EP0174019A1 - Bande d'acier munie d'un revêtement composite à base de zinc et de particules minérales - Google Patents

Bande d'acier munie d'un revêtement composite à base de zinc et de particules minérales Download PDF

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Publication number
EP0174019A1
EP0174019A1 EP85111166A EP85111166A EP0174019A1 EP 0174019 A1 EP0174019 A1 EP 0174019A1 EP 85111166 A EP85111166 A EP 85111166A EP 85111166 A EP85111166 A EP 85111166A EP 0174019 A1 EP0174019 A1 EP 0174019A1
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EP
European Patent Office
Prior art keywords
zinc
coating layer
steel strip
plated steel
surface coating
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.)
Granted
Application number
EP85111166A
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German (de)
English (en)
Other versions
EP0174019B1 (fr
Inventor
Minoru C/O Nippon Steel Corporation Kitayama
Yasuhiko C/O Nippon Steel Corporation Miyoshi
Kazumi C/O Nippon Steel Corporation Nishimura
Yoshio C/O Nippon Steel Corporation Shindo
Fumio C/O Nippon Steel Corporation Yamazaki
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 Corp
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Nippon Steel Corp
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Publication date
Application filed by Nippon Steel Corp filed Critical Nippon Steel Corp
Publication of EP0174019A1 publication Critical patent/EP0174019A1/fr
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Publication of EP0174019B1 publication Critical patent/EP0174019B1/fr
Expired legal-status Critical Current

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    • 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
    • C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
    • C23C2/26—After-treatment
    • C23C2/265—After-treatment by applying solid particles to the molten coating
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D15/00—Electrolytic or electrophoretic production of coatings containing embedded materials, e.g. particles, whiskers, wires
    • C25D15/02—Combined electrolytic and electrophoretic processes with charged materials

Definitions

  • the present invention relates to a zinc-plated steel strip with a zinc-based coating layer containing an inorganic dispersoid. More particularly, the present invention relates to a zinc-plated steel strip having at. least one zinc-based coating layer containing fine inorganic dispersoid particles and formed on at least one surface of the steel strip, which zinc-plated steel strip exhibits excellent resistance to corrosion, enhanced workability, and superior weldability and is useful for producing cars, building and construction materials, and home electric appliances.
  • surface-treated steel strips are required to exhibit a high resistance to corrosion not only before but also after being painted. That is, surface coated steel strips have to exhibit a satisfactory paint adhesion and satisfactory resistances to perforation corrosion and to red rust when the paint film layer is scratched.
  • surface-treated steel strips must exhibit excellent workability and weldability.
  • Japanese Unexamined Patent Publication (Kokai) No. 56-133,488 published on October 19, 1981, for Nippon Steel Corporation discloses a steel strip plated with two Zn-Fe coating layers.
  • Japanese Examined Patent Publication (Kokoku) No. 50-29821 discloses a steel strip plated with a Zn-Ni coating layer.
  • the above-mentioned conventional plated steel strips are not always satisfactory for the above-mentioned strict requirements.
  • An object of the present invention is to provide a zinc-plated steel strip which exhibits excellent resistance to corrosion even after the plated steel strip is painted and the paint film layer is scratched.
  • Another object of the present invention is to provide a zinc-plated steel strip which exhibits excellent workability and weldability.
  • the zinc-plated steel strip with a zinc-based coating layer of the present invention which comprises a substrate consisting of a steel strip and at least one surface coating layer plated on at least one portion of at least one surface of the steel strip substrate, the surface coating layer consisting essentially of a matrix consisting of at least one member selected from the group consisting of zinc and zinc alloys and fine dispersoid particles dispersed in the matrix and consisting of at least one member selected from the group consisting of oxides, carbides, nitrides, borides, phosphides, and sulfides of aluminum, iron, titanium, molybdenum, copper, zinc, nickel, cobalt, lanthanum, cerium, and silicon.
  • the zinc-plated steel strip of the present invention may further comprises an intermediate coating layer formed between the steel strip substrate and the surface coating layer and consisting of at least one member selected from the group consisting of zinc and zinc alloys.
  • the fine dispersoid particles consist of at least one member selected from the group consisting of oxides, carbides, nitrides, borides, phosphides and surfides of aluminum, iron titanium, molybdenum, copper, zinc, nickel, cobalt, lanthanum, and cerium.
  • the fine dispersoid particles consist of at least one member selected from the group consisitng of oxides, carbides, nitrides, borides, phosphides and sulfides of aluminum, iron titanium molybdenum, copper, zinc, nickel, cobalt, lanthanum, cerium, and silicon.
  • Figure 1 is a graph showing the relationship between the content of the specific inorganic dispersoid consisting of silicon dioxide (Si0 2 ) in the surface coating layer and the electric current value (KA) necessary for smoothly welding the resultant plated steel strip.
  • a zinc or zinc alloy-surface coating layer plated on a surface of a steel strip and containing specific inorganic dispersoid particles is highly effective for enhancing resistance of the steel strip to corrosion, especially perforation corrosion after the plated steel strip is painted and processed.
  • the reasons for the special effect of the above-mentioned specific zinc or zinc alloy coating layer are not completely clear. It is assumed, however, that the specific inorganic dispersoid particles in the surface coating layer form a sort of barrier against the corrosion so as to restrict undesirable corrosional oxidation-reduction reaction in the coating layer. Also, it was found by the inventors of the present invention that the surface coating layer containing the specific fine inorganic dispersoid particles is effective for enhancing the weldability, especially spot weldability, of the plated steel strip.
  • an intermediate coating layer consisting of zinc or zinc alloy and formed between the steel strip substrate and the surface coating layer containing the specific inorganic dispersoid particles is highly effective for enhancing the specific effects of the surface coating layer, especially, for enhancing the resistance to perforation corrosion of the processed portion and the workability, of the plated steel strip.
  • the term "workability of the plated steel strip” refers to a resistance of the plated steel strip to powdering of the coating layer, that is, peeling of the coating layer from the substrate when processed.
  • the reasons for the above-mentioned effects of the intermediate coating layer are not clear. It is supposed, however, that the surface coating layer and the intermediate coating layer have a synergistic effect on, the plated steel strip. Also, it is supposed that the intermediate coating layer exhibits a special type of lubricating effect between the substrate and the surface coating layer.
  • a substrate consisting of a steel strip has at least one plated surface coating layer consisting essentially of a matrix consisting of a plated zinc alloy and fine dispersoid particles dispersed in the matrix and consisting of at least one member selected from oxides, carbides, nitrides, borides, phosphides and sulfides of aluminum (Al), iron (Fe), titanium (Ti), molybdenum (Mo), copper (Cu), zinc (Zn), nickel (Ni), cobalt (Co), lanthanum (La), cerium (Ce), and silicon (Si) .
  • the steel strip usable as a substrate for the present invention is not limited to specific types of steel strips. However, usually, the steel strip is preferably selected from ordinary steel strips, Al-killed steel strips and high tensile steel strips.
  • the resultant surface coating layer exhibits an excellent effect in enhancing the resistance to corrosion and workability and weldability of the plated steel strip.
  • These effects of the surface coating layer of the present invention are excellent compared with those of other zinc or zinc alloy coating layers which are free from the specific inorganic dispersoid or contain other dispersoids.
  • the surface coating layer be in an amount of from 1 to 400 g/m 2 , and has a thickness of from 0.1 to 40 microns.
  • the matrix consists of zinc or a zinc alloy.
  • the zinc alloy is preferably selected from alloys of from 20% to 99.7% by weight of zinc with 0.3% to 80% by weight of at least one additional metal member selected from the group consisting of nickel, copper, cobalt, chromium, tellurium, lanthanium, cerium, iron, and manganese.
  • the above-mentioned specific additional metal in a content of from 0.3% to 80% by weight is effective for enhancing the paint adhesion of the surface coating layer to the steel strip substrate surface when the surface coating layer is scratched and for improving the resistance of the surface coating layer to corrosion, especially, to perforation corrosion within a strict corrosional environment.
  • the amount of inorganic dispersoid is preferably 0.01% or more, more preferably from 0.01% to 95%, still more preferably from 0.01% to 30 %, based on the entire weight of the surface coating layer.
  • the resultant plated steel strip exhibits unsatisfactory weldability.
  • Fig. 1 shows the relationship between the content of inorganic dispersoid consisting of silicon dioxide (Si0 2 ) dispersed in a surface coating layer matrix consisting of zinc and the electric current value necessary for appropriately spot-welding the resulting zinc plated steel strip.
  • Si0 2 silicon dioxide
  • a surface coating layer matrix consisting of zinc the electric current value necessary for appropriately spot-welding the resulting zinc plated steel strip.
  • the appropriate spot welding current value can be determined by measuring changes in the size of nuggets formed in response to changes in the spot welding current applied.
  • Figure 1 clearly shows that when the content of sio 2 dispersoid is less than 0.01%, the weldability of the plated steel strip is unsatisfactory.
  • the content of the inorganic dispersoid does not exceed 95% based on the entire weight of the surface coating layer. Also, when the plated steel strip is required to have excellent resistance to powdering after the plated steel strip is strictly processed, it is preferable to limit the content of the inorganic dispersoid to 30% or less based on the entire weight of the surface coating layer.
  • the fine inorganic dispersoid particles in the surface coating layer preferably have an average size of 5 microns or less, preferably, from 0.01 to 1 micron. Fine inorganic dispersoid particles having an average size of 5 microns or less are hiqhly effective for enhancing the resistance of the resultant plated steel strip to powdering when the strip is subjected to severe processing.
  • the term "average size” refers to a size of the particles in a largest distribution percentage.
  • the surface coating layer of the present invention may cover the entire surface of the steel strip substrate. Otherwise, the surface of the steel strip substrate may be partially covered by the surface coating layer, for example, in the form of a plurality of stripes.
  • an intermediate coating layer consisting of zinc or a zinc alloy may be formed between the steel strip substrate and the surface coating layer.
  • the intermediate coating layer may be formed so as to partially cover or entirely cover the surface of the steel strip substrate.
  • the intermediate coating layer consists of zinc or a zinc alloy.
  • the zinc alloy is selected from alloys of 20% to 99% by weight of zinc and 1% to 80% by weight of at least one metal other than zinc, preferably selected from the group consisting of nickel, cobalt, chromium, iron, and molybdenum.
  • the intermediate coating layer is preferably in an amount of from 0.5 to 400 g/m 2 , more preferably, from 1 to 200 g/m 2 , and preferably has a thickness of from 0.1 to 20 microns.
  • the surface coating layer in the zinc-plated steel strip of the present invention may have a covering layer formed thereon by means of a silane-coupling treatment or a chemical conversion treatment.
  • silane-coupling treatment refers to a treatment of the surface of the surface coating layer with a silane-coupling agent, for example, vinylchlorosilane or vinyltrimethoxysilane.
  • chemical conversion treatment refers to a phosphate treatment or a chromate treatment applied to the surface coating layer of the plated steel strip.
  • the silane-coupling treatment and chemical conversion treatment are effective for enhancing the primary adhering property of the surface of the plated steel strip to lacquer.
  • the surface coating layer can be produced on a surface of the steel strip substrate by means of an electric plating or a vacuum evaporation plating procedure in the presence of fine inorganic dispersoid particles.
  • the electric plating method is applied to the production of the surface coating layer.
  • the electric plating procedure is carried out in a plating bath containing sulfate or chloride of zinc or zinc and at least one additional metal having a pH of 1 to 3 at a current density of 1 to 200 A/dm 2 at a line speed of 1 to 250 m/min.
  • the inorganic dispersoid particles are deposited in the plated metal matrix. It is assumed that the dispersoid particles are deposited due to the attraction caused by static electricity or the mechanical force applied thereto.
  • the intermediate coating layer can be produced by means of electric plating, vacuum evaporation plating, or hot galvanizing.
  • the zinc-plated steel strip of the present invention may have only one surface coating layer formed on only one surface of the substrate, two surface coating layers formed on both the surfaces of the substrate, or a combination of a surface coating layer and an intermediate coating layer formed on only one surface of the substrates or on each surface of the substrate.
  • the other surface of the substrate may be plated with a coating layer other than the surface coating layer and the intermediate coating layer of the present invention or with the same coating layer as the intermediate coating layer of the present invention.
  • the resistance of a specimen to corrosion was determined as follows.
  • a specimen was subjected to a dipping type chemical conversion treatment with zinc phosphate.
  • the treatment specimen was coated with a cathodic ED coating layer having a thickness of 20 microns.
  • the painted specimen was subjected to a cyclic corrosion test (CCT) in which a salt spray test was combined with a drying-wetting-cooling test.
  • CCT cyclic corrosion test
  • the specimen was tested for perforation corrosion of the processed portion of the steel strip was of a lapped panel. This test was carried out over 4 weeks, and the maximum depth of pits formed in the specimen was measured. The workability of the specimen was evaluated by a deep drawing test.
  • the resistance of the deep drawn specimen to powdering was determined by a tape test.
  • the weldability of the specimen was determined as follows. Two zinc-plated specimens were laid back to back with the plated surfaces outside. These were then spot-welded. The size of the nuggets formed in the welded portion was measured to determine the appropriate welding current for the specimens.
  • the surface rusting test was carried out by a cross-cut method.
  • the paint adhesion of the scratched portion of the specimen was determined by a cross-cut method in which the cross-cut specimen was subjected to the CCT for 4 weeks and the maximum width of blisters formed in the specimen was measured.
  • the results of the above-mentioned tests were evaluated as follows:
  • the content of the inorganic dispersoid particles in the surface coating layer be 0.01% or more, based on the entire weight of the surface coating layer, in order to enhance the weldability of the plated steel strip.
  • the preferable inorganic dispersoid particles should consist of aluminum, iron, or titanium.
  • examples 55 to 63 it is preferable for the purpose of enhancing the adhering property of scratched portion of the plated steel strip to control the content of the inorganic dispersoid particles to the level of 0.3% or more based on the entire weight of the surface coating layer. Also, it is preferable for the purpose of enhancing the pitting corrosion resistance and rust resistance to limit the content of the inorganic dispersoid particles to a level not exceeding 80% based on the entire weight of the surface coating layer.
  • Comparative Examples 1 to 6 the same substrate as that mentioned above was plated with an intermediate coating layer and then with a surface coating layer each having the composition and thickness in Table 2 (7).
  • Example 203 a surface of the substrate was covered partially with the intermediate coating layer at a covering rate of 50%.
  • the surface of the surface coating layer was treated with a silane-coupling agent.
  • Comparative Example 1 wherein the intermediate coating layer contains Si0 2 particles whereas the surface coating layer is free from the inorganic dispersoid particles, the resultant plated steel strip exhibited a very poor perforation corrosion resistance, whereas the paint adhesion of the scratched portion to lacquer was excellent.
  • the surface coating layer contained no inorganic dispersoid. This feature resulted in poor weldability of the resultant plated steel strip.
  • the preferable dispersoids for the zinc-nickel alloy matrix in the surface coating layer are oxides of aluminum, iron, titanium, and silicon.
  • the preferable metals to be alloyed with zinc in the surface coating layer are nickel, cobalt, chromium, iron, and manganese.
  • the resultant plated steel strips having an intermediate coating layer consisting of zinc or a zinc alloy and a surface coating layer containing dispersoid particles consisting of Si0 2 and having an average size of 5 microns or less exhibited excellent corrosion resistance, workability, and weldability and, therefore, are most preferable products of the present invention.
  • the preferable thickness of the surface coating layer is in the range of from 0.1 to 40 microns. Also, in view of Examples 228 to 232, it is preferable that the thickness of the intermediate coating layer is in the range of from 0.1 to 20 microns.
  • Examples 190 to 193 suggested that when the average size of the dispersoid particles is 5 microns or less, the resultant plated steel strip exhibited an enhanced powdering resistance.
  • Examples 203 and 204 showed that the plated steel strips having surface and intermediate coating layers or a surface coating layer in the form of a plurality of stripes are satisfactory.

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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)
  • Laminated Bodies (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)
EP85111166A 1984-09-06 1985-09-04 Bande d'acier munie d'un revêtement composite à base de zinc et de particules minérales Expired EP0174019B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP59185300A JPS6164899A (ja) 1984-09-06 1984-09-06 Ｚｎ系複合めつき鋼板
JP185300/84 1984-09-06

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EP0174019A1 true EP0174019A1 (fr) 1986-03-12
EP0174019B1 EP0174019B1 (fr) 1989-03-01

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JP (1) JPS6164899A (fr)
DE (1) DE3568459D1 (fr)

Cited By (14)

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EP0290836A2 (fr) * 1987-05-11 1988-11-17 Nippon Kokan Kabushiki Kaisha Bande d'acier munie d'un revêtement électrolytique composite zinc-silice ayant une excellente résistance à la corrosion
DE3819517A1 (de) * 1987-06-08 1988-12-22 Occidental Chem Co Verzinktes stahlblech mit verbesserter widerstandsschweissbarkeit und widerstandsschweissverfahren
FR2766844A1 (fr) * 1997-07-29 1999-02-05 Lorraine Laminage Tole luminescente economique et resistant a l'usure, procede de fabrication et utilisations
GB2340131A (en) * 1998-07-29 2000-02-16 Ford Motor Co Corrosion resistant surface coating based on zinc
WO2001027343A1 (fr) * 1999-10-07 2001-04-19 Bethlehem Steel Corporation Composition d'enrobage pour produit en acier; produit en acier enrobe, et procede d'enrobage d'un produit en acier
WO2001051681A3 (fr) * 2000-01-11 2001-12-27 C & C Cours Gmbh Surfaces metalliques brillantes
FR2822582A1 (fr) * 2001-03-26 2002-09-27 Korea Atomic Energy Res Procede d'inhibition de la fissuration par corrosion sous contraintes dans le circuit secondaire, dans des tubes de generateur de vapeur nucleaire
EP1348773A1 (fr) * 2002-03-25 2003-10-01 Bethlehem Steel Corporation Composition de revêtement pour produit en acier, produit en acier revêtu, et procédé de sa fabrication
FR2839729A1 (fr) * 2002-05-16 2003-11-21 Univ Toulouse Procede de protection d'un substrat en acier ou alliage d'aluminium contre la corrosion permettant de lui conferer des proprietes tribologiques, et substrat obtenu
US7211323B2 (en) * 2003-01-06 2007-05-01 U Chicago Argonne Llc Hard and low friction nitride coatings and methods for forming the same
US20150165727A1 (en) * 2012-01-23 2015-06-18 Jfe Steel Corporation Galvannealed steel sheet
US9486984B2 (en) 2014-05-05 2016-11-08 National Taiwan University Steel sheet and fabrication method thereof
CN113005494A (zh) * 2021-03-03 2021-06-22 无锡益联机械有限公司 一种含表面镀层的子午线轮胎胎圈钢丝及其制备方法
CN113512724A (zh) * 2021-06-22 2021-10-19 中山大学 一种含铜钼合金层的耐腐蚀钛钢复合材料及其制备方法

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Cited By (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0290836A2 (fr) * 1987-05-11 1988-11-17 Nippon Kokan Kabushiki Kaisha Bande d'acier munie d'un revêtement électrolytique composite zinc-silice ayant une excellente résistance à la corrosion
EP0290836B1 (fr) * 1987-05-11 1993-06-30 Nippon Kokan Kabushiki Kaisha Bande d'acier munie d'un revêtement électrolytique composite zinc-silice ayant une excellente résistance à la corrosion
DE3819517A1 (de) * 1987-06-08 1988-12-22 Occidental Chem Co Verzinktes stahlblech mit verbesserter widerstandsschweissbarkeit und widerstandsschweissverfahren
FR2766844A1 (fr) * 1997-07-29 1999-02-05 Lorraine Laminage Tole luminescente economique et resistant a l'usure, procede de fabrication et utilisations
GB2340131A (en) * 1998-07-29 2000-02-16 Ford Motor Co Corrosion resistant surface coating based on zinc
WO2001027343A1 (fr) * 1999-10-07 2001-04-19 Bethlehem Steel Corporation Composition d'enrobage pour produit en acier; produit en acier enrobe, et procede d'enrobage d'un produit en acier
WO2001051681A3 (fr) * 2000-01-11 2001-12-27 C & C Cours Gmbh Surfaces metalliques brillantes
FR2822478A1 (fr) * 2001-03-26 2002-09-27 Korea Atomic Energy Res Inhibition de la fissuration sous contrainte par corrosion de tubes de generateur de vapeur nucleaire par du borure de lanthane
FR2822582A1 (fr) * 2001-03-26 2002-09-27 Korea Atomic Energy Res Procede d'inhibition de la fissuration par corrosion sous contraintes dans le circuit secondaire, dans des tubes de generateur de vapeur nucleaire
EP1348773A1 (fr) * 2002-03-25 2003-10-01 Bethlehem Steel Corporation Composition de revêtement pour produit en acier, produit en acier revêtu, et procédé de sa fabrication
FR2839729A1 (fr) * 2002-05-16 2003-11-21 Univ Toulouse Procede de protection d'un substrat en acier ou alliage d'aluminium contre la corrosion permettant de lui conferer des proprietes tribologiques, et substrat obtenu
EP1365046A1 (fr) * 2002-05-16 2003-11-26 UNIVERSITE PAUL SABATIER (TOULOUSE III) Etablissement public a caractère scientifique, culturel et professionnel Procédé de protection d'un substrat en acier ou alliage d'alumium contre la corrosion permettant de lui conferer des propriétés tribologiques, et substrat obtenu
US7211323B2 (en) * 2003-01-06 2007-05-01 U Chicago Argonne Llc Hard and low friction nitride coatings and methods for forming the same
US20150165727A1 (en) * 2012-01-23 2015-06-18 Jfe Steel Corporation Galvannealed steel sheet
US9821534B2 (en) * 2012-01-23 2017-11-21 Jfe Steel Corporation Galvannealed steel sheet
US9486984B2 (en) 2014-05-05 2016-11-08 National Taiwan University Steel sheet and fabrication method thereof
CN113005494A (zh) * 2021-03-03 2021-06-22 无锡益联机械有限公司 一种含表面镀层的子午线轮胎胎圈钢丝及其制备方法
CN113512724A (zh) * 2021-06-22 2021-10-19 中山大学 一种含铜钼合金层的耐腐蚀钛钢复合材料及其制备方法

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EP0174019B1 (fr) 1989-03-01
JPS6316479B2 (fr) 1988-04-08
DE3568459D1 (en) 1989-04-06
JPS6164899A (ja) 1986-04-03

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