet of the present invention having two plating layers and excellent in antifriction, corrosion resistance and plating adaptability is described below with reference to the drawings.
  • the plated steel sheet of the present invention excellent in antifriction, corrosion resistance and painting adaptability comprises a steel sheet, a zinc plating layer as a lower layer formed on at least one surface of the steel sheet and an electroplating layer as an upper layer formed on the zinc plating layer.
  • the zinc plating layer as the lower layer formed on at least one surface of the steel sheet has a function of imparting an excellent corrosion resistance to the plated steel sheet.
  • the zinc plating layer is formed by either of the electroplating method and the dip-plating method, which are now widely diffused as an industrialized processes.
  • a zinc electroplating bath is selected from among a bath containing sulfate, a bath containing chloride and a bath containing a mixture of sulfate and chloride.
  • any one of the commonly utilized zinc dip-plating baths is used.
  • the plating weight of the zinc plating layer as the lower layer exerts an important effect on corrosion resistance, antifriction and press-formability of the plated steel sheet.
  • a plating weight of the zinc plating layer of under 25 g/m2 per surface of the steel sheet a desired corrosion resistance necessary for a rust-preventive steel sheet used as a material for an automobile body is not available.
  • a plating weight of the zinc plating layer of over 150 g/m2 per surface of the steel sheet on the other hand, when forming same by the electroplating method, zinc crystals of the zinc electroplating layer become coarser.
  • a uniform electroplating layer as the upper layer cannot be formed on the zinc electroplating layer, thus making it impossible to obtain an effect of improving antifriction described later by the electroplating layer as the upper layer.
  • a plating weight of the zinc plating layer of over 150 g/m2 per surface of the steel sheet when forming the zinc plating layer by the dip-plating method, a zinc deposition in the width direction of the steel sheet shows a very non-uniform distribution, thus making it difficult to conduct the press-forming of the plated steel sheet.
  • the plating weight of the zinc plating layer as the lower layer should therefore be limited within a range of from 25 to 150 g/m2 per surface of the steel sheet.
  • the electroplating layer as the upper layer which is formed on the zinc plating layer as the lower layer and comprises at least one element selected from the group consisting of chromium, manganese, iron, cobalt and nickel, has a function of imparting an excellent painting adaptability as typically represented by a high cratering resistance and an excellent antifriction. Since all the above-mentioned elements have a high melting point, it is difficult to form a plating layer of these elements as the upper layer on the zinc plating layer by the dip-plating method.
  • the electroplating layer of these elements as the upper layer is therefore formed by the electroplating method with the use of an electroplating bath such as a bath containing sulfate, a bath containing chloride, a bath containing a mixture of sulfate and chloride, or a bath containing borofluoride.
  • an electroplating bath such as a bath containing sulfate, a bath containing chloride, a bath containing a mixture of sulfate and chloride, or a bath containing borofluoride.
  • Fig. 1 is a graph illustrating, for the plated steel sheet of the present invention, which has a zinc plating layer as a lower layer formed on the surface of the steel sheet and an electroplating layer as an upper layer formed on the zinc plating layer, the relationship between a frictional coefficient of the plated steel sheet and a plating weight of the electroplating layer as the upper layer. More particularly, a zinc electroplating layer as a lower layer having a plating weight of 60 g/m2 per surface of a steel sheet was formed by the electroplating method on one surface of the steel sheet. Then, a nickel electroplating layer as an upper layer was formed on the zinc electroplating layer by the electroplating method while changing the plating weight of the nickel electroplating layer. A frictional coefficient was measured for the plated steel sheet having the thus formed two plating layers.
  • the plated steel sheet has a high frictional coefficient.
  • the plating weight of the nickel electroplating layer as the upper layer is under 1 g/m2 per surface of the steel sheet, the plated steel sheet has a high frictional coefficient.
  • the plating weight of the nickel electroplating layer as the upper layer is over 10 g/m2 per surface of the steel sheet, on the other hand, the plated steel sheet has a constant frictional coefficient at a level of up to 0.1, which does not decrease to below this level.
  • the frictional coefficient of the plated steel sheet is high as described above, so that antifriction of the plated steel sheet is deteriorated.
  • the frictional coefficient of the plated steel sheet becomes constant at a level of up to 0.1.
  • the plating weight of the electroplating layer as the upper layer which comprises at least one element selected from the group consisting of chromium, manganese, iron, cobalt and nickel, should therefore be limited within a range of from 1 to 10 g/m2 per surface of the steel sheet.
  • an excellent antifriction is imparted to the plated steel sheet, by forming the electroplating layer as the upper layer, which has a plating weight within a range of from 1 to 10 g/m2 per surface of the steel sheet and comprises at least one element selected from the group consisting of chromium, manganese, iron, cobalt and nickel, on the zinc plating layer as the lower layer.
  • the reason of this is estimated to be as follows:
  • the zinc plating layer of the zinc plated steel sheet has a relatively low hardness. Therefore, the zinc plating layer having a low hardness is deformed upon the press-forming of the zinc plated steel sheet.
  • both a cold-rolled steel sheet and a zinc alloy plating layer of a zinc alloy plated steel sheet have a high hardness.
  • the surface of the cold-rolled steel sheet or the zinc alloy plating layer are hard to deform.
  • a small contact area between the surface of the cold-rolled steel sheet or the zinc plating layer and the pressing portion of the press leads to a low frictional coefficient.
  • the cold-rolled steel sheet or the zinc alloy plated steel sheet is therefore excellent in antifriction. The above description suggests that a higher hardness of the surface of a steel sheet provides a more excellent antifriction of the steel sheet.
  • the electroplating layer as the upper layer has a remarkably higher hardness than that of the zinc plating layer as the lower layer.
  • the zinc plating layer as the lower layer deforms because of the low hardness thereof
  • the electroplating layer as the upper layer is hard to deform because of the high hardness thereof.
  • a small contact area between the surface of the electroplating layer and the pressing portion of the press leads to a low frictional coefficient of the plated steel sheet.
  • the plated steel sheet of the present invention is therefore excellent in antifriction.
  • the plating weight of the electroplating layer as the upper layer is under 1 g/m2 per surface of the steel sheet, most part of the surface of the zinc plating layer as the lower layer is exposed, and the contact area between the electroplated steel sheet and the pressing portion of the press becomes larger. This results in a high frictional coefficient of the plated steel sheet as in the above-mentioned zinc plated steel sheet.
  • the plating weight of the electroplating layer as the upper layer increases from 1 g/m2 per surface of the steel sheet, the electroplating layer as the upper layer more sufficiently covers the zinc plating layer as the lower layer, thus eliminating the exposed part of the zinc plating layer as the lower layer. This results in a smaller contact area between the plated steel sheet and the pressing portion of the press.
  • the frictional coefficient of the plated steel sheet becomes very low.
  • a plating weight of the electroplating layer as the upper layer of over 10 g/m2 per surface of the steel sheet results in a constant frictional coefficient at a low level, which no longer decreases from this level.
  • the electroplating layer as the upper layer which comprises at least one element selected from the group consisting of chromium, manganese, iron, cobalt and nickel, imparts an excellent painting adaptability, i.e., an excellent cratering resistance to the plated steel sheet.
  • a hydrogen gas if produced non-uniformly when forming a painting film by the electropainting on the surface of the plated steel sheet, is confined in the painting film, thus resulting in the occurrence of craters in the painting film.
  • the electroplating layer as the upper layer of the plated steel sheet of the present invention which comprises at least one element selected from the group consisting of chromium, manganese, iron, cobalt and nickel, has a low hydrogen overvoltage, a hydrogen gas is uniformly produced when forming a painting film by the electropainting. This results in a very rare occurrence of craters in the painting film, thus leading to an excellent painting adaptability, i.e., an excellent cratering resistance of the plated steel sheet.
  • the plated steel sheet of the present invention having the two plating layers and excellent in antifriction, corrosion resistance and painting adaptability, is described further in detail by means of examples while comparing with examples for comparison.
  • Each of cold-rolled steel sheets having a thickness of 0.7 mm was subjected to a conventional degreasing treatment and a conventional pickling treatment to remove rust from the both surfaces thereof. Then, the steel sheet from the both surfaces of which rust was thus removed, was subjected to an electroplating under the conditions shown in Table 1 to form a zinc electroplating layer as a lower layer on each of the both surfaces of the steel sheet.
  • each of the steel sheets having the zinc electroplating layer or the zinc dip-plating layer formed on each of the both surfaces thereof was subjected to another electroplating under another conditions shown also in Table 1 to form an electroplating layer as an upper layer, which comprised at least one element selected from the group consisting of chromium, manganese, iron, cobalt and nickel, on the zinc electroplating layer or the zinc dip-plating layer.
  • an electroplating layer as an upper layer, which comprised at least one element selected from the group consisting of chromium, manganese, iron, cobalt and nickel, on the zinc electroplating layer or the zinc dip-plating layer.
  • the plating weight per surface of the steel sheet of the zinc electroplating layer or the zinc dip-plating layer, elements and the contents thereof of the electroplating layer, and the plating weight per surface of the steel sheet of the electroplating layer are shown also in Table 1.
  • each of steel sheets identical with those in the samples of the invention Nos. 1 to 54 was subjected to a conventional degreasing treatment and a conventional pickling treatment to remove rust from the both surfaces thereof. Then, the steel sheet from the both surfaces of which rust was thus removed, was subjected to an electroplating under the conditions shown in Table 2 to form a zinc electroplating layer as a lower layer on each of the both surfaces of the steel sheet.
  • each of the steel sheets having the zinc electroplating layer formed on each of the both surfaces thereof was subjected to another electroplating under another conditions shown also in Table 2 to form an electroplating layer as an upper layer on the zinc electroplating layer.
  • samples of the electroplated steel sheet outside the scope of the present invention hereinafter referred to as the "samples for comparison" Nos. 1 to 7 were prepared.
  • Each of the samples for comparison Nos. 1 and 7 had only a zinc electroplating layer as a single layer.
  • the plating weight per surface of the steel sheet of the zinc electroplating layer as the lower layer for each of the samples for comparison Nos. 1 to 7, as well as elements and the contents thereof of the electroplating layer as the upper layer, and the plating weight per surface of the steel sheet of the above-mentioned electroplating layer for each of the samples for comparison Nos. 2 to 6 are also shown in Table 2.
  • a mineral oil type anticorrosive oil for a steel sheet (product name: NOX RUST 530F40) manufactured by Parker Industries, Inc. was applied onto one surface of each of the samples of the invention Nos. 1 to 54 and the samples for comparison Nos. 1 to 6, and a high-viscosity lubricant oil (product name: FERROCOTE 61-MAL-HCL-1) manufactured by Nippon Quaker Chemical Co., Ltd. was applied onto one surface of the sample for comparison No. 7.
  • the apparatus for measuring frictional coefficient of the sample comprised, as shown in Fig. 2, a rack 2; a supporting stand 5, provided on the rack 2 vertically movably along a plurality of guide rods 12 and 13 attached vertically to the rack 2, and having a plurality of rollers 6 on the upper end thereof; a supporting stand driving mechanism (not shown) for vertically moving the supporting stand 5; a first load cell 8, provided between the supporting stand 5 and the rack 2, for measuring the force applied vertically to the supporting stand 5; a pressing block 4 fitted to a frame 3 fixed to the rack 2 so as to project toward the supporting stand 5; a horizontally movable sliding table 7 mounted on the rollers 6 of the supporting stand 5 between the supporting stand 5 and the pressing block 4; a sliding table driving mechanism (not shown), provided on another rack 11, for horizontally moving the sliding table 7; and a second load cell 9, provided between an operating rod 10 connected to the sliding table driving mechanism and one end of the sliding table 7, for measuring the force applied horizontally to the sliding table 7.
  • the supporting stand driving mechanism By operating the supporting stand driving mechanism, the supporting stand 5 was moved upward to lift up the sliding table 7 on the upper surface of which a sample 1 was placed. Thus the upper surface of the sample 1 was pressed against the lower end of the pressing block 4, and the force N applied in the arrow A direction was measured by means of the first load cell 8. Then, by operating the sliding table driving mechanism, the sliding table 7 was horizontally moved in the arrow B direction, together with the sample 1 placed on the upper surface thereof, and the force F applied in the arrow B direction to the sliding table 7 was measured by means of the second load cell 9, at the moment when the sliding table 7 reached the moving speed of 1 m/minute. The ratio of the force F to the force N, i.e., the ratio F/N was determined, and the thus determined value was used as the value of frictional coefficient.
  • each of the samples having a width of 70 mm and a length of 150 mm was subjected to a dipping type phosphating for a steel sheet for automobile in a phosphating solution (product name: PBL 3080) manufactured by Nihon Perkerizing Co., Ltd., to form a phosphate film on the surface of the sample. Then, the sample was subjected to a cation type electropainting with the use of a paint (product name: ELECRON 9400) manufactured by Kansai Paint Co., Ltd. under the following conditions to form a painting film having a thickness of 20 ⁇ m on the phosphate film:
  • Cratering resistance was evaluated by means of the number of craters produced in the painting film during the formation of the painting film as described above.
  • the criteria for evaluation were as follows:
  • Corrosion resistance was evaluated by means of perforation resistance and blister resistance as follows:
  • a phosphate film was formed on the surface of each of the samples, and a painting film having a thickness of 20 ⁇ m was formed on the phosphate film by means of the electropainting. Then, a notch was provided in the thus formed painting film.
  • Each of the samples having the thus notched painting film was then subjected to 60 cycles of corrosion tests, each cycle comprising a salt water spray, a drying, a dipping into salt water, and a drying for 24 hours. Then, the painting film and corrosion products produced during the corrosion test, were removed from each sample thus subjected to the 60 cycles of corrosion tests, and the maximum corrosion depth produced in the steel sheet was measured. Perforation resistance was evaluated by means of the thus measured maximum corrosion depth. The criteria for evaluation were as follows:
  • a phosphate film was formed on the surface of each of the samples, and a lower painting film having a thickness of 10 ⁇ m was formed on the phosphate film by means of the electropainting. Then, an intermediate painting film having a thickness of 35 ⁇ m and an upper painting film having a thickness of 35 ⁇ m were formed on the thus formed lower painting film. Then, a notch was provided on the thus formed triple-layer painting film. A salt spray test was carried out on each of the samples having the thus notched triple-layer painting film.
  • each sample was exposed to the open air for a period of one year, during which salt water having a sodium chloride content of 5 wt.% was sprayed over the sample at a rate of twice a week. Then, the maximum blister width of the painting film was measured on one side of the notch on the sample after the salt spray test, and blister resistance was evaluated by means of the thus measured maximum blister width of the painting film.
  • the criteria for evaluation were as follows:
  • All the samples of the invention Nos. 1 to 54 were excellent in painting adaptability as typically represented by a high cratering resistance with the number of craters of up to 10 produced within a circle of a diameter of 40 mm at the center of the sample, as evaluated by A.
  • the sample for comparison No. 1 having the zinc electroplating layer as the single layer and applied with the anticorrosive oil for a steel sheet on the surface thereof had a large frictional coefficient of 0.3.
  • the sample for comparison No. 2 having a low plating weight of the nickel electroplating layer as the upper layer outside the scope of the present invention had a large frictional coefficient of 0.28.
  • the sample for comparison No. 3 having a high plating weight of the nickel electroplating layer as the upper layer outside the scope of the present invention was poor in perforation resistance and blister resistance.
  • a high-viscosity lubricant oil (product name: FERROCOTE 61-MAL-HCL-1) manufactured by Nippon Quaker Chemical Co., Ltd. was applied onto the zinc electroplating layer as the single layer of the sample for comparison No. 7, and an antifriction test as described above was effected on the sample for comparison No. 7 applied with the high-viscosity lubricant oil on the zinc electroplating layer thereof.
  • the above-mentioned sample for comparison No. 7 had a frictional coefficient of 0.11. This revealed that the samples of the invention Nos. 1 to 54 applied with the easily removable anticorrosive oil had substantially the same antifriction as that of the sample for comparison No. 7 applied with the high-viscosity lubricant oil which was very difficult to remove.
EP91106540A 1989-11-13 1991-04-23 Plated steel sheet having two plating layers and excellent in antifriction, corrosion resistance and painting adaptability Withdrawn EP0510224A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP1294380A JPH03153883A (ja) 1989-11-13 1989-11-13 潤滑性、耐食性および塗装適合性に優れた複層めつき鋼板
JP1298416A JPH03158495A (ja) 1989-11-13 1989-11-16 潤滑性、耐食性および塗装仕上がり性に優れた複層めつき鋼板

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EP0510224A1 true EP0510224A1 (en) 1992-10-28

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EP91106540A Withdrawn EP0510224A1 (en) 1989-11-13 1991-04-23 Plated steel sheet having two plating layers and excellent in antifriction, corrosion resistance and painting adaptability

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8218765B2 (en) 2001-02-23 2012-07-10 Hewlett-Packard Development Company, L.P. Information system
US8219496B2 (en) 2001-02-23 2012-07-10 Hewlett-Packard Development Company, L.P. Method of and apparatus for ascertaining the status of a data processing environment
US10041175B2 (en) 2014-04-08 2018-08-07 Nippon Steel & Sumitomo Metal Corporation Plated steel sheet
US20190144963A1 (en) * 2016-04-29 2019-05-16 Arcelormittal A press hardening method
CN111575597A (zh) * 2020-06-10 2020-08-25 苏州普热斯勒先进成型技术有限公司 一种锰系镀覆钢板及其热成型方法和热成型产品

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GB2161499A (en) * 1984-07-06 1986-01-15 Phenix Works Sa Hot-galvanized steel product for phosphating

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GB2161499A (en) * 1984-07-06 1986-01-15 Phenix Works Sa Hot-galvanized steel product for phosphating

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8218765B2 (en) 2001-02-23 2012-07-10 Hewlett-Packard Development Company, L.P. Information system
US8219496B2 (en) 2001-02-23 2012-07-10 Hewlett-Packard Development Company, L.P. Method of and apparatus for ascertaining the status of a data processing environment
US10041175B2 (en) 2014-04-08 2018-08-07 Nippon Steel & Sumitomo Metal Corporation Plated steel sheet
US20190144963A1 (en) * 2016-04-29 2019-05-16 Arcelormittal A press hardening method
CN111575597A (zh) * 2020-06-10 2020-08-25 苏州普热斯勒先进成型技术有限公司 一种锰系镀覆钢板及其热成型方法和热成型产品

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JPH03158495A (ja) 1991-07-08
JPH03153883A (ja) 1991-07-01

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